- Email: [email protected]
Li-Secondary Battery
CHAPTER
LI-SECONDARY BATTERY: SPECIAL RISKS
11
CHAPTER OUTLINE 11A A Specific Risks During Transport and Storage ............................................................................. 456 11A.1 Transport ............................................................................................................... 456 11A.1.1 Introduction ..................................................................................................... 456 11A.1.2 Dangerous Goods............................................................................................. 458 11A.1.3 UN Lithium Battery Testing Requirements......................................................... 460 11A.1.4 Safe Shipping of Lithium Batteries .................................................................... 461 11A.1.5 Approvals for Special Shipping of Lithium Batteries ........................................... 467 11A.1.6 Lithium Batteries Permitted for Passengers in Aircraft ....................................... 468 11A.2 Storage (Written Only by J. Garche).......................................................................... 469 Abbreviations .................................................................................................................... 470 References ....................................................................................................................... 471 11B Specific Risks of Lithium Batteries at End of Life .......................................................................... 472 11B.1 Introduction........................................................................................................... 472 11B.1.1 The Nature of Incidents.................................................................................... 474 11B.1.2 The Approach .................................................................................................. 476 11B.1.3 Battery Aging ................................................................................................... 477 11B.2 Legislative and Regulatory Framework ...................................................................... 477 11B.2.1 The EU Waste Framework Directive and the Daughter Directives on Waste......................................................................................... 478 11B.2.2 The Waste Framework Directive....................................................................... 478 11B.2.3 The End of Life Vehicle Directive ..................................................................... 479 11B.2.4 The Waste Electrical and Electronic Equipment Directive.................................. 479 11B.2.5 The Batteries Directive .................................................................................... 479 11B.2.6 The Basel Convention ..................................................................................... 480 11B.2.7 The International Transport Regulation............................................................. 481 11.B.2.8 Note to the Reader: Hazardous Waste and Dangerous Goods........................... 481 11B.3 Transport of Lithium Batteries for Disposal or Recycling ............................................ 481 11B.3.1 Special Provisions SP377 and SP636 (B) (ADR) for Lithium Batteries Transported for Disposal or Recycling................................................. 482 11B.3.2 Special Provision SP376 for the Transport of Damaged and Defective Lithium Batteries............................................................................... 484 11B.4 Communication Tools as Preventive Measures........................................................... 486 11B.4.1 The Prevention and Response to Incidents ....................................................... 486 11B.4.2 Results of Tests................................................................................................ 487 11B.4.3 Recalled Batteries ............................................................................................ 487 11B.4.4 Recommendations for the Safe Storage of Waste Lithium Batteries.................... 488 Electrochemical Power Sources: Fundamentals, Systems, and Applications. DOI: https://doi.org/10.1016/B978-0-444-63777-2.00011-6 © 2019 Elsevier B.V. All rights reserved.
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11B.4.5 Fire Fighting First Responders .......................................................................... 488 11B.4.6 Waste Batteries Collection Organization ............................................................ 488 11B.4.7 The Traffic Light Approach ............................................................................... 489 11B.5 Electrical Hazard Control: Technical Solutions .......................................................... 490 11B.5.1 Electrical Hazard.............................................................................................. 491 11B.5.2 Deactivation ..................................................................................................... 492 11B.5.3 UN Transport Regulation .................................................................................. 493 11B.5.4 Use of Cushioning Material in Packaging and Storage ....................................... 493 11B.5.5 Wet Deactivation Via “Immersion” .................................................................... 494 11B.5.6 The Redox Shuttle Approach ............................................................................ 495 11B.5.7 Deactivation Through a Controlled Load............................................................ 495 11B.5.8 Other Means to Deactivate a Battery................................................................. 495 11B.6 Reuse and Second Use ........................................................................................... 496 11B.6.1 Definitions........................................................................................................ 498 11B.6.2 The Extended Producer Responsibility (EPR) .................................................... 499 11B.6.3 EPR and Directives on New Products ............................................................... 499 11B.6.4 EPR and Waste Directives ................................................................................ 500 11B.7 Conclusions ........................................................................................................... 501 Acknowledgments.............................................................................................................. 502 Abbreviations .................................................................................................................... 503 References ....................................................................................................................... 503
SUBCHAPTER
11A
A SPECIFIC RISKS DURING TRANSPORT AND STORAGE
George A. Kerchner1 and Ju¨rgen Garche2 1
PRBA-The Rechargeable Battery Association, Washington, DC, United States 2FCBAT, Ulm, Germany
11A.1 TRANSPORT 11A.1.1 INTRODUCTION Billions of lithium-ion and lithium-metal cells and batteries are manufactured annually by different manufacturers all over the world. The overwhelming part of the cell production takes place in Asia and from there cells and batteries are packaged and shipped globally by all modes of transport. The safe transport of lithium-ion and lithium-metal cells and batteries (referred to herein as “lithium batteries”) is critical because the batteries have a very high energy content and the possible presence of a flammable electrolyte and/or metallic lithium. Therefore, lithium batteries are classified and regulated as “dangerous goods”. Their safe transport is governed by a number international and national dangerous goods regulations depending on the mode of transport used to ship or transport the batteries.
11A.1 TRANSPORT
Transport mode:
All Modes
Air
Sea
Opinion forming:
Subcommittee
DGP
DSC
Decisions:
Committee
Council
MSC
ECOSOC Geneva
ICAO Montreal
IMO London
UN
Road, Europe
WP 15
IAEA Vienna
ECE Geneva
Rail, Europe
RID Committee
OTIF Bern
IATA
NGO International:
Radioactive Material
457
Model Regulations, Manual of Tests and Criteria
TI
DGR
IMDG Code
ADR
RID
FIGURE 11A.1 International organizations responsible for dangerous goods transportation. Reproduced from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1].
Air: ICAO IATA Sea: IMO
Road (Europe) ECE (or UNECE) Rail (Europe) OTIF
—International Civil Aviation Organization with DGP—Dangerous Goods Panel and TI—Technical Instructions —International Air Transport Association with DGR—Dangerous Goods Regulations —International Maritime Organization with DSC—Sub-Committee on Dangerous Goods, Solid Cargoes and Containers and MSC—Maritime Safety Committee and IMDG—International Maritime Dangerous Goods Code. —United Nations Economic Commission for Europe with ADR—European Agreement concerning the International Carriage of Dangerous Goods by Road —Intergovernmental Organization for International Carriage by Rail with RID—Regulations Concerning the International Carriage of Dangerous Goods by Rail
The United Nations established a system for the classification, packaging, marking, and labeling of dangerous goods in general. The United Nations Recommendations on the Transport of Dangerous Goods Model Regulations and the United Nations Manual of Tests and Criteria provide a basis for development of these harmonized regulations for all modes of transport. This harmonization of regulations facilitates trade and the safe, efficient transport of all dangerous goods, including lithium batteries. The UN Model Regulations, which were first published in 1957, establishes minimum requirements applicable to the transport of dangerous goods. The UN Model Regulations established by ECOSOC (United Nations Economic and Social Council) are valid for all transport modes and incorporated into special dangerous goods regulations by international organizations for transport in air, sea, road, and rail (see Fig. 11A.1).
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The air transport regulations for lithium batteries have become particularly complex and are more stringent than the regulations for sea, road, or rail transport. Each set of regulations include requirements for how dangerous goods must be packaged, labeled and transported. These regulations are updated on a 2-year cycle. Over the course of the last 25 years, the lithium battery dangerous goods regulations in the UN Model Regulations, ICAO Technical Instructions, and IATA Dangerous Goods Regulations have undergone tremendous change, which has resulted in a complex set of regulatory requirements that are very difficult to understand even for the most experienced dangerous goods experts. In addition, the regulations will continue to evolve and likely change every 2 years as new issues arise and battery technology changes. Meetings of UN working groups on amending the lithium battery tests in the UN Manual also are frequently held in order to accommodate new battery technologies and the ongoing lessons learned from testing lithium batteries. Non-governmental organizations like PRBA The Rechargeable Battery Association and RECHARGE The Advanced Rechargeable & Lithium Batteries Association have been instrumental in helping to update the UN38.3 tests and lithium battery dangerous goods regulations over the past 20 years. This present chapter addresses the requirements for the safe transport of lithium batteries and the applicable dangerous goods regulations.
11A.1.2 DANGEROUS GOODS “Dangerous goods” (also referred to as “hazardous materials” in the United States) are substances (including mixtures) and articles presenting a potential hazard to human health and safety, infrastructure, and/or their means of transport and property. UN Model Regulations cover principles of classification and definition of classes, listing of the principal dangerous goods, general packaging requirements, testing procedures, marking, labeling, placarding, and transport documents. There are, in addition, special requirements related to particular classes of dangerous goods. With this harmonized system of classification, listing, packaging marking, labeling, placarding, and documentation in general use, carriers, consignors, and inspecting authorities benefit from a harmonized regulatory system governing the transport of dangerous goods.
11A.1.2.1 Dangerous goods classification The dangerous goods subject to the regulations given in the introduction are assigned to one of the nine classes listed below with their label according to the hazard or the most predominant of the hazards they present in transport. Some of these classes are subdivided into divisions (Figs. 11A.2 11A.4). Electrochemical power sources relevant in in Class 9 include: • • • • •
Lithium-ion batteries Lithium-metal batteries Battery powered equipment Battery powered vehicles Fuel cell engines Therefore, lithium batteries in general are regulated as Class 9 Miscellaneous Dangerous Goods.
FIGURE 11A.2 Labeling of dangerous goods related to UN [2].
FIGURE 11A.3 Class 9 hazard label: Miscellaneous Dangerous Goods—left old, right new. Adapted from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1].
FIGURE 11A.4 Hazardous material shipping label: Cargo Aircraft Only. Reproduced from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1]
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11A.1.2.2 UN numbers and proper shipping names of dangerous goods The different dangerous goods listed in the regulations have a specific identification number or “UN number” (ranging from UN0001 to about UN3600) and “proper shipping name” associated with it. The following UN numbers and proper shipping names apply to lithium batteries: UN3480—Lithium-ion batteries UN3481—Lithium-ion batteries contained in equipment UN3481—Lithium-ion batteries packed with equipment UN3090—Lithium-metal batteries UN3091—Lithium-metal batteries contained in equipment UN3091—Lithium-metal batteries packed with equipment
11A.1.3 UN LITHIUM BATTERY TESTING REQUIREMENTS In general, lithium batteries are subject to a series of tests found in the United Nations Manual of Tests and Criteria. This manual contains test methods and procedures to be used for the classification of dangerous according to the provisions of the UN Model Regulations. In Part III, subsection 38.3, a series of eight lithium cell and battery tests are listed. These tests are often referred to as the “UN 38.3” lithium battery tests. These tests are listed below and may be conducted by cell and battery manufacturers or a third-party test lab. Currently (6/2017), the 6th revised edition (2015) is in effect [3]. The following tests are required for primary and secondary cells and/or batteries with the exception of Test T7—Overcharge, which applies only to secondary batteries. T1—Altitude Simulation (Primary and Secondary Cells and Batteries) Assesses the influence of low pressure (#11.6 kPa for $ 6 h) on cells/batteries during transport. T2—Thermal Test (Primary and Secondary Cells and Batteries) Assesses the influence of rapid (30 min) and extreme (40 C 3 70 C) temperature variations on cells/batteries during transport. T3—Vibration (Primary and Secondary Cells and Batteries) Assesses the effect of vibration during transport (varying amplitudes 7 Hz 3 200 Hz) on cells/batteries. T4—Shock (Primary and Secondary Cells and Batteries) Assesses the effect of possible impact (half-sine shock, peak acceleration 150 gn, pulse duration 6 ms; for larger cell/batteries: 50 gn, 11 ms with a sliding scale depending on the mass of the battery) during transport to cells/batteries. T5—External Short Circuit (Primary and Secondary Cells and Batteries) Assesses the effect of an external short circuit (#0.1 Ω, 55 C) during transport to cells/batteries. T6—Impact, Crush (Primary and Secondary Cells) Impact: Assesses the effect of an impact (mass of 9.1 kg dropped from 61 cm on a steel bar l 5 6 cm, Ø 15.8 mm, which is located on a sample) on cells during transport.
11A.1 TRANSPORT
461
Crush: Assesses the effect of a crush (cell between two flat surfaces, speed: 1.5 cm s21 up to applied force of 13 kN or a voltage drop of $ 100 mV or deformed by 50%) on cells not more than 20 mm in diameter during transport. T7—Overcharge (Secondary Batteries) Assesses the effect of overcharge (Ioverch52 3 manufacturer’s recommended continuous Ich for 24 h) on batteries. T8—Forced Discharge (Primary and Secondary Cells) Assesses the effect of forced discharge (discharged for a time interval, h, equal to its rated capacity, Ah, divided by the initial test current, A) on cells. These tests are also adopted by other transport organizations such as IATA (DGR— Section 3.9.2.6) and IMO (IMDG Code—Section 2.9.4). There is only one exception where lithium cells and batteries are not required to be tested in accordance with UN 38.3 as a prerequisite for transport. This exception applies to preproduction prototype lithium cells and batteries if these samples are transported for testing, or low production runs (i.e., a production run consisting of no more than 100 lithium cells and batteries per year). Once the cells and batteries pass the UN tests, retesting is not required unless there is a change in the cell or battery design type as noted in section 38.3.2.2 of the UN Manual. Technical changes that may be considered to a previously tested cell or battery type are listed in Section 38.3.2.2 and include mass change ( . 0.1 g or .20%), energy change (20%), voltage change ( . 20%), change of chemical cell material change, change of protective devices, including hardware and software, change of safety design (e.g., vent), change of cell numbers in a battery, change of cell connecting mode in a battery, and to mass change in relation.
11A.1.4 SAFE SHIPPING OF LITHIUM BATTERIES 11A.1.4.1 Fully-regulated dangerous goods shipping If a lithium battery does not qualify for any of the “exceptions” in the regulations, a shipper must offer the package of lithium batteries as “fully-regulated” dangerous goods. This means the package must carry a specific diamond-shaped label to indicate the hazard associated with the package and certain markings required by the regulations. For lithium batteries, this means a Class 9 label as in Fig. 11A.3 (left). A new Class 9 label especially for lithium cells and batteries in Fig. 11A.3 (right) was incorporated into the dangerous goods regulations in 2017 and will be required on packages of fully-regulated shipments of lithium batteries starting on January 1, 2019. However, the new label may be used by shippers of lithium batteries starting on January 1, 2017. The air transport regulations applicable to lithium batteries that are found in the ICAO Technical Instructions and IATA Dangerous Goods Regulations have become increasingly complex and more stringent. For example, ICAO now prohibits the transport of lithium batteries as cargo on passenger aircraft. This prohibition means shippers are required to place the Cargo Aircraft Only label shown in Fig. 11A.4 on their packages of lithium batteries. The label is not only required for fully-regulated shipments by air but also for shipments offered under the exceptions to the regulations. In addition, lithium-ion cells and batteries (UN 3480) may not exceed 30% state of charge (SOC) of the nominal capacity when shipped by air. (For the influence of SOC on a thermal runaway event, see e.g., Chapter 12C: Ignition and Extinction of Battery Fires.)
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CHAPTER 11 LI-SECONDARY BATTERY: SPECIAL RISKS
Lithium-ion cells and batteries at a SOC greater than 30% can be shipped by air but only with the approval of the State of Origin and the State of the Operator under the written conditions established by those authorities, see Special Provision A331 of the ICAO TI and IATA DGR The 30% SOC limit does not apply to lithium ion cells and batteries packed with or contained in equipment (UN 3481). Shippers who want to take advantage of any exceptions in the regulations for air transport are limited to placing no more than two batteries or eight cells in a single package. And, these excepted packages may not be consolidated (i.e., overpacked) together. The air transport requirements for lithium batteries (UN 3480, UN 3481, UN 3090, UN 3091) are also often dependent on an airline’s specific acceptance policy (also known as “operator variations”). A good overview about the policies of a specific airline is given in [4]. The Interline (or Interchange) Message Procedure-Code (IMP Code) of IATA for shipping fully regulated lithium cells and batteries is for lithium ion batteries: Restricted Lithium-ion—Cargo (RLI); and for lithium metal batteries: Restricted Lithium-metal—Cargo (RLM). Due to the complexity of the lithium battery dangerous goods regulations and the risks associated with these batteries in transport, reputable companies that are in the business of manufacturing, shipping, or transporting lithium batteries have adopted very comprehensive training programs for their dangerous goods employees in accordance with the regulations. The regulations generally require dangerous goods training every 2 years. Any employee who prepares or transports lithium batteries should be trained to ensure they fully understand the hazards associated with lithium batteries and the importance of complying with the testing, packaging, marking, labeling, and documentation requirements in the dangerous goods regulations. These training programs are one of the keys to ensuring the safe transport of lithium batteries. A further important prerequisite for safe shipping is a high safety standard by the manufacturer of the cells and batteries which will have a significant impact on compliance with the UN 38.3 tests. Therefore, all of the dangerous goods regulations require that manufacturers of lithium batteries follow a quality management program that addresses, e.g., quality control, quality assurance, and process operation instructions [5].
11A.1.4.2 Exceptions from fully-regulated dangerous goods shipping The UN Model Regulations, IMDG Code, and European ADR and RID contain a Special Provision 188 that provides an “exception” from the regulations for smaller lithium cells and batteries, which means they are not offered for transport as fully-regulated dangerous goods. The most important point of the exceptions is related to the energy of cells or batteries given in Watt hours (Wh) for lithium-ion and lithium metal content given in gramm for lithium-metal cells/batteries. These Wh and lithium metal content limits enable most consumer-type products with lithium cells and batteries to be shipped under the exceptions and thus under a less onerous regulatory scheme than larger lithium batteries used in industrial applications such as hybrid-electric and electric vehicles. While excepted cells and batteries are provided some relief from the regulations, they generally require some type of hazard mark or label on packages to indicate the presence of the lithium batteries. A new lithium battery mark was incorporated into the dangerous goods regulations in 2017 and will be required on most packages of excepted lithium batteries starting on January 1, 2019. However, the new mark may be used by shippers of lithium batteries starting on January 1, 2017.
11A.1 TRANSPORT
463
FIGURE 11A.5 Lithium Battery Mark— indicates a place for the applicable UN number (UN 3090, UN 3091, UN 3480 or UN 3481), for phone number. Reproduced from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1].
As mentioned in the legend of Fig. 11A.5 this mark requires the entry at “ ” of the applicable UN number (UN 3090, UN 3091, UN 3480 or UN 3481) and at “ ” of the phone number of the responsible shipper or an emergency response company or organization. This new lithium battery mark also will appear in the IMDG Code, ICAO Technical Instructions, IATA Dangerous Goods Regulations, and European ADR and RID. This harmonized approach to marking packages containing excepted lithium batteries will help to facilitate the safe transport of lithium batteries and products packed with them. The Interline (or Interchange) Message Procedure-Code (IMP Code) of IATA shipping excepted lithium cells and batteries is for Li-ion batteries Excepted Lithium-ion—Cargo (ELI); and for Li-metal batteries Excepted Lithium-metal—Cargo (ELM). The dangerous goods regulations that govern shipments of excepted lithium cells and batteries generally do not require employees to be trained in accordance with the regulations. However, for air transport, these employees must receive “adequate instructions” commensurate with their responsibilities.
11A.1.4.3 Packaging requirements Shipments of lithium cells and batteries must comply with very stringent packaging requirements found in all of the dangerous goods regulations. Logically, the air transport regulations in the ICAO Technical Instructions and IATA Dangerous Goods Regulations contain the most restrictive and stringent packaging requirements based on the quantity or net mass of the batteries per package. Under the UN Model Regulations, most packaging must meet or exceed minimum standards of performance before it can be authorized for transporting dangerous goods. Package performance is established by subjecting packaging to the tests described in Chapter 6.1 of the UN Model Regulations. These tests include, but are not limited to, drop, leak proofness, internal pressure, and stacking. If a package design passes the tests, all subsequent packages manufactured to the same specification are marked accordingly to indicate they comply with the applicable tests (Table 11A.1).
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CHAPTER 11 LI-SECONDARY BATTERY: SPECIAL RISKS
Table 11A.1 Limited Energy Level and Lithium Metal Content for Excepted Li-Ion and Li-Metal Cells and Batteries-related to IATA-DGR [3a] Proper Shipping Name
Limited Energy Level and Lithium Metal Content Per Unit
Lithium-Ion Cells Lithium-Ion Batteries Lithium-Metal Cells Lithium-Metal Batteries
# 20 Wh # 100 Wh # 1 g Li # 2 g Li
Table 11A.2 UN Number, Proper Shipping Name, Packaging Instruction (PI), Energy Limitations of Cells/Batteries, Net Weight and Numerical Limitations Per Packages, Relevant Sections, Subsections, and IMP Codes (related to IATA-DGR [3])
UN Number
Proper Shipping Name
UN3480
Lithium-ion batteries
PI 965
Energy or Li Metal Cont. Limitations, Cell/Battery Section I IMP: RLI
Energy or Li Metal Cont. Limitations, Cell/Battery Section II IMP: ELI
Section IA: C: .20 Wh
C: # 20 Wh B: # 100 Wh
B: .100 Wh
Section IB: C: # 20 Wh
UN3481
Lithium-ion batteries packed with equipment
966
B: # 100 Wh C: .20 Wh
C: # 20 Wh
UN3481
Lithium-ion batteries contained in equipment
967
B: .100 Wh C: .20 Wh
B: # 100 Wh C: # 20 Wh
B: .100 Wh
B: # 100 Wh
Net Weight Limitations, Package Section I IMP: RLI
Energy or Li Metal Content and Numerical Limit., Package Section II IMP: ELI
Section IA: PAX A/C: forb. CAO: 35 kg
Only 1 package, package limits: • # 2.7 Wh/cell 5 max. 2.5 kg • 2.7 Wh— # 20 Wh/ cell 5 max. 8 cells • . 2.7 Wh— # 100 Wh/batt 5 max 2 batt. PAX A/C: forb.
Section IB: PAX A/C: forb. CAO: 10 kg PAX A/C: 5 kg. CAO: 35 kg PAX A/C: 5 kg. CAO: 35 kg
PAX A/C: 5 kg CAO: 5 kg PAX A/C: 5 kg CAO: 5 kg
11A.1 TRANSPORT
465
Table 11A.2 UN Number, Proper Shipping Name, Packaging Instruction (PI), Energy Limitations of Cells/Batteries, Net Weight and Numerical Limitations Per Packages, Relevant Sections, Subsections, and IMP Codes (related to IATA-DGR [3]) Continued
UN Number
Proper Shipping Name
UN3090
Lithium-metal batteries
PI 968
Energy or Li Metal Cont. Limitations, Cell/Battery Section I IMP: RLI
Energy or Li Metal Cont. Limitations, Cell/Battery Section II IMP: ELI
Section IA: C: .1 g Li
C: # 1 g Li B: # 2 g Li
B: .2 g Li
Section IB: C: # 1 g Li
UN3091
Lithium-metal batteries packed with equipment
969
B: # 2 g Li C: .1 g Li
C: # 1 g Li
UN3091
Lithium-metal batteries contained in equipment
970
B: .2 g Li C: .1 g Li
B: # 2 g Li C: # 1 g Li
B: .2 g Li
B: # 2 g Li
Net Weight Limitations, Package Section I IMP: RLI
Energy or Li Metal Content and Numerical Limit., Package Section II IMP: ELI
Section IA: PAX A/C: forb. CAO: 35 kg
Only 1 package, package limits: 2 0.3 g Li/ cell 5 max. 2.5 kg 2 0.3 g # 1 g Li/ cell 5 max. 8 cells 2 . 0.3 # 2 g Li/ batt 5 max 2 batteries PAX A/C: forb.
Section IB: PAX A/C: forb. CAO: 2.5 kg PAX A/C: 5 kg. CAO: 35 kg PAX A/C: 5 kg. CAO: 35 kg
PAX A/C: 5 kg. CAO: 5 kg PAX A/C: 5 kg. CAO: 5 kg
Adapted from H. Huo, Y. Xing, M. Pecht, B.J. Zu¨ger, N. Khare, A. Vezzini, Energies 10 (2017) 793 [1].
For each of the lithium battery entries there is a specific packaging instruction (PI) in the IATA DGR (see Table 11A.2). Table 11A.2 gives an overview of the relevant air shipping parameter related to IATA DGR. All shipments in Section I also must be accompanied by a Shipper’s Declaration for Dangerous Goods (DGD) [6]. In addition to the requirements shown in Table 11A.2, shipping regulations published by IATA and ICAO, the flow charts in Fig. 11A.6 (Li-ion) and Fig. 11A.7 (Li-metal) provide guidance for shipping excepted and fully-regulated lithium cells/batteries by air.
FIGURE 11A.6 Requirements for shipping lithium-ion cells/batteries by air based on the IATA DGR. Reproduced from IATA (2017) Lithium Battery Guidance Document [6].
FIGURE 11A.7 Requirements for shipping lithium-metal cells/batteries based on the IATA DGR. Reproduced from IATA (2017) Lithium Battery Guidance Document [6].
11A.1 TRANSPORT
467
As previously noted, lithium cells and batteries in the prototype state and from low production runs (#100 pcs/a) do not require testing according to UN 38.3. These cells and batteries may be shipped by ground or sea as fully-regulated Class 9 dangerous goods in Packing Group I or II packaging depending on the mode of transport used. Shipments by Cargo aircraft are possible but only if approved by the appropriate authority of the State of origin and the requirements in Packing Instruction 910 of the Supplement to the ICAO Technical Instructions are met (see Special Provision A55, A88). Securing air transport approvals from aviation authorities in certain countries may take as long as 6 months.
11A.1.5 APPROVALS FOR SPECIAL SHIPPING OF LITHIUM BATTERIES Often shippers of lithium batteries are unable to comply with certain provisions of the lithium battery dangerous goods regulations or, as noted above, require authorization to ship by air prototype or low production lithium batteries that have not been subject to the required UN lithium battery tests. In these cases, the dangerous goods regulations authorize a “competent authority” to issue approvals to shippers authorizing an alternative method of packaging and shipping their lithium cells/batteries. Over the years, competent authorities have issued many approvals that authorize the transport by air of lithium cells/batteries that exceed the 35 kg cargo aircraft package net mass limit or that authorize shipments of prototype or low production lithium batteries. It is quite common to exceed the upper weight limitation of 35 kg for EV and HEV lithium ion batteries. The weight of these batteries on average range from to 200 500 kg. Because most of the EV manufacturers are shipping their batteries globally, it is necessary for these manufacturers to secure multiple approvals from various countries such as the United States, China, and Germany. Other examples of special shipping are given below.
11A.1.5.1 Shipping damaged or defective lithium batteries The transport of damaged or defective lithium batteries has garnered a significant amount of regulatory attention due to the potential for an incident involving these batteries. Therefore, Special Provisions and Packing Instructions governing the transport of these batteries were incorporated into the various dangerous goods regulations in 2015, which include detailed and stringent packaging requirements. This is also valid for lithium cells and batteries installed inside equipment such as mobile phones, laptops, or tablets where the devices are subject to recall due to manufacturing defects. In all cases, the damaged or defective lithium batteries must be shipped as fully-regulated Class 9 dangerous goods and often are packaged in metal drums or expensive and customized fire-resistant packaging. The transport of damaged or defective lithium cells and batteries by air is strictly prohibited. The inability to ship damaged or defective lithium cells/batteries by air has created significant problems for manufacturers. If a cell or battery has had a thermal event, a manufacturer often wants to conduct a failure analysis as quickly as possible. However, due to the lack of authority to ship by air, conducting a failure analysis in short order is impossible.
11A.1.5.2 Disposal and recycling of lithium batteries Also in 2015, new Special Provisions and Packing Instructions for shipping lithium cells and batteries for disposal or recycling were incorporated into the dangerous goods regulations. These new
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requirements were particularly critical to help facilitate shipments of waste lithium batteries that are being transported internationally by sea from countries that do not have lithium battery recycling facilities. Please see also in this book Chapter 11B, Specific Risks of Lithium Batteries at End of Life.
11A.1.6 LITHIUM BATTERIES PERMITTED FOR PASSENGERS IN AIRCRAFT 11A.1.6.1 Carry-on baggage checked at the gate or planeside allowed in the cabin Passengers can carry most consumer-type lithium batteries and portable electronic devices (PEDs) powered by lithium batteries for their own personal use in carry-on baggage. Spare batteries are prohibited in checked baggage. Spare lithium batteries in carry-on baggage must be protected from damage and short circuit. Battery-powered devices must be protected from damage and accidental activation and heat generation. Damaged, defective, or recalled batteries, including when in a device, must not be carried. Lithium batteries allowed in carry-on baggage include: Lithium-ion batteries: All consumer-sized lithium-ion batteries (up to max. 100 Wh) alone or in an equipment. With airline approval, devices can contain larger lithium-ion batteries (101 160 Wh), but spares of this size are limited to two batteries. Lithium-metal batteries: All consumer-sized lithium-metal batteries up to maximum of 2 g Li/ battery alone or in equipment are authorized.
11A.1.6.2 Checked baggage includes bags checked at the gate or planeside [7] Spare (uninstalled) lithium metal and lithium ion batteries, including power banks, are prohibited in checked baggage. Except for electronic cigarettes and vaporizers, only lithium batteries installed in equipment are allowed in checked baggage. Electronic cigarettes and vaporizers are strictly prohibited in checked baggage and must be placed in carry-on baggage. The summary for batteries allowed on board passenger aircrafts is shown in Table 11A.3. Note that medical devices with up to 8 grams of lithium metal are also authorized in carry-on baggage.
Table 11A.3 Overview About Batteries Permitted for Passengers in Aircrafts (related to IATA-DGR) Li-Ion System # 100 Wh/Batt.
Li-Metal Systems 101 160 Wh/batta
# 2 g Li/Battery
Battery Alone
Batt. in Device
Battery Alone
Batt. in Device
Battery Alone
Batt. in Device
Carry-on
Permitt.
Permitt.
Permitt.a
Permitt.
Permitt.
Checked-in
Banned
Permitt.
Max. 2 pieces Banned
Permitt.a
Banned
Permitt.
a
Only by permission of the airline. Adapted from H. Huo, Y. Xing, M. Pecht, B.J. Zu¨ger, N. Khare, A. Vezzini, Energies 10 (2017) 793 [1].
11A.2 STORAGE (WRITTEN ONLY BY J. GARCHE)
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11A.2 STORAGE (WRITTEN ONLY BY J. GARCHE) Many transportation regulations are in principal also useable as regulations for storage of lithium ion batteries. During storage of lithium ion batteries, however, one should consider the significantly higher numbers of cells and batteries, higher total energy of the stored batteries (partially . MWh), and often long storage times. The lithium-ion cell and battery manufacturers give various instructions for storage. Thus, it is preferred to store at room temperature of about 25 C and at a state-of-charge (SOC) of about 20% 40%. It is recommended to store the cells in original packaging whose materials are related to fire relevant packaging regulations. Some manufacturers recommend checking the charge level of the battery every three months and recharging if necessary, which is, however, quite time-consuming. Particularly important is the control of cells which have just been formed, because in that post formation time micro shorts could be occurred. Typical risks in storage processes, such as electrical risk, dropping, and damage caused by mechanical influences, are normally not strong risk factors due to existing measures and established processes. The cell and battery storage rooms should be equipped with fire and temperature sensors, preferably with measurements near in the cell and battery batch. For effective risk minimization, protective concepts such as automatic fire extinguish systems, for example, sprinkler, foam, or inter gas flooding are recommended. Due to high fire loads (plastic of the components, packaging) and the high energy content of the cells/batteries, conventional sprinkler systems may be not sufficient. Sprinkler systems with water misting show considerably higher cooling capacities caused by small water drop diameters. Water is currently the recommended extinguishing agent, which, in addition to the cooling effect, also inhibits the fire by limiting the air access to the brand center. For smaller rooms, CO2 can also be used. Large volumes of extinguishing water which are contaminated with higher concentrations of electrolytes should be collected. More on fire extinction can be found in Chapter 12C, Ignition and Extinction of Battery Fires. For fire prevention, lowering the oxygen partial pressure in storage rooms is also used [7]. The combustibility of solids in an atmosphere with # 15.9% O2 and liquids with # 13% O2 can be radically reduced. The storage building construction materials must be in accordance to the relevant building codes, for example in Germany, DIN 4102—Fire behavior of building materials and building components. Of the usual fire resistance classes, at least the class F90—“fireproofed” (function maintenance over 90 minutes)—should be used. When evaluating the fire loads of cells/batteries, the packaging material which is usually first burned during thermal propagation is also to be assessed. The German Insurance Association (GDV) provides specifications for storage of cells and batteries based on the mass of lithium cells and batteries and their energy content in three categories [7]. For all classes there should be no mixed storage with other goods. •
Low energy— # 2 g Li (Li-metal) or # 100 Wh per battery (Li-ion) This includes, among others, (small) batteries and individual cells, which are mainly used in the field of computers, multimedia, small electromechanical devices, and small tools. There are no special safety requirements for the low energy class. If the cell/battery volume is .7 m3 or . six euro-pallets, however, the requirements of the medium energy class are to be considered.
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Medium energy— . 2 g Li (Li-metal), or .100 Wh per battery (Li-ion), and # 12 kg gross per battery This includes medium sized individual cells and batteries, e.g., for E-bikes, E-scooter, lightelectric vehicle, larger gardening tools, various small vehicles. Storage places for the medium energy class require a distance of .5 m to other places if they are not constructed with fireproofed materials at least of the class F90. The storage places must be fitted with a fire alarm system. If, however, the cell/battery storage area is .60 m2 and/or a storage height of .3 m is used the requirements, of the high energy class are to be considered. • High energy— . 2 g Li (Li-metal), .100 Wh per battery (Li-ion), and .12 kg gross per battery. This includes large sized cells and batteries for EVs as well as network-independent large devices. The storage places for the high energy class require also a distance of .5 m to other places if they are not constructed with fireproofed materials at least of the class F90. The GDV requirements in Germany are not “standard” in all countries. Especially the costs of fireproof construction materials as e.g., F90. are, for example, for smaller warehouses, prohibitively expensive. Two fire codes used in the United States - the International Fire Code (IFC) and NFPA 1 - have been considering substantial changes to address the storage of “used” and “off specification” lithium cells and batteries. New requirements for energy storage systems were adopted in the 2018 IFC.
•
ABBREVIATIONS Aircraft European Agreement concerning the International Carriage of Dangerous Goods by Road (ECE) Battery Management System Cargo Aircraft Only Shipper’s Declaration for Dangerous Goods Dangerous Goods Regulations (IATA) Dangerous Goods Panel (ICAO) Sub-Committee on Dangerous Goods, Solid Cargoes and Containers (IMO) United Nations Economic Commission for Europe (also UNECE) Excepted Lithium ion—Cargo IMP-Code for “small” Lithium ion batteries according to Part II of PI ELM Excepted Lithium-metal—Cargo IMP-Code for “small” Lithium-metal batteries according to Part II of PI ECOSOC United Nations Economic and Social Council EV Electric vehicle GDV German Insurance Association IATA International Air Transport Association ICAO International Civil Aviation Organization IMDG International Maritime Dangerous Goods Code (IMO) IMO International Maritime Organization IMP Interline (or Interchange) Message Procedure-Code Code A/C ADR BMS CAO DGD DGR DGP DSC ECE ELI
REFERENCES
LBSG MAG MSC OTIF PAX A/C PI RID RLI RLM SOC TI UN UN 38.3 UNECE
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IATA Lithium Battery Shipping Guidelines Miscellaneous goods (Class 9, dangerous goods) Maritime Safety Committee (IMO) Intergovernmental Organization for International Carriage by Rail Passenger Aircraft Packing Instruction—IATA DGR Regulations Concerning the International Carriage of Dangerous Goods by Rail (OTIF) Restricted Lithium ion—Cargo IMP-Code for Lithium ion batteries according to Part IB and Part I / IA of PI Restricted Lithium-metal—Cargo IMP-Code for Lithium metal batteries according to Part IB and Part I / IA of PI State of Charge of a cell/battery, normally in % Technical Instructions (ICAO) United Nations Subsection 38.3 of part III of the UN Manual of Tests and Criteria United Nations Economic Commission for Europe (also ECE)
REFERENCES [1] H. Huo, Y. Xing, M. Pecht, B.J. Zu¨ger, N. Khare, A. Vezzini, Energies 10 (2017) 793. [2] https://en.wikipedia.org/wiki/Dangerous_goods. [3] http://www.unece.org/trans/areas-of-work/dangerous-goods/legal-instruments-and-recommendations/unmanual-of-tests-and-criteria/rev6-files.html. [3a] https://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-guidance-document-2017-en.pdf. [4] https://www.lithium-batterie-service.de/app/index.php/?lang5en-gb. [5] J. Schnell, G. Reinhart, Procedia CIRP 57, pp. 568 573, 2016. [6] https://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-guidance-document-2017-en.pdf. [7] GDV, G. d. (VdS 3103: 2016-05 (02)). Lithium-Batterien GDV-Merkblatt zur Schadenverhu¨tung. Publikation der deutschen Versicherer (GDV e. V.). https://vds.de/fileadmin/vds_publikationen/ vds_3103_web.pdf.
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SUBCHAPTER
11B
SPECIFIC RISKS OF LITHIUM BATTERIES AT END OF LIFE
Jean-Pol Wiaux Consultant. Route d’Annecy, Geneva, Switzerland
11B.1 INTRODUCTION At end of service life, the potential hazards developed by waste lithium batteries (WLB) are similar to those of new batteries when placed on the market but the environment in which they may develop is different. The potential hazards are linked to the consequences of a short circuit (inner or outer) and the rapid release of stored electrical energy as well as the possibility of a thermal runaway resulting from exposure to high temperature of flammable components (solvent and additives) contained in lithium batteries. A specific attention needs to be paid also to residual high voltage (above 48 VDC) that may be present in large batteries used, for example, for electric mobility or energy storage. The risk level of an incident may be increased in the case of ignorance by a carrier or a waste storage facility operator about the presence of waste lithium batteries in the transport unit or the waste storage facility. The absence of information about the properties of such batteries in a given waste stream (e.g., lithium batteries in electrical and electronic equipment) is also perceived as a source of concern. Fig. 11B.1 gives a simplified representation of various hazard sources for waste lithium batteries. There are major management options for lithium batteries after their initial service life. As illustrated in Fig. 11B.2, a lithium battery reaching an end of its first service life (EOL) may be returned for repair or remanufacturing for reuse within the same application. When considered as waste, it is transferred to a waste company for final treatment or disposal. It may also undergo repurposing for a different use than the initial one: this represents the “second use” of the battery (Section 11B.6 of this chapter will address specifically this issue). Lithium batteries at end of life, when qualified as waste, may be collected by public or private organizations or taken back by producers, for recycling, as the result of voluntary initiatives or mandatory requirements. This chapter will not review the case of waste lithium batteries sent for disposal. The complexity of the end of life management is increased by the different types of lithium batteries placed on the market (pom) among others: lithium-metal primary and secondary (Li-M), rechargeable batteries with intercalation electrodes (Li-ion) and new rechargeable systems that use metallic Li electrodes.
11B.1 INTRODUCTION
Internal factors
473
External factors Fire Solid particles emissions Liquid & gas releases
Thermal runaway
Thermal stress (e.g. exposure to sunlight)
Temperature increase Mechanical damage Opening a short circuit
Internal short External short
Sudden release of electrical energy or Short circuit
Mechanical damage / damaged battery With Li B and with other waste batteries Storage in humid environment External short Unknown residual voltage
Li batteries at end of life
Lack of info on Li battery composition Non selective storage Non controlled transport Ignorance of the presence of Li batteries In transport unit or storage facility
FIGURE 11B.1 Major hazard sources for waste lithium batteries.
Service life (1st)
End of first service life (EOL) Reuse
Waste
Repair or Remanufacturing
Take back B2B
Repurposing
Collection C2B Second use Recycling
FIGURE 11B.2 Illustration of various management options for lithium batteries at end of first service life (EOL).
As illustrated in Fig. 11B.3, each of these return or collection routes are presenting different potential hazard levels due to their specific environment, the nature of the returned batteries and their residual electrical energy content—from a few Wh per cell (communication applications) to several kWh per module (E-mobility) up to the MWh per battery (energy storage).
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3. WLB separate collection (from dedicated commercial activity (*))
1. WLB mixed with other types of batteries (C2B)
Sorting
2. WLB installed in waste electrical & electronic equipment
Waste lithium batteries (WLB) take back & collection routes
Recycling
(*) e.g. Photo or watches shops, electronic equipment shops, cordless tools (DIY)…
4. WLB separate collection (from specific industrial applications (**)) (B2B) (**) e.g. Flow meters, e-bikes, electric vehicles, stand-by power units (UPS)…
FIGURE 11B.3 Illustration of various take back and collection routes for waste lithium batteries (WLB).
11B.1.1 THE NATURE OF INCIDENTS The large differences which exist in packaging and transport conditions between new and waste lithium batteries are illustrated in Fig. 11B.4. New cells out of works are packed separately in blisters or in trays to prevent short circuits. At the collection stage waste lithium batteries are transported in packaging with limited individual protection and sometimes in bulk conditions. The following circumstances have been at the origin of incidents involving waste lithium batteries: • • • • • • • • • • •
Unsafe storage in open air conditions (e.g., exposure to rain). Unsafe storage due to exposure to sunlight. Storage with other hazardous waste such as volatile organic solvents. Presence of large quantities of charged cells/batteries in noncontrolled storage areas (e.g., temperature control). No separation in storage between batteries of different chemistries. Storage of bare cells with metal housing offering opportunities for short-circuits between cells or batteries. Storage of mixed batteries in damaged conditions in absence of external protection. Handling of waste batteries subject to mechanical shock (e.g., during waste management operations). Presence of large quantities of charged cells in noncontrolled storage areas. Presence of large lithium-ion batteries in lead-acid battery flows entering a lead-acid battery recycling plant. Etc. . . An illustrative representation of lithium batteries-based incidents is reported in Fig. 11B.5.
11B.1 INTRODUCTION
FIGURE 11B.4 Differences in packaging conditions for new and waste lithium metal cells.
FIGURE 11B.5 Illustrative representation of some incidents sources involving lithium batteries.
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1. Lithium batteries at end of life hazard mitigation tools 2. Legislative and regulatory context Waste management legislation Basle convention Transport of dangerous goods 1. Waste lithium batteries 2. Damaged & defective lithium batteries
3. Communication Battery information factsheet Good practice guidance Emergency response guidance
4. Prevention Collection Safe storage Cushioning materials Insurance comp. Express courier Fire brigade connection
5. Control Depowering Recall actions Fire 1st responders Recycling plants 6. Reuse and second use
FIGURE 11B.6 Illustration of the content of this chapter.
11B.1.2 THE APPROACH In order to deliver to the reader some useful information for the handling and storage of waste lithium batteries, the approach taken in this chapter is described below and illustrated in Fig. 11B.6. Section 11B.2 will concentrate on the key legislative and regulatory acts in force to control the flow of waste lithium batteries at the end of service life at EU level as well as at international level. The specific requirements of the International Regulation for the Transport of Dangerous Goods will be summarized; indeed lithium batteries are classified as dangerous goods by the UN Model Regulation for the Transport of Dangerous Goods. In this context, the provisions of the Transport Regulation for Waste and Damaged and Defective batteries will be reviewed in Section 11B.3. In Section 11B.4, importance will be given to various sources of information available about the potential hazards offered by waste lithium batteries. References to major Good Practice Guidance documents will be given in this paragraph on “Prevention through Communication.” The paragraph will also review practical measures recommended or adopted by several commercial actors to mitigate the hazard at the end of life value chain. When waste lithium batteries with unknown residual energy are transported or entering recycling facilities, special procedures need to be implemented to identify and control the hazards that could develop due to the presence of high density electrical power sources in waste streams. This will be considered in Section 11B.5 on “Electrical Hazard Control.”
11B.2 LEGISLATIVE AND REGULATORY FRAMEWORK
477
Several technical solutions have been considered to deactivate, depower, or inert the battery before transport or treatment when this is feasible: they will be briefly reviewed. The protection of portable batteries collected and transported in bulk will be addressed separately. In the context of a circular economy, the importance of recycling waste batteries and the recovery of raw materials has been placed as a priority by the EU institutions. In addition, “Reuse and Second use” are options to be considered before recycling. This will be further discussed in a final Section 11B.6 as a complementary regulation needs to be developed to deal with the producer responsibility aspects of a second use and a second placing on the market of rechargeable lithium batteries.
11B.1.3 BATTERY AGING The link between battery aging and safety has not been developed in this chapter as there is not sufficient data available to correlate the aging of waste lithium battery components and the safe handling of these batteries at end of life. But for the general influence of aging on safety please see Chapter 7E, Effect of Electrical Energy and Aging on Cell Safety. The Transport Regulation requires the knowledge of the history of the damaged or defective battery before its shipment. Therefore parameters such as abnormal aging, abuse, excessive temperature elevation during normal conditions of use all have their importance when considering the impact of aging on the safe behavior of lithium batteries at the end of life stage. This aspect of the safety issue will be reviewed in Section 11B.3.
11B.2 LEGISLATIVE AND REGULATORY FRAMEWORK During the last 10 years, the collection of waste batteries in general and waste lithium batteries has gained some momentum on a worldwide basis. In North America, Call2Recycle is operating a voluntary waste rechargeable battery collection program that covers waste lithium batteries and their processing in authorized recycling facilities [1]. The collection program covers North America (United States, Canada, and Mexico). In Japan, the Japan Battery Recycling Center (JBRC) is also operating a voluntary National Waste Rechargeable Battery Recycling and Collection Scheme [2]. In Australia, the voluntary collection of waste batteries is organized via the Australian Battery Recycling Initiative (ABRI) [3]. In Europe, portable batteries [4] that are separately collected from consumers have to be processed in a recycling plant as it is forbidden to landfill or incinerate separately collected waste batteries. Obviously, those batteries that are not collected separately will end up in municipal waste streams and will either be landfilled or incinerated. Waste industrial batteries that are taken back by producers or collected by professional waste management companies have to be processed in a recycling facility in accordance with the EU Batteries Directive. For the definitions of portable, industrial, and automotive batteries the reader is invited to consult the Batteries Directive 2006/66/ EC, Article 3 [4].
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11B.2.1 THE EU WASTE FRAMEWORK DIRECTIVE AND THE DAUGHTER DIRECTIVES ON WASTE The EU waste legislation concentrates at first on the protection of workers and of the environment during the production, the handling, and the processing of (hazardous) waste. When the management of waste batteries is considered, the mother piece of legislation (Waste Framework Directive) is complemented by Daughter Directives such as the End of Life Vehicle Directive and the Directive on Waste Electrical and Electronic Equipment (WEEE) and the Batteries Directive.
11B.2.2 THE WASTE FRAMEWORK DIRECTIVE National environmental authorities secure the implementation of the requirements of the EU Waste Directives regarding specific waste streams management. Directive 2008/98/EC [5] sets the basic concepts and definitions related to waste management, such as definitions of waste, recycling, recovery. It explains when waste ceases to be waste and becomes a secondary raw material (so called end-of-waste criteria), and how to distinguish between waste and by-products. The Directive lays down some basic waste management principles: it requires that waste be managed without endangering human health and harming the environment, and in particular without risk to water, air, soil, plants, or animals. The Directive introduces the “polluter pays principle” and the “extended producer responsibility.” It incorporates provisions on hazardous waste and includes two new recycling and recovery targets to be achieved by 2020: 50% preparing for reuse and recycling of certain waste materials from households and other origins similar to households, and 70% preparing for reuse, recycling, and other recovery of construction and demolition waste. The EU Waste Hierarchy principle is illustrated in Fig. 11B.7.
Product/article Prevention Preparation for reuse Preparation for 2nd use
Recovery Recycling Disposal Waste
FIGURE 11B.7 The EU Waste Hierarchy. Adapted from http://ec.europa.eu/environment/waste/framework/.
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479
According to the EU Waste Catalogue [6], batteries containing cadmium, mercury, and lead (or mixtures of batteries containing these batteries) are classified as hazardous waste. Currently, in Europe, waste lithium batteries are not classified as hazardous waste by the EU Waste Catalogue (see below for the distinction between hazardous waste and dangerous goods). Nevertheless, there is an exception in Austria where waste lithium batteries are considered by the National Austrian Legislation as hazardous waste. Therefore the lithium batteries collected in Austria are recycled in Austria, avoiding the issue of the transboundary movement of hazardous waste. There are discussions at EU level for classifying waste lithium batteries as hazardous waste. In Europe, changes in WLB classification is still under evaluation on a country basis. The following Daughter Directives have implications for waste lithium batteries.
11B.2.3 THE END OF LIFE VEHICLE DIRECTIVE Every year, end-of-life vehicles (ELV) [7] generate between 7 and 8 million tonnes of waste in the European Union which should be managed correctly. Directive 2000/53/EC on end-of life vehicles aims at making dismantling and recycling of ELVs more environmentally friendly. It sets clear quantified targets for reuse, recycling, and recovery of the ELVs and their components. The ELV Directive covers certain categories of vehicles, including their components, such as batteries. In its Annex 1 y3, the End of Life Vehicles Directive requires the separate removal of batteries contained in vehicles. This has been applied successfully for lead-acid starter batteries and is now implemented for lithium-ion batteries used in HEV, PHEV, or Full Electric vehicles (EV).
11B.2.4 THE WASTE ELECTRICAL AND ELECTRONIC EQUIPMENT DIRECTIVE The first WEEE Directive (Directive 2002/96/EC) entered into force in February 2003. The Directive provided for the creation of collection schemes where consumers return their WEEE free of charge. These schemes aim to increase the recycling of WEEE and/or reuse. In December 2008, the European Commission proposed to revise the Directive in order to tackle the fast increasing waste stream. The new WEEE Directive 2012/19/EU entered into force on 13 August 2012 [8]. In its Annex 7 yI, the WEEE Directive requires the separate removal of batteries contained in WEEE. This mandatory requirement is applied in all Member States through WEEE operators with a variable efficiency.
11B.2.5 THE BATTERIES DIRECTIVE The EU legislation on waste batteries is embodied in the Batteries Directive [4]. It intends to contribute to the protection, preservation, and improvement of the quality of the environment by minimizing the negative impact of batteries and accumulators and waste batteries and accumulators. To achieve these objectives, the Directive prohibits the marketing of batteries containing some hazardous substances, defines measures to establish schemes aiming at high level of collection and recycling, and fixes targets for batteries collection and recycling. The Directive also sets out provisions on labeling of batteries and their removability from equipment.
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It also aims to improve the environmental performance of all operators involved in the life cycle of batteries and accumulators, for example, producers, distributors, and end-users, and, in particular, those operators directly involved in the treatment and recycling of waste batteries and accumulators. Producers of batteries and accumulators and producers of other products incorporating a battery or accumulator are given responsibility for the waste management of batteries and accumulators that they place on the market. In 2008, the European Batteries Directive 2006/66/EC entered into force in all EU Member States [4]. As a result of the EU Batteries Directive implementation, waste lithium batteries were collected and returned to recycling plants via several major routes as illustrated in Fig. 11B.3: 1. in a mix with other nonlithium batteries as a result of the collection of all types of batteries from consumer applications; 2. after sorting, from streams of collected waste electrical and electronic equipment in a B2B operation; 3. in a separate collection stream when collected in specialized commercial entities; 4. from industrial applications where the waste lithium batteries are returned to industrial waste operators for consolidation before shipment to recycling plants. With the recent development of electric mobility, an increasing quantity of batteries are returned to recycling plants after separation from the application and collection, e.g., from electric bike shops or Authorized Treatment Facilities for cars at End of Life. Industrial batteries used for hybrid and full electric vehicles are generally under the controlled logistic of the car manufacturing company or its authorized representative.
11B.2.6 THE BASEL CONVENTION In addition when waste is transferred between countries and has to cross borders, the shipment have to fulfill the requirements of the Basel Convention on the transboundary movement of hazardous waste [9].
11B.2.6.1 Objective The overarching objective of the Basel Convention is to protect human health and the environment against the adverse effects of hazardous wastes. Its scope of application covers a wide range of wastes defined as “hazardous wastes” based on their origin and/or composition and their characteristics, as well as two types of wastes defined as “other wastes”—household waste and incinerator ash.
11B.2.6.2 Aims and provisions The provisions of the Convention are concentrating around the following main objectives: • • •
the reduction of hazardous waste generation and the promotion of environmentally sound management of hazardous wastes, wherever the place of disposal; the restriction of transboundary movements of hazardous wastes except where it is perceived to be in accordance with the principles of environmentally sound management; and a regulatory system applying to cases where transboundary movements are permissible.
In particular such hazardous waste cannot be shipped to a non-OECD country that has not signed the Basel Convention.
11B.3 TRANSPORT OF LITHIUM BATTERIES FOR DISPOSAL
481
There is a need of Prior consent for the transfer of this hazardous waste (each country involved during the transfer (transport) needs to give its authorization). There is a requirement of financial guarantees to be organized to secure the avoidance of orphan waste or to secure the treatment of orphan waste. The shipment of hazardous waste requires obviously significant administrative work between the shipper and the competent authorities of all countries crossed by the shipment of hazardous waste. Authorization may be granted only after 6 months or one year. . .depending on the number of the transit countries. This administrative work is not necessary for the shipment of nonhazardous waste which is done on a nonregulated free trade basis.
11B.2.7 THE INTERNATIONAL TRANSPORT REGULATION As we shall detail in the next paragraph, lithium batteries are classified as dangerous goods by the UN Model Regulations for the Transport of Dangerous Goods [10,11]. When they are transported to a recycling facility, a disposal center or an incineration facility, the transport of waste lithium batteries is governed by the Special Provision SP377 and its associated packing instruction P909. The transport of Damaged or Defective Lithium Batteries (D&D Lithium Batteries) is regulated independently by SP376 and P908. In Europe, the transport by road is regulated by the ADR [12] (the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR 2015)). The transport by sea is regulated by IMDG Code [13]. It is forbidden to transport waste batteries by air unless authorized by the National/local competent transport authority (See IATA [14]). These requirements will be reviewed in the next paragraph.
11.B.2.8 NOTE TO THE READER: HAZARDOUS WASTE AND DANGEROUS GOODS In the EU, the Dangerous Goods Transport Regulation is independent from the Waste Management Legislation. The terminology “dangerous goods” is used for the transport of new and waste lithium batteries. It corresponds to an international classification as proposed by the UN Recommendations on the Transport of Dangerous Goods—Model Regulations [10]. Currently dangerous goods such as Li batteries transported for disposal or recycling are not classified as hazardous waste. The terminology “hazardous waste” is used for waste batteries classified as hazardous in accordance with the EU Waste Catalogue [6,15].
11B.3 TRANSPORT OF LITHIUM BATTERIES FOR DISPOSAL OR RECYCLING The United Nations (UN) Model Regulations on the Transport of Dangerous Goods regulates the conditions of transport of Dangerous Goods such as lithium batteries listed under the reference numbers UN3090 and UN3091 (for lithium-metal batteries) and UN3480 and UN3481 (for lithiumion batteries).
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The objective of the UN Transport Regulation for Dangerous Goods is to define the rules/provisions under which the safe transport of dangerous goods is guaranteed. The UN Recommendations for the Transport of Dangerous Goods (Model Regulation—20th Edition) are structured around Special Provisions and associated Packing Instructions [10,11]. In principle the Special Provision defines the scope of application of the transport conditions while the associated Packing Instruction(s) addresses the technical details on the way to transport safely dangerous goods such as waste lithium batteries and damaged and defective lithium batteries. These provisions and instructions are aimed to be applied on a worldwide basis by any consignor to prevent and control the potential hazards that can originate in the mishandling of lithium batteries during transport. In addition, the UN Model Regulation is complemented by the specific Modal Transport Regulation, e.g., the ADR for Road and Rail Transport (ADR 2017) [12]. General for transport regulations see also Chapter 11A, Special Risks During Transport and Storage.
11B.3.1 SPECIAL PROVISIONS SP377 AND SP636 (B) (ADR) FOR LITHIUM BATTERIES TRANSPORTED FOR DISPOSAL OR RECYCLING In the specific case of lithium batteries transported for disposal or recycling, Special Provision SP377 and Packing Instruction P909 apply. NB. The UN Model Regulation does not use the terminology “waste” to characterize the load of lithium batteries when transported for disposal or recycling. Special Provision SP377 defines the scope of application of the Transport Regulation such as the type of lithium batteries as well as the marking requirements; reference is also made to the applicable Packing Instructions P909 that regulates the packing of lithium batteries carried for disposal or recycling. Under certain conditions, P903 for new lithium batteries can also apply to waste lithium batteries transported for disposal or recycling (See P903 (2c) when such batteries are still in compliance with testing requirements). P909 applies to lithium batteries transported for disposal or recycling either packed together with or packed without nonlithium batteries. it also regulates the transport of lithium batteries contained in equipment (see P909 (3)). The application of the UN Recommendations through the various transport modes is summarized in Table 11B.1. When the modal transportation is considered, the ADR Transportation regulation contains a specific Special Provision for the transport of waste lithium batteries (SP636 (b) (ADR 2015)) in relation with Packing Instruction P909. Special Provision SP636b (ADR) provides for some relaxation from the Packing Instruction P909. Indeed SP636 is considering the special conditions under which waste lithium batteries are collected from consumers. In Europe a significant ratio of waste lithium batteries is collected with other non-lithium batteries (e.g., zinc-alkaline batteries). The commercial entity, the private or administrative office, or the civil amenities collecting waste lithium batteries in a mix with other types of batteries do not have the knowledge about the composition of the returned batteries at the collection point. Therefore the Packing Instruction tolerates the return of these mixes of batteries in controlled quantities to the intermediate processing facility under not fully regulated transport conditions. This is illustrated in Fig. 11B.8.
Table 11B.1 Summary of the Transport Regulations for the Various Transport Modes for Waste Lithium Batteries Transported for Disposal or Recycling Specific Regulatory Requirements Waste Lithium Batteries (a)
Transport Modes 1.1.
1.2. 1.3. 1.4.
UN Model Regulation For the Transport of Dangerous Goods (Ref. 11). ADR—Road Transport (Specific in addition to 1.1.) (Ref. 12). IMDG—International Maritime Transport Regulation (Ref. 13). IATA—International Air Transport Association (Ref. 14).
UN SP377 and P909 (with the possibility to use P903 (2) under certain specific conditions) for waste Lithium batteries. In addition to 1.1. above and for Waste Lithium Batteries SP636b—ADR needs to be considered for Road Transport. To be considered: SP377, P909 and SP636b identical to Road Transport. IATA Dangerous Goods Regulations, Special Provision A154. Not allowed except when approved by the National Transport Authority of the State of Origin and the State of the Operator (Recycler—Disposal Facility).
a
Batteries transported for disposal or recycling.
Waste lithium batteries UN3090 & UN3480 and UN3091 & UN3481
SP636b
ADR road transport (specific)
SP377 & P909 or P903
Excepted from full regulation
Subject to full regulation
Modes road transport only
Modes road and maritime (not allowed by air mode)
1. Scope Li-M 20 Wh per cell 1.0 g Li per cell Li-ion 100 Wh per battery 2.0 g Li per battery < 500 g (cells and batteries) Together with or without other non-Li batteries 2. Conditions Up to the intermediate processing facility Quality insurance system in place < 333 kg (cells and batteries) per load P909 applies except add req 1 & 2 May not be protected individually against short circuit May contain not identified D&D Li batteries (see SP377) 3. Packaging Strong outer resistant packaging up to 30 kg gross mass
4. Marking Marking required Class 9 UN numbers
UN model regulation
1. Scope Full range of energy content All sizes (from small to large) Only lithium batteries and lithium batteries contained in equipment 2. Conditions Identified damaged & defective batteries need to follow SP376 For Li cells and batteries in equipment : outer packaging not PGII For Li cells and batteries > 12.0 kg with a strong outer resistant outer casing, a strong outer packaging may be used
3. Packaging Approved packaging of PG II performance level. or up to 30 kg >>> nonapproved packaging (strong outer packaging) Batteries should be secured against movement inside the outer packaging Packed to prevent short circuits and dangerous evolution of heat 4. Marking
Lithium batteries for recycling Not required Not required
Marking Class 9 Un numbers
Lithium batteries for recycling Required Required
In addition WLB may be transported as new batteries under P903 (2c)
FIGURE 11B.8 Summary table of the transport requirements for waste lithium batteries under the UN Model Regulation and ADR.
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11B.3.2 SPECIAL PROVISION SP376 FOR THE TRANSPORT OF DAMAGED AND DEFECTIVE LITHIUM BATTERIES The carriage of damaged and defective lithium batteries is regulated by a dedicated special provision SP376 and a packing instruction P908 (for batteries up to 400 kg net mass). A separate Large Packing Instruction LP904 covers the transport conditions for large batteries that are damaged or defective with a net mass above 400 kg. When a battery has undergone one or more severe mechanical damages leading, for example, to electrolyte spill out or structural damages or in case where it shows evidences of instable thermal behavior, such a battery is considered as damaged and needs to receive a dedicated attention for packaging and marking from the shipper/consignor. Similarly, a battery may be considered as defective when it has lost some of its functional properties that may lead to some instability such as abnormal thermal behavior, even when it has not been through mechanical damages. The International Transport Regulation has adopted a Special Provisions SP376 that considers the cases where a battery needs to receive the appropriate handling due to its defects or damages or its potential thermal instability: Table 11B.2 summarizes these specific regulatory requirements. Packing Instruction P908 allows the return of these damaged and defective batteries in controlled quantities per package to recycling plants under fully regulated transport conditions illustrated in Fig. 11B.9. It is advisable for the reader to refer to reference books prepared by qualified organizations such as “Lithium Batteries Transport and Packaging Instructions (A Multimodal Approach)” that can be also consulted on the referenced website [16]. This book is summarizing the transport regulation for lithium batteries with dedicated chapters on the transport of waste lithium batteries. the practical aspects of the packing instructions and packaging requirements are also described in the publication prepared by Dr. M. Ottaviani [16]. The publication of Label Master on the subject is another reliable source of information [17].
Table 11B.2 Summary of the Transport Regulation for the Various Transport Modes for Damaged and Defective Lithium Batteries Transport Modes 1.1.
UN Model Regulation For the Transport of Dangerous Goods
1.2.
ADR - Road Transport (Specific in addition to 1.1.) IMDG - Road and Maritime Transport. IATA - Air Transport
1.3. 1.4.
Specific Regulatory Requirements Damaged and Defective Lithium Batteries SP376 and P908 and LP904 NB. SP376 Overruled SP377 for identified D&D Batteries. SP376 and P908 and LP904 SP376 and P908 and LP904 IATA Dangerous Goods Regulations, Special Provision A154. Not allowed except when approved by the National Transport Authority of the State of Origin.
11B.3 TRANSPORT OF LITHIUM BATTERIES FOR DISPOSAL
485
Damaged & defective lithium batteries UN3090 & UN3480 and UN3091 & UN3481
SP376 and P908
(UN model regulation and ADR)
Subject to full regulation Road and maritime (not allowed by air mode) 1. Scope Full range of energy content All sizes (from small to large) Large batteries > 400 kg are covered by LP904 2. Conditions The use of PGII is required. Cell of a net mass > 30 kg: one cell per packaging. 3. Packaging Each D&D battery shall be individually packed in an inner packaging and placed inside an outer packaging Each inner packaging shall be surrounded by non-combustible and nonconductive thermal insulation material Adopt measures to minimize the vibrations effects during transport Absorbent material to be used for leaking batteries
4. Marking Marking Class 9 UN numbers
Damaged/defective Lithium batteries Required Required
FIGURE 11B.9 Summary table of the transport requirements for damaged and defective lithium batteries under the UN Model Regulation and ADR.
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11B.4 COMMUNICATION TOOLS AS PREVENTIVE MEASURES The number of commercial actors dealing with lithium batteries is increasing significantly as the lithium battery technology is under continuous technical development and used in a broader range of applications. Therefore, it is important for battery manufacturers to communicate about the properties of their product down the value chain. In parallel, end of the pipe actors such as collectors and recyclers are also increasing while receiving larger quantities of various types of waste lithium batteries. When waste lithium batteries are reaching an intermediate storage facility, a waste management plant for consolidation or sorting, or a recycling plant before treatment, the local operators need to be informed with the most updated information regarding the lithium battery composition and their physical and chemical properties. In response to this concern, Competent Authorities and Private Organizations have prepared communication tools where good practice guidance, emergency response guidance, or battery information factsheets are made available to professionals.
11B.4.1 THE PREVENTION AND RESPONSE TO INCIDENTS Batteries associations such as RECHARGE and PRBA, supported by their members representing the lithium battery industry, have developed communication tools describing the potential hazards of lithium batteries [18]. This type of information contains also appropriate information regarding the prevention and response to incidents. Good Practice Guidance and Emergency Response Guidance prepared by National Transport Authorities [19] and industry represent key communication tools about the potential hazardous properties of lithium batteries. They describe the basic safety measures to adopt for handling or storing new lithium batteries and waste lithium batteries. The first Emergency Responses Guides were published in the mid-2000s by the US Department of Transport (DOT): the Pipeline and Hazardous Materials Safety Administration (PHMSA) issued an updated version of its Emergency Response Guidebook in 2016 [20]. The Guide N 138 addresses the specific issues of lithium primary batteries while the Guide N 147 is dealing with lithium-ion batteries. The Emergency Response Guidebook is used by emergency services personnel to provide guidance for initial response to hazardous material and dangerous goods incidents. This publication helps to provide consistent emergency response procedures for hazardous materials in North America, and is an essential tool for preparedness, planning and training. The preparation of this Guidebook is a joint effort between the transportation agencies of Mexico, Canada and USA.
More recently, RECHARGE the European Advanced Rechargeable Battery Association has published a Lithium-Ion Battery Information Factsheet [21] that covers the handling of lithium batteries at end of life. In cooperation with CTIF, the Factsheet was used to prepare an appropriate emergency response in case of incident at the attention of first and second fire responders [22]. Call2recycle [23] has published safety tips on how to recycle safely lithium batteries. The organization is also proposing a detailed set of information regarding the packaging of batteries for mail delivery.
11B.4 COMMUNICATION TOOLS AS PREVENTIVE MEASURES
Do • Carry out a risk assessment before you start any activity involving used batteries. • Ensure that appropriate firefighting equipment is available in case of a battery fire. • Ensure that Material Safety Data Sheets (MSDS) are readily accessible. • Comply with all packaging and transport requirements in the Australian Dangerous Goods Code if you are collecting, transporting, or storing a lithium or lithium ion battery consignment. • If lithium batteries are mixed with other nonlithium batteries for recycling, follow the requirements in Dangerous Goods exemption 010/12. A quality assurance system must be in place to ensure that the total amount of lithium batteries per transport unit does not exceed 333kg and the total weight of each container does not exceed 400kg. A copy of the exemption must be carried by the driver. • Ensure that the site where lithium batteries are collected and stored, and the transport vehicle, have a satisfactory level of security to ensure that only trained people have access. • Train employees in spill and emergency response. • During storage and transport ensure that batteries are protected from the weather and excessive humidity, in a well ventilated area, and easily accessible in case of a fire. • Always wear thick gloves and safety glasses if handling batteries. • Wash your hands thoroughly with water should contact be made with leaking or damaged batteries. • Ensure that storage containers are appropriately labeled.
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Don't • Don't store used batteries near any heat source (strong light, sun, oven, machinery). • Don't store used batteries near other chemicals or food. • Don't touch used batteries without protection. • Don't store batteries too close to inhabited buildings. • Don't attempt to lift heavy loads manually. Always seek help or put controls in place (removal trolley or forklift). • Don't handle used batteries if you haven't been trained. • Avoid vibrations and micro-movements caused by transportation, machines, fork-lift, etc. as they increase the risk of short circuits. • Don't transport used handheld batteries with other batteries weighting more than 500g or used lead acid batteries (ULABs). These need to be packaged separately as they have different regulatory requirements. • Don't deliberately break open lithium batteries as lithium is a reactive metal and if exposed to humid air may react and spontaneously catch on fire. Care needs to be taken to avoid physical damage to the batteries. • Don't store batteries for more than 6 months. They should be transported to recyclers regularly.
FIGURE 11B.10 List of recommendations for the handling of waste lithium batteries.
The Australian Battery Recycling Initiative (ABRI) is a not-for-profit association established in 2008 to promote responsible environmental management of batteries at end of life. More information on battery recycling can be found on their website where the organization is proposing safety guidance for the transport and recycling of lithium batteries [24]. A list of recommendations for the storage and handling of lithium batteries as proposed by the Australian Battery Recycling Initiative is reproduced in Fig. 11B.10.
11B.4.2 RESULTS OF TESTS The information gathered by laboratories or institutions that are performing tests on lithium batteries is essential for the professionals that are handling and storing large quantity of waste lithium batteries. The pioneering work of the National Fire Protection Agency (NFPA-USA) [25] and of The Institut National d’Etude des Risques (INERIS-F; [26] ) need to be mentioned as they analyze the consequences of a severe incident and the appropriate measure to be taken by responders [27].
11B.4.3 RECALLED BATTERIES Air carriers such as UPS and DHL are issuing regularly recommendations about the transport of recalled lithium batteries for recycling [28,29]. Their basic recommendation is not to ship by air batteries recalled by the manufacturer for safety reasons, as such shipments are prohibited by regulation (i.e., IATA Dangerous Goods Regulations, Special Provision A154).
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Table 11B.3 Set of Recommendations for the Safe Storage of Waste Lithium Batteries as Published by VDA (Ref. 30) • Compliance with all requirements of the manufacturer regarding safety through its safety data sheet. • Prevention of short circuits by adequate protection of battery terminals. • Prevent internal short circuits, e.g., during mechanical damage. • Prompt disposal wanted for trial products via waste management professionals. • Do not expose to high temperature heat sources or expose directly to sunlight. In the case of Mixed Storage of goods/articles, organize a separate storage area for lithium batteries. Maintain a distance of 2.5 m from other goods storage area. Comply with fire safety equipment or store in separate areas (e.g., dedicated containers). Safety cabinet, hazardous substance containers, . . . Appropriate staff training for handling of lithium batteries (according to similar Dangerous Goods/Hazardous materials). Prepare dedicated fire intervention tools. Maintain contact with local authorities and official fire responders.
As mentioned in Section 11B.3 above, waste lithium batteries collected for recycling are not to be sent via air services as the shipment of waste batteries by air is forbidden unless an authorization is granted specifically by the National Air Transport Authority.
11B.4.4 RECOMMENDATIONS FOR THE SAFE STORAGE OF WASTE LITHIUM BATTERIES The German Insurance Association [30] has issued recommendations for the storage of lithium batteries that applies both to new and waste lithium batteries. Such recommendations can be found in one of their publications where they mainly concentrate on the conditions for storage. Some of their recommendations are listed in Table 11B.3. For safe storage see also Chapter 11A.2, Storage.
11B.4.5 FIRE FIGHTING FIRST RESPONDERS Fire fighting first responders have also considered the new type of hazards developed by electrically powered vehicle, hybrid, plug-in hybrid, or full electric equipped with lithium batteries. Among their concern comes the first response to a fire and, after, the management of the battery when such an incident is under control. At the initiative of CTIF, an IEC Standard on the Information Sheet is in preparation by Fire Fighters Organizations [31]. For fire fighting see also Chapter 12C, Ignition and Extinction of Battery Fires.
11B.4.6 WASTE BATTERIES COLLECTION ORGANIZATION EUCOBAT is the European association of national collection schemes for batteries [32]. The Members of EUCOBAT ensure that all collected waste batteries are recycled in an ecological
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sound way. These advisory notes are based upon the experience and the best practices of the members of EUCOBAT and to the best knowledge of the compliance organizations. They are subject to permanent evaluation and improvement. They have published in 2013 a series of Safety Advisory Notes. Their recommendations should be consulted before collecting and shipping waste lithium batteries collected from end users.
11B.4.7 THE TRAFFIC LIGHT APPROACH In order to minimize the hazards linked to waste lithium batteries storage and transport, the recommendations developed by GRS (Battery Collection and Recycling Foundation (Germany)—one of EUCOBAT’s members) are illustrated by the traffic light approach (Fig. 11B.11) where three different levels of hazards are associated with the collection of waste lithium batteries [33]. The Green level concerns the collection and storage of lithium batteries of low nominal energy content (e.g., less than 100 Wh) in a mix with other nonlithium batteries. This is typical of the collection of waste consumer batteries from sales points. The Yellow/Orange level concerns the collection of mono-fractions of primary and secondary lithium batteries of known composition. The Red level is attributed to the collection of damaged portable or industrial batteries with a high energy content: typically, damaged e-bikes batteries would enter this category.
FIGURE 11B.11 The traffic light approach: basic principles for a differentiated hazard approach when handling, storing, and transporting waste lithium batteries. GRS—http://www.grs-batterien.com/fileadmin/user_upload/Download/Batteriebriefe/GRS-Batteriebrief_EN.pdf.
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As an evaluation tool for their clients, GRS has also developed a questionnaire with recommendations to categorize the batteries in accordance with the traffic light approach and to adopt the appropriate attitude before the transport of such batteries from such collection points. In a similar way some of the members of the German automotive industry have adopted a traffic light approach for the transport of damaged and defective lithium batteries used for E-mobility [34]. It concerns mainly the qualification of lithium batteries that have undergone an accident while installed in an electric vehicle. The following progressive scale of hazards has been retained in order to supply the most appropriate packaging and transport recommendations to the damaged battery. Green: Yellow: Red:
Batteries not damaged, not defective. Batteries may be damaged but not showing any potential evolution of heat. Batteries suspected to be “unstable” that may undergo heat evolution (uncontrolled).
The associated recommendations for packaging and transport can be obtained by contacting directly the referenced authors.
11B.5 ELECTRICAL HAZARD CONTROL: TECHNICAL SOLUTIONS Lithium batteries collectors and recyclers have to deal with primary lithium-metal batteries and rechargeable lithium-ion batteries for processing in their plant. As shown in Fig. 11B.12 there is a wide range of energy content in new lithium-ion batteries that may or may not be present when the waste battery flow reaches the recycling plant. In a similar way in the case of lithium-metal batteries, the recyclers may accept button cells (less than one Ah nominal capacity) as well as large
FIGURE 11B.12 Range of the initial energy content of new lithium ion batteries that may be present in a waste battery stream.
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491
batteries built for industrial applications with energy content up to the kWh and higher. They may also accept manufacturing rejects with more than 80% charge or batteries only partially discharged. This paragraph will elaborate on the control of the electrical risk that may be present in waste lithium batteries due to a residual electrical charge and the way to mitigate it.
11B.5.1 ELECTRICAL HAZARD The processing of waste lithium batteries for recycling requires in most cases their handling in several preliminary steps, in particular when they have been assembled to deliver high energy and power, for example, for electric mobility. When entering a recycling facility, industrial lithium batteries may still contain a significant residual electrical energy. Due to their weight and volume, these batteries are disassembled into smaller components (modules or cells) in order to feed the recycling process. The preliminary treatment steps will secure the protection against two major hazards: the electrical shock from high voltage and high power batteries (e.g., above 48 VDC) and the chemical hazard linked mainly to the presence of organic substances in the battery. For large batteries, the end of life management will generally involve four steps, including: 1. Pretreatment. A pretreatment step for the removal of fluids (such as cooling fluid) or external cleaning. 2. Disassembly. A dismantling step where the battery is disassembled into basic modules and where the various metallic or plastic components (connectors, wiring, etc. . .) are separated. 3. Recycling. A treatment where the battery (or its modules) is entering a process to separate and/ or recover added value materials involving among others, mechanical handling, thermal treatment, chemical processing. 4. Waste Disposal. A final treatment step for residues not recovered under previous step(s). For safety reasons, the battery may be deactivated in order to reduce its voltage and electrical energy content to a minimum value and therefore to prevent electrical shocks. This deactivation may occur before or during step 2 above (disassembly) according to the design of the battery and its technical characteristics. In this chapter, we shall concentrate on references to various methods used for the electrical deactivation of lithium-ion batteries. In the literature, deactivation is synonymous of other terminology such as depowering, inerting, de-energizing, . . . Deactivation targets one objective: the reduction of the residual electrical energy content of the waste battery to a minimum value where the electrical hazard is eliminated. The reported methods apply to industrial batteries well above the 100 Wh range. Typically, deactivation applies to “industrial batteries” used in E-mobility or energy storage applications. The methods of deactivation have also been considered for lower energy containing batteries (,100 Wh), but this practice has not been implemented at industrial scale. It is worth mentioning the recent publication of the United States Advanced Battery Consortium (USABC) on the Recommended Practice for Recycling of xEV Batteries (electrochemical energy storage systems [35]). This set of recommendations shows how important it is to be informed about the battery content and the design of the battery to facilitate a safe end of life processing as well as the recovery of added value materials.
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11B.5.2 DEACTIVATION 11B.5.2.1 Deactivation or de-energizing, depowering, or inerting a Lithium Battery The disassembly of a large EV batteries offering nominal voltages higher than 100 Volts and capacities higher than 10 20 Ah up to 100 Ah requires well informed operators. The deactivation of large EV batteries is an operation that requires trained manpower, special skills and tools, the knowledge of the architecture (design) of the battery, as well as its chemical composition. Generally the E-car manufacturer wants to keep this task inside a circle of qualified and well trained technicians. For safety reasons, it is advisable to inform the “recycler” about the exact design and composition of the battery in order to evaluate the hazards associated to the handling of the chemicals contained in the battery (see Section 11B.4 of this chapter). A well-documented manufacturer’s guide on the safe design of batteries as perceived by a battery manufacturer has been prepared by Jim McDowall [36]: A Guide to Lithium—Ion Battery Safety. In Fig. 11B.13, we have summarized various options considered to deactivate a lithium-ion battery. At end of life, three potential routes have been identified to handle the battery: the example of deactivation of a damaged and defective battery has been selected.
Damaged & defective Batteries (D&D) Objective : secure safety during transport Control the reactivity of the D&D battery 1. UN = SP376
3. Wet process (deactivation)
Discharge
No need for
/external
deactivation
3. Discharge in salt water
2. Dry process (deactivation)
2.2. 2.1. Disassembly
Controlled pyrolysis
2.1.1. Separated D&D module
2.1.2. Separated not D&D modules
2.2.1. Metals & powder
2.3.
load
2.3.1. Low voltage battery
Packaging requirements P908 or LP904
3.1. After drying
3.2. Wet as processed
Safer transport conditions (D&D Batteries Transported for Recycling)
SP 376 &
Like a new
PI908 (See
battery SP 188
Case 1)
P903
Waste battery SP 377 & PI909
Waste or HAZ. waste ?
Waste battery or not?
Waste battery SP 377 & PI909
SP 376 & PI908
Like a new battery SP 188 P903
Waste battery SP 377 & PI909
Use of cushioning materials
Waste or HAZ. waste ?
Waste or HAZ. waste ?
Waste battery or not?
Waste battery or not?
Waste battery
Waste battery
SP 377 & PI909
SP 377 & PI909
FIGURE 11B.13 Various technical alternatives for the deactivation (depowering) of waste lithium batteries.
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493
1. The application of the UN Model Regulation Requirements (SP376 & P908&LP904) and the use of cushioning materials; 2. The application of a dry deactivation based on electrical, thermal, mechanical means; 3. The use of a wet deactivation process in an appropriate water-based electrolyte. Each one of these methods has some advantages and constraints that will be reviewed. In addition, there are many questions raised after the deactivation of a battery. We have also considered the complexity of the handling of the deactivated battery. Indeed some operators are deactivating the battery to classify it as chemical waste and not as a waste battery. The examples illustrated in Fig. 11B.13 show the potential complexity of the problems and the decision processes.
11B.5.3 UN TRANSPORT REGULATION When a damaged and defective battery is transported according to the UN requirements of Special Provision SP376, the importance is placed at the level of the knowledge of the history of the battery (SP376) and at the level of the packing requirements (P908). As mentioned in Section 11B.3, one objective of the UN Transport Regulation is to propose packing instructions that will secure the safe transport of batteries for disposal or recycling. The safety aspects have to be secured by the “consignor,” where the consignor means any person, organization, or government which prepares a consignment for transport, as defined in the UN Model Regulation. One of the requirements of P908 is the use of cushioning materials that will allow to control the abnormal evolution of heat inside a packaging containing lithium batteries (e.g., in the case of thermal runaway). The cushioning material may also be used to absorb any liquid leakage out of the battery.
11B.5.4 USE OF CUSHIONING MATERIAL IN PACKAGING AND STORAGE In order to mitigate the hazard during the transport of lithium batteries for recycling, the regulator requires the use of cushioning materials to prevent among others short circuits during transport and also to avoid the movement of batteries when their packaging is handled and transported (see P908 or P909 of the UN Model Regulation). The technical requirements of the packaging material imposed by the regulator are as follows: Non-combustible, non-conductive (electrically), thermal insulator, chemically inert, cushioning effect and absorbent,. . .
The company ACCUREC GmbH [37] performed recently a study on the use of cushioning materials in transport conditions. The authors have considered that the cushioning materials selected must protect batteries against movements during transport. In addition, the material needs to be handled in a practical way at a realistic cost. In the study, ACCUREC has considered the thermal properties of five cushioning agents: Vermiculite, Sand, SORBIX, Absorbent and Pyro-Bubbles. The various types of cushioning materials are represented in Fig. 11B.14.
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FIGURE 11B.14 Illustration of the various types of cushioning agents studied by accurec gmbh (Ref. [37]).
ACCUREC concludes that thermal conductivity and heat capacity are the important factors in the selection of the cushioning material. As a result of their tests, they identified sand as being the cushioning material that offers the best ratio of technical performances versus cost. Technical performances include control of a thermal runaway and its heat impact to surrounding cells.
11B.5.5 WET DEACTIVATION VIA “IMMERSION” Facing the constraints of the UN Model Regulation, several industrial actors have considered that a “deactivated” battery is safer for transport. The procedure of immersion of the battery in salted water was first developed by battery manufacturing companies and by waste management companies. It consists generally of the immersion of the battery in salted water where the ionic-conductivity of the solution offers slow discharge conditions to the individual elements of the battery by creating an external short via the salted solution. Corrosion occurs with time which allows the salted solution to penetrate deeply into the battery elements, modules, or cells. The discharge of the battery ends when all cells have been exposed to the salted solution and the voltage of the cells or battery is reduced to a minimum value. The method suffers of a few major drawbacks: • • •
The discharge time is strongly dependent of the residual capacity of the battery. The salted electrolyte access to the cells is variable and dependent of the battery design. The end of the discharge is not controlled with accuracy.
11B.5 ELECTRICAL HAZARD CONTROL: TECHNICAL SOLUTIONS
• • • •
495
Lithium-ion batteries that have been discharged by this method have been reported to catch fire when drying. The evolution of hydrogen and other flammable gases during the discharge process requires gas exhaust equipment. The salted solutions need to be handled as hazardous waste at the end of the process. These considerations limit the use and control of a discharge by immersion to qualified employees and to facilities equipped with a waste water treatment unit.
The obvious advantage is the (theoretical) minimum initial investment for equipment (large pool and salted water). The wet deactivation process raises the question: is the deactivated battery still considered as a battery or can it be considered as hazardous waste? The response to this question varies with the level of achievement of the deactivation process. It certainly relies on the type of waste electrolytes produced at the end of the process and the remaining electrical charge in the deactivated battery.
11B.5.6 THE REDOX SHUTTLE APPROACH This approach is an improved version of the immersion process. By adding a selective redox system to the salted electrolyte in which the battery is immersed, the full discharge of the battery is guaranteed, leading to a safer behavior of the waste battery [38]. The advantages of adding such a Redox Shuttle Additive (RSA) in the immersion solution is the avoidance of gas evolution and the possibility to reach a discharged status in a reproducible manner. The methodology was known as early as the 1980s when it was discovered that RSA can be used as reversible overcharge protection of lithium-ion batteries. Details of this approach which is under development have been described by M. Wachtler and al. [39].
11B.5.7 DEACTIVATION THROUGH A CONTROLLED LOAD The use of an external load is a dry method that is attractive for large EV batteries at end of life [40]. In addition, when these batteries are defective and modules need to be replaced the selective discharge through an external load may be applied specifically to the defective module. The removal of energy from the battery or battery sections will make them safer for transportation. Deactivation or depowering can be performed on battery packs and modules most probably when the battery is removed from the vehicle. The dry deactivation generally offers the possibility to transport the deactivated battery under the lighter regime of SP376 as it is less susceptible to develop a dangerous evolution of heat due to a short circuit.
11B.5.8 OTHER MEANS TO DEACTIVATE A BATTERY 11B.5.8.1 Controlled thermal deactivation The principle of thermal deactivation has been recently described by the University of Loeben (Austria). Details can be obtained from the project leader, Mrs. A. Arnberger [41].
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The process consists of heating the battery to a controlled temperature range, below the critical temperature where a thermal runaway can develop. The result of the treatment is the deactivation of the cell from its chemical reactivity (solvent removal) and electrical sensitivity due to the absence of conductivity inside the cell at the end of the process.
11B.5.8.2 De-activation by cooling The handling of lithium-metal batteries under liquid nitrogen is a process used by TOXCO [42]. Recently, some types of lithium-metal rechargeable batteries have been transported at end of life under refrigerated conditions. Low temperatures are used to lower the conductivity of the electrolyte as well as the kinetic of hazard reactions and, therefore, to reduce the hazard of a thermal runaway during transport or batteries processing.
11B.6 REUSE AND SECOND USE The purpose of this paragraph is to define “reuse and second use” of rechargeable lithium batteries, describe the legal context where it can be applied, investigate how the Extended Producer Responsibility Principle applies for their reuse or second use and decide whether minimum requirements are needed to recommend reuse and second use of lithium batteries. With the market development of new rechargeable battery technologies offering longer service life and the possibility to power other applications than the one they were designed for originally, the “reuse” and the “second use” of rechargeable lithium batteries has been proposed to enhance their service life and/or to optimize their cost/performance ratio. It is also a way to reduce their environmental impact while enhancing their usage. The content of this paragraph is based on a report [43] issued recently by RECHARGE where an analysis is proposed of the various issues linked to the reuse or second use of lithium batteries. On December 2, 2015, the European Commission adopted an ambitious new Circular Economy Package [44] to help European businesses and consumers to make the transition to a stronger and more circular economy where resources are used in a more sustainable way. The proposed actions will contribute to “closing the loop” of product life cycles through greater recycling and reuse, and bring benefits for both the environment and the economy. Circular Economy keeps the added value in products as long as possible in order to minimize waste. The objective is also to keep resources within the economy when a product has reached the end of its (first) service life in order to create additional value of this product. The priorities of the legislator evolve into the direction of: 1. Extension of the product’s service life (e.g., by appropriate design, increasing materials performances,. . .). 2. Reuse or second-use (preventing early waste production). 3. Recycling (to recover value added materials or products). These policy options have been presented schematically in Fig. 11B.7.
11B.6 REUSE AND SECOND USE
497
In the Electric Vehicle Regulatory Reference Guide [45] prepared by the UNECE Electric Vehicle and the Environment Informal Working Group, it is mentioned that: As Lithium batteries dominate the cost of electrified vehicles and are typically deemed unusable from a mobility standpoint after degrading to between 70 and 80% of fully-chargeable capacity, there is a compelling reason to take a serious look at re-using these batteries in other applications. Battery re-use post-mobility represents a wide gap that will be challenging to govern given the highly variable nature of battery wear and inherent differences in chemistry, construction, and power management. In order to ensure the success of battery re-use or second use, guidelines and regulations that govern the implementation, as well as ensure the reliability and durability of such systems are crucial. There may also be a need for additional regulation/legislation in this field to prevent misuse or abuse of rechargeable batteries offered for second use.
A number of research initiatives and pilot projects have been developed to evaluate the economics and viability of second use of (mainly industrial) lithium batteries. These projects link the industrial battery used in e-mobility with the household electricity grid in a so-called combined energy storage. As long as the project is run under the responsibility of the battery producer, there does not seem to be an issue with extended producer responsibility principle as the producer controls the first and second placing on the market. A nonexhaustive list of projects evaluating the possibility to have a second use for EV Batteries is presented in Table 11B.4 while Fig. 11B.15 offers an illustration of the various management options of lithium batteries at end of life. Table 11B.4 Nonexhaustive List of Minimum Requirements to be Considered for Allowing Reuse or Second Use of Lithium Batteries (Recharge)
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Life cycle Design
Article
Applications
(Re)Processes Reuse * Application A
New product Application A
Manufacturing assembly
Repurposing Redesigning
Repurposed for a different application
New battery Incorporated or private label
Incorporated or Relabeled
PoM Remanufactured,... same design product, same application (*)
PoM
In use
In use
Used, D&D or from repair...
Used, D&D, Rep.
EoL Waste
EoL Waste
* includes integration of the original battery (component) into the product to obtain same functionalities as before.
** includes changes in electronics, software, communication system (e.g., battery management unit)
Use phase In use
Used defective damaged Repaired
Remanufacturing (2) Rebuilding Refurbishing Reconditioning Repairing
(3) EoW
End-of-Life recycling
EoL Waste
Waste treatment Preparation for recycling
Re-enter life cycle as raw material
Second use ** Application B
End of Waste Recycling Energy recovery landfill
(4)
FIGURE 11B.15 Illustration of various management options for lithium batteries at end of first service life.
In this section, the author will concentrate on definitions issues and on the producer responsibility associated to the additional commercial step where a lithium battery could be commercialized for a second use.
11B.6.1 DEFINITIONS The literature offers a wide variety of terminology to qualify a technical and commercial step where the service life of lithium batteries is enhanced: second hand use, double use, repurposing, refurbishment, remanufacturing, repairing, redesigning, reconditioning, etc. These terms need to be placed in their context to avoid confusion and misunderstanding of the issues [46]. In the Batteries Directive 2006/66/EC, the term “reuse” is not defined. Such a definition is supplied in the Waste Framework Directive and other Daughter Directives such as the WEEE and the ELV Directives (see Section 11B.2 for the reference to the Directives). In contrast, the term
11B.6 REUSE AND SECOND USE
499
“second use” is not defined at all in the various Waste Directives (neither in the Waste Framework Directive nor in other Daughter Directives) that are governing the end of service life of substances, mixtures, equipment or articles. We are proposing the following definitions for reuse and for second use. Reuse. Any operation by which articles (products or components) that are not waste are used again for the same purpose for which they were conceived. This definition is supplied in Article 3 (y13) of the Waste Framework Directive 2008/98/EC (WFD). RECHARGE interprets that reuse is meaning the complete or partial reuse of the battery for the original purpose/application it was designed for (possibly after inspection or remanufacturing or refurbishment) when placed on the market for the 1st time. The definition of reuse is based on the “same/original purpose.” One could argue about the fact that batteries—being a component—in the case of reuse, need to be reused in the original application in order to secure all technical performances and safety aspects. Second use is not mentioned in any of the Directives listed above. RECHARGE interprets second use as any operation by which articles (products or components) that are not waste are used for a different purpose for which they were conceived and placed on the market for the 1st time. The absence of definitions for the “second use” of a battery opens the door to a misunderstanding of the operation of second use and its legal consequences. Therefore some caution is advised to readers as in many documents the terminology “second use” is being utilized to describe either second hand use, or second life, or even to describe reuse. . .
11B.6.2 THE EXTENDED PRODUCER RESPONSIBILITY (EPR) The producer responsibility is at first regulated when a product or article is placed on the market by an identified producer. The producer responsibility has been further extended to the management of waste lithium batteries. When lithium batteries are concerned, the legislation covers the first placing on the market. The absence of a legal background raises the issue of the extended producer responsibility for such batteries that are either reused or offered to the market for a second use. Beyond the need for harmonized definitions across the different waste directives, there is also a need to clarify the minimum requirements under which the legal context could further develop.
11B.6.3 EPR AND DIRECTIVES ON NEW PRODUCTS The producer responsibilities are well defined in the Directive 2001/95/EC on General Product Safety where Article 2 (e) defines the producer and its responsibilities regarding the safety of the products or article sold under its brand name. In addition, Directive 85/374/EEC on liability for defective products in Article 3, producer means the manufacturer of a finished product, the producer of any raw material or the manufacturer of a component part and any person who, by putting his name, trade mark, or other distinguishing feature on the product presents himself as its producer. More precisely, a battery producer will indicate on its battery or in the user’s manual that the battery cannot be used in any other application than the appliance it was placed on the market with.
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This applies evenly to lithium batteries for digital cameras, cordless power tools, lawnmowers, or electric vehicles.
11B.6.4 EPR AND WASTE DIRECTIVES Within the context of the Waste Directives such as WEEE (2012/19/EC), Batteries (2006/66/EC) and ELV (2000/53/EC) Directives, Member States shall ensure that producers set up schemes for the collection and recycling of WEEE, batteries and accumulators and vehicles. EPR is based upon the principle that producers have the greatest control over product design and marketing and that these same companies have the greatest ability and responsibility to reduce waste and improve resource efficiency. EPR may take the form of a reuse, take-back, or recycling program. To encourage manufacturers to design environmentally friendly-conscious products the EPR is holding producers responsible for the costs of managing their products at end of life. The producer may also choose to delegate this responsibility to a third party, a so-called producer responsibility organization (PRO), which is paid by the producer for the management of its own products at end of life. In this way, the producer secures its responsibility for waste management by a third party while fulfilling its obligations versus the local (national) authority. The EPR principle shifts the responsibility for waste management from government to private industry, requesting producers, importers, and/or sellers to internalize waste management costs in their product prices and ensuring the safe management of their products at end of life. The link between EPR and the Batteries Directive 2006/66/EC can be found in the definition of “producer” in Article 3. y12.: “any person in a Member State that, irrespective of the selling technique used, including by means of distance communication. . .places batteries, including those incorporated into appliances or vehicles, on the market for the first time within the territory of that Member State on a professional basis.” The Article 3 y 14 defining the “placing on the market,” is complementary to the definition of the “battery producer.” Two cases are detailed below and illustrated in Fig. 11B.16. Case 1. In the case where the battery is reused (after refurbishment or remanufacturing) for its initial purpose, the producer is still controlling the placing on the market of the battery and the waste management flow of the battery (Case 1). Case 2. In the case where the battery is placed on the market for the second use by the producer (who first placed the battery on the market), this producer will keep the responsibility of the battery offered for the second use (Case 2a). This scenario does not create any concern as the “first producer” will keep the responsibility of the battery through its second use and its end of life. There will be cases where the “second use” will request a transfer of ownership of the battery and a second placing on the market (Case 2b). It is also anticipated that the “second use” will not be known by the first producer. Therefore, the possibility to have a battery offered for a second use is opening the question of the responsibilities of the “second” producer which are not defined in the Batteries Directive. In the case where the battery is offered for a second use by a third party for another application than for which the battery was designed initially (and put on the market for the 1st time), this new
11B.7 CONCLUSIONS
501
Producer 1
Case 1
Case 2 Case 2A POM 1
POM 1
Reuse as USE 1
USE 1
USE 1
(Includes 2nd hand)
EOL
Case 2B
Producer 1
Producer 2
2nd POM
2nd POM
2nd USE
2nd USE
EOL
EOL
(Producer 1)
(Producer 2)
(Producer 1)
Covered by the batteries directive
Not covered by any waste legislation
FIGURE 11B.16 Application of the EPR principle for lithium batteries according to the reuse or second use options.
commercial actor becomes a (second) producer and should take responsibility for the end of life management of the battery. Indeed, the new commercial actor is acting as a second producer placing the battery on the market for a second time. The responsibilities of this operation are not covered by the current definitions of Article 3 y 12 and y 14 of the Batteries Directive.
11B.7 CONCLUSIONS As a result of the development of new batteries technologies opening the road to a wider range of applications and the possibility offered to use a battery in multiple applications during its service life, several additional technical and regulatory issues are raised by the multiple/sequential transfer of ownership and the possibility to use the battery for a different application than the one offered during the first placing on the market. The fact that a second producer is now possible in the value chain of the battery service life requires the development of the legislation to cover their responsibilities. Indeed the battery design must probably be adapted to the new application, including the battery management system. The performances of the batteries and the associated warranty will also be
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CHAPTER 11 LI-SECONDARY BATTERY: SPECIAL RISKS
adapted. In addition, the UN Model Regulation for the transport of Dangerous Goods applies to lithium batteries. For safety reasons, it requires specific testing requirements in accordance with defined design and technical specifications. This needs to be performed on the new design before the second use of the battery. For reuse, the conditions for EPR of the first producer can be respected. For second use, the conditions for EPR could potentially not be respected because they may be out of control of the initial producer who has placed the battery on the market for the first time. The duties of the EPR for batteries extend to the registration as a producer, reporting of quantities of batteries placed on the market for portable batteries, marking requirements, participation to collection schemes for portable batteries and automotive batteries, as well as take back obligations for industrial batteries. All these requirements should apply to the “second” producer. RECHARGE proposes to define minimum requirements to evaluate the possibility to reuse or to allow a second use of lithium batteries. The most critical factor is to maintain the EPR and the transfer of ownership under a legal framework. These minimum requirements are illustrated in Table 11B.4 below [47]. When the proposed minimum requirements in the table are fulfilled, RECHARGE supports the reuse of rechargeable batteries for their original applications. This requires that quality, performances, and safety standards are observed before placing the lithium battery for a second time on the market. In the presence of legal uncertainties, RECHARGE is not supporting the second use of lithium batteries except when the battery remains under the responsibility of the first producer acting as the legal entity placing the battery on the market for this second use. In the absence of a legal basis and clear minimum requirements, RECHARGE does not support the second use of lithium batteries, when there is a transfer of ownership and a new commercial entity placing the battery for a second time on the market. Indeed, currently, there are too many unknown factors that could impact a product’s reliability and end users’ safety in a nonregulated second use. More precise regulation is needed for a clear application of the EPR, more precise description in case of second use of batteries: the conditions of transfer of the EPR to the “second placing on the market” should be regulated. This is necessary for a level playing field to be developed in the “second life” market. This is critical for the traceability at end of life. This issue has not yet received detailed attention in order to define the boundaries of its implementation. In the case of second use, there is an urgent need to develop an appropriate legal basis to define the EPR and avoid unfair business. Reuse is a practice that can be encouraged, as long as it proposed under professional conditions (see Table 11B.4). Under regulated conditions, the development of a sustainable business in the field of second use of batteries could be a promising objective, allowing for an extended use of batteries for the benefit of all actors of the value chain of a lithium battery.
ACKNOWLEDGMENTS The author is thankful to his colleagues within RECHARGE, Mr. Claude Chanson and Mr. Willy Tomboy for supporting the preparation of this Chapter.
REFERENCES
503
ABBREVIATIONS The European Agreement concerning the International Carriage of Dangerous Goods by Road (Latest Edition 2015) B2B Business to Business C2B Consumer to Business CTIF International Association of Fire and Rescue Services - Comit´e Technique International de Pr´evention and Extinction du Feu DHL Express Delivery Services & International Shipping DOT Department of Transport (USA) EOL End Of Life (or End Of Service Life) EPR Extended Producer Responsibility Principle EU European Union EUCOBAT European Association of National Collection Schemes for Batteries EV Full Electric Vehicle GDV German Insurance Association GRS Battery Collection and Recycling Foundation (Germany) Stiftung Gemeinsames Ru¨cknahmesystem Batterien (GRS Batterien) HEV Hybrid Electric Vehicle IATA International Air Transport Association ICAO International Civil Aviation Organization IMDG International Martitime Dangerous Goods Code NFPA National Fire Protection Agency (USA) PHEV Plug-In Hybrid Electric Vehicle PHMSA Pipeline and Hazardous Materials Safety Agency PRBA The Rechargeable Batteries Association PRO Producer Responsibility Organization RECHARGE The Advanced Rechargeable and Lithium Batteries Association RSA Redox Shuttle Additive SP Special Provisions (UN Model regulations Dangerous Goods Transport) UN United Nations UPS United Parcel Service USABC United States Advanced Battery Consortium WEEE Waste Electrical and Electronic Equipment WLB Waste Lithium Batteries ADR
REFERENCES ,http://www.call2recycle.ca/contact-us/.. ,http://www.baj.or.jp/e/recycle/recycle05.html.. ,http://www.batteryrecycling.org.au/home.. ,http://ec.europa.eu/environment/waste/batteries/legislation.html.. ,http://ec.europa.eu/environment/waste/framework/.. ,http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri 5 CONSLEG:2000D0532:20020101:EN:PDF.. ,http://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri 5 CELEX:02000L005320130611&qid 5 1405610569066&from 5 EN.. [8] ,http://eur-lex.europa.eu/legal-content/EN/TXT/?uri 5 celex%3A32012L0019..
[1] [2] [3] [4] [5] [6] [7]
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CHAPTER 11 LI-SECONDARY BATTERY: SPECIAL RISKS
[9] BASEL CONVENTION : ,http://www.basel.int/TheConvention/Overview/tabid/1271/Default.aspx.. [10] UN Model Regulation. Recommendations for the Transport of Dangerous Goods 19th Revised Edition. ,http://www.unece.org/index.php?id 5 40533&L 5 0.. [11] UN Model Regulation ,http://www.unece.org/index.php?id 5 40533&L 5 0.. [12] ADR ,http://www.unece.org/index.php?id 5 36678&L 5 0.. [13] ,https://en.wikipedia.org/wiki/International_Maritime_Dangerous_Goods_Code.. [14] IATA ,http://www.iata.org/whatwedo/cargo/dgr/Pages/lithium-batteries.aspx.. [15] Waste Catalogue : ,http://ec.europa.eu/environment/waste/framework/list.htm.. [16] ,http://www.hyperedizioni.com/sezioni/213/the-lithium-batteries.. [17] ,http://www.labelmaster.com/lithium-battery-shipping.. [18] ,http://www.rechargebatteries.org/wp-content/uploads/2013/07/Li-ion-safety-July-9-2013-Recharge-. pdf.. [19] ,http://phmsa.dot.gov/pv_obj_cache/pv_obj_id_7410989F4294AE44A2EBF6A80ADB640BCA8E4200/ filename/ERG2012.pdf.. [20] ,http://www.thecompliancecenter.com/publications/erg.htm.. [21] ,http://www.rechargebatteries.org/wp-content/uploads/2013/04/Li_Ion-BIF_EN-May-2013-PART-1-2-34.pdf.. [22] ,http://www.rechargebatteries.org/wp-content/uploads/2015/01/RESCUE-AND-TRAINING-MANUALLITHIUM-BATTERY-IN-STORAGE-2014-12-05.pdf.. [23] ,http://www.call2recycle.org/safety-tips/.. [24] ,http://www.batteryrecycling.org.au/home.. [25] Hazard Assessment of Lithium Ion Energy Storage Systems. Fire Protection Research Foundation February 2016. ,www.nfpa.org/foundation.. [26] Investigation on the fire-induced hazards of Lithium-ion battery cells by fire calorimetry, INERIS. G. Gachot, P. Ribie`re and al. Anal. Chem., 2011, 83 (2), 478 485. [27] P. Ribie`re, S. Grugeon, et al., Energy Environ. Sci. 5 (2012) 5271. [28] ,https://www.ups.com/media/news/fr/ca/intl_lithium_battery_regulations.pdf.. [29] ,http://www.dhl.com/en/express/shipping/shipping_advice/lithium_batteries.html.. [30] Deutschen Insurance Association (GDVl) ,http://www.gdv.de/tag/lithium-batterien/. and ,http:// www.gdv.de/2015/12/lagerung-und-bereitstellung-von-lithium-batterien-aktualisierung/.. [31] Personal communication. Mr Kurt Volmacher: [email protected] ISO 17840 Road vehicles Information for first and second responders. [32] ,http://www.eucobat.eu/system/files/Eucobat%20-%20Safety%20Advisory%20Notes%20v4.1.pdf.. [33] ,http://www.grs-batterien.com/fileadmin/user_upload/Download/Batteriebriefe/GRS-Batteriebrief_EN. pdf.. [34] F.-A. Polonius, S. Spiez, Bescha¨digte lithium batterien in der automobile industrieFachkonferenz Lithium Batterien - Frankfurt/Main, SpringerVerlag, 2016GefahrGut. Available from: www.gefarhtgutonline.de/lithium2016. [35] file:///C: /Users/jpwiaux/Downloads/DisassemblyRP_USABC_2013_finalr1%20(2).pdf. [36] ,http://www.battcon.com/PapersFinal2014/1%20McDowall%20Paper%202014%20Final.pdf.. [37] Accurec Recycling GmbH, D-45472 Mu¨lheim am der Ruhr, Germany. Dr R. Weyhe and al. ,www. accurec.de.. [38] M. Wachtler, B. Emmermacher, M. Wohlfahrt-Mehrens, H. Do¨ring PD-18 Safe Discharge of Damaged Li-Ion Batteries, Battery Conference 2015, Aachen, April 27 29, 2015. [39] Safe Discharge of Damaged Li-Ion Batteries. M. Wachtler and al. ZSW Zentrum fu¨r Sonnenenergie und Wasserstoff-Forschung Helmholtzstrasse, 8 89081 Ulm. Germany. E-Mail. ,[email protected]..
REFERENCES
505
[40] ,http://www.midtronics.com/shop/products-1/battery-chargers-and-maintenance-products/diagnosticchargers/gr-series/grx-5100.. [41] Personal communication. Mrs A. Arnberger : [email protected].. [42] ,http://www.toxcommc.com/toxco.html.. [43] ,http://www.rechargebatteries.org/wp-content/uploads/2014/04/RECHARGE-Information-Paper-on-Reuse-and-second-use-October-2014-v.14.pdf.. [44] ,http://europa.eu/rapid/press-release_IP-15-6203_en.htm.. [45] ,http://www.unece.org/fileadmin/DAM/trans/doc/2014/wp29/ECE-TRANS-WP29-2014-81e.pdf.. [46] Extracted from REF. (43) PART I. [47] Extracted from REF. (43) PART II - ANNEXES.
LI-SECONDARY BATTERY: SPECIAL RISKS
11
CHAPTER OUTLINE 11A A Specific Risks During Transport and Storage ............................................................................. 456 11A.1 Transport ............................................................................................................... 456 11A.1.1 Introduction ..................................................................................................... 456 11A.1.2 Dangerous Goods............................................................................................. 458 11A.1.3 UN Lithium Battery Testing Requirements......................................................... 460 11A.1.4 Safe Shipping of Lithium Batteries .................................................................... 461 11A.1.5 Approvals for Special Shipping of Lithium Batteries ........................................... 467 11A.1.6 Lithium Batteries Permitted for Passengers in Aircraft ....................................... 468 11A.2 Storage (Written Only by J. Garche).......................................................................... 469 Abbreviations .................................................................................................................... 470 References ....................................................................................................................... 471 11B Specific Risks of Lithium Batteries at End of Life .......................................................................... 472 11B.1 Introduction........................................................................................................... 472 11B.1.1 The Nature of Incidents.................................................................................... 474 11B.1.2 The Approach .................................................................................................. 476 11B.1.3 Battery Aging ................................................................................................... 477 11B.2 Legislative and Regulatory Framework ...................................................................... 477 11B.2.1 The EU Waste Framework Directive and the Daughter Directives on Waste......................................................................................... 478 11B.2.2 The Waste Framework Directive....................................................................... 478 11B.2.3 The End of Life Vehicle Directive ..................................................................... 479 11B.2.4 The Waste Electrical and Electronic Equipment Directive.................................. 479 11B.2.5 The Batteries Directive .................................................................................... 479 11B.2.6 The Basel Convention ..................................................................................... 480 11B.2.7 The International Transport Regulation............................................................. 481 11.B.2.8 Note to the Reader: Hazardous Waste and Dangerous Goods........................... 481 11B.3 Transport of Lithium Batteries for Disposal or Recycling ............................................ 481 11B.3.1 Special Provisions SP377 and SP636 (B) (ADR) for Lithium Batteries Transported for Disposal or Recycling................................................. 482 11B.3.2 Special Provision SP376 for the Transport of Damaged and Defective Lithium Batteries............................................................................... 484 11B.4 Communication Tools as Preventive Measures........................................................... 486 11B.4.1 The Prevention and Response to Incidents ....................................................... 486 11B.4.2 Results of Tests................................................................................................ 487 11B.4.3 Recalled Batteries ............................................................................................ 487 11B.4.4 Recommendations for the Safe Storage of Waste Lithium Batteries.................... 488 Electrochemical Power Sources: Fundamentals, Systems, and Applications. DOI: https://doi.org/10.1016/B978-0-444-63777-2.00011-6 © 2019 Elsevier B.V. All rights reserved.
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11B.4.5 Fire Fighting First Responders .......................................................................... 488 11B.4.6 Waste Batteries Collection Organization ............................................................ 488 11B.4.7 The Traffic Light Approach ............................................................................... 489 11B.5 Electrical Hazard Control: Technical Solutions .......................................................... 490 11B.5.1 Electrical Hazard.............................................................................................. 491 11B.5.2 Deactivation ..................................................................................................... 492 11B.5.3 UN Transport Regulation .................................................................................. 493 11B.5.4 Use of Cushioning Material in Packaging and Storage ....................................... 493 11B.5.5 Wet Deactivation Via “Immersion” .................................................................... 494 11B.5.6 The Redox Shuttle Approach ............................................................................ 495 11B.5.7 Deactivation Through a Controlled Load............................................................ 495 11B.5.8 Other Means to Deactivate a Battery................................................................. 495 11B.6 Reuse and Second Use ........................................................................................... 496 11B.6.1 Definitions........................................................................................................ 498 11B.6.2 The Extended Producer Responsibility (EPR) .................................................... 499 11B.6.3 EPR and Directives on New Products ............................................................... 499 11B.6.4 EPR and Waste Directives ................................................................................ 500 11B.7 Conclusions ........................................................................................................... 501 Acknowledgments.............................................................................................................. 502 Abbreviations .................................................................................................................... 503 References ....................................................................................................................... 503
SUBCHAPTER
11A
A SPECIFIC RISKS DURING TRANSPORT AND STORAGE
George A. Kerchner1 and Ju¨rgen Garche2 1
PRBA-The Rechargeable Battery Association, Washington, DC, United States 2FCBAT, Ulm, Germany
11A.1 TRANSPORT 11A.1.1 INTRODUCTION Billions of lithium-ion and lithium-metal cells and batteries are manufactured annually by different manufacturers all over the world. The overwhelming part of the cell production takes place in Asia and from there cells and batteries are packaged and shipped globally by all modes of transport. The safe transport of lithium-ion and lithium-metal cells and batteries (referred to herein as “lithium batteries”) is critical because the batteries have a very high energy content and the possible presence of a flammable electrolyte and/or metallic lithium. Therefore, lithium batteries are classified and regulated as “dangerous goods”. Their safe transport is governed by a number international and national dangerous goods regulations depending on the mode of transport used to ship or transport the batteries.
11A.1 TRANSPORT
Transport mode:
All Modes
Air
Sea
Opinion forming:
Subcommittee
DGP
DSC
Decisions:
Committee
Council
MSC
ECOSOC Geneva
ICAO Montreal
IMO London
UN
Road, Europe
WP 15
IAEA Vienna
ECE Geneva
Rail, Europe
RID Committee
OTIF Bern
IATA
NGO International:
Radioactive Material
457
Model Regulations, Manual of Tests and Criteria
TI
DGR
IMDG Code
ADR
RID
FIGURE 11A.1 International organizations responsible for dangerous goods transportation. Reproduced from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1].
Air: ICAO IATA Sea: IMO
Road (Europe) ECE (or UNECE) Rail (Europe) OTIF
—International Civil Aviation Organization with DGP—Dangerous Goods Panel and TI—Technical Instructions —International Air Transport Association with DGR—Dangerous Goods Regulations —International Maritime Organization with DSC—Sub-Committee on Dangerous Goods, Solid Cargoes and Containers and MSC—Maritime Safety Committee and IMDG—International Maritime Dangerous Goods Code. —United Nations Economic Commission for Europe with ADR—European Agreement concerning the International Carriage of Dangerous Goods by Road —Intergovernmental Organization for International Carriage by Rail with RID—Regulations Concerning the International Carriage of Dangerous Goods by Rail
The United Nations established a system for the classification, packaging, marking, and labeling of dangerous goods in general. The United Nations Recommendations on the Transport of Dangerous Goods Model Regulations and the United Nations Manual of Tests and Criteria provide a basis for development of these harmonized regulations for all modes of transport. This harmonization of regulations facilitates trade and the safe, efficient transport of all dangerous goods, including lithium batteries. The UN Model Regulations, which were first published in 1957, establishes minimum requirements applicable to the transport of dangerous goods. The UN Model Regulations established by ECOSOC (United Nations Economic and Social Council) are valid for all transport modes and incorporated into special dangerous goods regulations by international organizations for transport in air, sea, road, and rail (see Fig. 11A.1).
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The air transport regulations for lithium batteries have become particularly complex and are more stringent than the regulations for sea, road, or rail transport. Each set of regulations include requirements for how dangerous goods must be packaged, labeled and transported. These regulations are updated on a 2-year cycle. Over the course of the last 25 years, the lithium battery dangerous goods regulations in the UN Model Regulations, ICAO Technical Instructions, and IATA Dangerous Goods Regulations have undergone tremendous change, which has resulted in a complex set of regulatory requirements that are very difficult to understand even for the most experienced dangerous goods experts. In addition, the regulations will continue to evolve and likely change every 2 years as new issues arise and battery technology changes. Meetings of UN working groups on amending the lithium battery tests in the UN Manual also are frequently held in order to accommodate new battery technologies and the ongoing lessons learned from testing lithium batteries. Non-governmental organizations like PRBA The Rechargeable Battery Association and RECHARGE The Advanced Rechargeable & Lithium Batteries Association have been instrumental in helping to update the UN38.3 tests and lithium battery dangerous goods regulations over the past 20 years. This present chapter addresses the requirements for the safe transport of lithium batteries and the applicable dangerous goods regulations.
11A.1.2 DANGEROUS GOODS “Dangerous goods” (also referred to as “hazardous materials” in the United States) are substances (including mixtures) and articles presenting a potential hazard to human health and safety, infrastructure, and/or their means of transport and property. UN Model Regulations cover principles of classification and definition of classes, listing of the principal dangerous goods, general packaging requirements, testing procedures, marking, labeling, placarding, and transport documents. There are, in addition, special requirements related to particular classes of dangerous goods. With this harmonized system of classification, listing, packaging marking, labeling, placarding, and documentation in general use, carriers, consignors, and inspecting authorities benefit from a harmonized regulatory system governing the transport of dangerous goods.
11A.1.2.1 Dangerous goods classification The dangerous goods subject to the regulations given in the introduction are assigned to one of the nine classes listed below with their label according to the hazard or the most predominant of the hazards they present in transport. Some of these classes are subdivided into divisions (Figs. 11A.2 11A.4). Electrochemical power sources relevant in in Class 9 include: • • • • •
Lithium-ion batteries Lithium-metal batteries Battery powered equipment Battery powered vehicles Fuel cell engines Therefore, lithium batteries in general are regulated as Class 9 Miscellaneous Dangerous Goods.
FIGURE 11A.2 Labeling of dangerous goods related to UN [2].
FIGURE 11A.3 Class 9 hazard label: Miscellaneous Dangerous Goods—left old, right new. Adapted from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1].
FIGURE 11A.4 Hazardous material shipping label: Cargo Aircraft Only. Reproduced from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1]
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11A.1.2.2 UN numbers and proper shipping names of dangerous goods The different dangerous goods listed in the regulations have a specific identification number or “UN number” (ranging from UN0001 to about UN3600) and “proper shipping name” associated with it. The following UN numbers and proper shipping names apply to lithium batteries: UN3480—Lithium-ion batteries UN3481—Lithium-ion batteries contained in equipment UN3481—Lithium-ion batteries packed with equipment UN3090—Lithium-metal batteries UN3091—Lithium-metal batteries contained in equipment UN3091—Lithium-metal batteries packed with equipment
11A.1.3 UN LITHIUM BATTERY TESTING REQUIREMENTS In general, lithium batteries are subject to a series of tests found in the United Nations Manual of Tests and Criteria. This manual contains test methods and procedures to be used for the classification of dangerous according to the provisions of the UN Model Regulations. In Part III, subsection 38.3, a series of eight lithium cell and battery tests are listed. These tests are often referred to as the “UN 38.3” lithium battery tests. These tests are listed below and may be conducted by cell and battery manufacturers or a third-party test lab. Currently (6/2017), the 6th revised edition (2015) is in effect [3]. The following tests are required for primary and secondary cells and/or batteries with the exception of Test T7—Overcharge, which applies only to secondary batteries. T1—Altitude Simulation (Primary and Secondary Cells and Batteries) Assesses the influence of low pressure (#11.6 kPa for $ 6 h) on cells/batteries during transport. T2—Thermal Test (Primary and Secondary Cells and Batteries) Assesses the influence of rapid (30 min) and extreme (40 C 3 70 C) temperature variations on cells/batteries during transport. T3—Vibration (Primary and Secondary Cells and Batteries) Assesses the effect of vibration during transport (varying amplitudes 7 Hz 3 200 Hz) on cells/batteries. T4—Shock (Primary and Secondary Cells and Batteries) Assesses the effect of possible impact (half-sine shock, peak acceleration 150 gn, pulse duration 6 ms; for larger cell/batteries: 50 gn, 11 ms with a sliding scale depending on the mass of the battery) during transport to cells/batteries. T5—External Short Circuit (Primary and Secondary Cells and Batteries) Assesses the effect of an external short circuit (#0.1 Ω, 55 C) during transport to cells/batteries. T6—Impact, Crush (Primary and Secondary Cells) Impact: Assesses the effect of an impact (mass of 9.1 kg dropped from 61 cm on a steel bar l 5 6 cm, Ø 15.8 mm, which is located on a sample) on cells during transport.
11A.1 TRANSPORT
461
Crush: Assesses the effect of a crush (cell between two flat surfaces, speed: 1.5 cm s21 up to applied force of 13 kN or a voltage drop of $ 100 mV or deformed by 50%) on cells not more than 20 mm in diameter during transport. T7—Overcharge (Secondary Batteries) Assesses the effect of overcharge (Ioverch52 3 manufacturer’s recommended continuous Ich for 24 h) on batteries. T8—Forced Discharge (Primary and Secondary Cells) Assesses the effect of forced discharge (discharged for a time interval, h, equal to its rated capacity, Ah, divided by the initial test current, A) on cells. These tests are also adopted by other transport organizations such as IATA (DGR— Section 3.9.2.6) and IMO (IMDG Code—Section 2.9.4). There is only one exception where lithium cells and batteries are not required to be tested in accordance with UN 38.3 as a prerequisite for transport. This exception applies to preproduction prototype lithium cells and batteries if these samples are transported for testing, or low production runs (i.e., a production run consisting of no more than 100 lithium cells and batteries per year). Once the cells and batteries pass the UN tests, retesting is not required unless there is a change in the cell or battery design type as noted in section 38.3.2.2 of the UN Manual. Technical changes that may be considered to a previously tested cell or battery type are listed in Section 38.3.2.2 and include mass change ( . 0.1 g or .20%), energy change (20%), voltage change ( . 20%), change of chemical cell material change, change of protective devices, including hardware and software, change of safety design (e.g., vent), change of cell numbers in a battery, change of cell connecting mode in a battery, and to mass change in relation.
11A.1.4 SAFE SHIPPING OF LITHIUM BATTERIES 11A.1.4.1 Fully-regulated dangerous goods shipping If a lithium battery does not qualify for any of the “exceptions” in the regulations, a shipper must offer the package of lithium batteries as “fully-regulated” dangerous goods. This means the package must carry a specific diamond-shaped label to indicate the hazard associated with the package and certain markings required by the regulations. For lithium batteries, this means a Class 9 label as in Fig. 11A.3 (left). A new Class 9 label especially for lithium cells and batteries in Fig. 11A.3 (right) was incorporated into the dangerous goods regulations in 2017 and will be required on packages of fully-regulated shipments of lithium batteries starting on January 1, 2019. However, the new label may be used by shippers of lithium batteries starting on January 1, 2017. The air transport regulations applicable to lithium batteries that are found in the ICAO Technical Instructions and IATA Dangerous Goods Regulations have become increasingly complex and more stringent. For example, ICAO now prohibits the transport of lithium batteries as cargo on passenger aircraft. This prohibition means shippers are required to place the Cargo Aircraft Only label shown in Fig. 11A.4 on their packages of lithium batteries. The label is not only required for fully-regulated shipments by air but also for shipments offered under the exceptions to the regulations. In addition, lithium-ion cells and batteries (UN 3480) may not exceed 30% state of charge (SOC) of the nominal capacity when shipped by air. (For the influence of SOC on a thermal runaway event, see e.g., Chapter 12C: Ignition and Extinction of Battery Fires.)
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Lithium-ion cells and batteries at a SOC greater than 30% can be shipped by air but only with the approval of the State of Origin and the State of the Operator under the written conditions established by those authorities, see Special Provision A331 of the ICAO TI and IATA DGR The 30% SOC limit does not apply to lithium ion cells and batteries packed with or contained in equipment (UN 3481). Shippers who want to take advantage of any exceptions in the regulations for air transport are limited to placing no more than two batteries or eight cells in a single package. And, these excepted packages may not be consolidated (i.e., overpacked) together. The air transport requirements for lithium batteries (UN 3480, UN 3481, UN 3090, UN 3091) are also often dependent on an airline’s specific acceptance policy (also known as “operator variations”). A good overview about the policies of a specific airline is given in [4]. The Interline (or Interchange) Message Procedure-Code (IMP Code) of IATA for shipping fully regulated lithium cells and batteries is for lithium ion batteries: Restricted Lithium-ion—Cargo (RLI); and for lithium metal batteries: Restricted Lithium-metal—Cargo (RLM). Due to the complexity of the lithium battery dangerous goods regulations and the risks associated with these batteries in transport, reputable companies that are in the business of manufacturing, shipping, or transporting lithium batteries have adopted very comprehensive training programs for their dangerous goods employees in accordance with the regulations. The regulations generally require dangerous goods training every 2 years. Any employee who prepares or transports lithium batteries should be trained to ensure they fully understand the hazards associated with lithium batteries and the importance of complying with the testing, packaging, marking, labeling, and documentation requirements in the dangerous goods regulations. These training programs are one of the keys to ensuring the safe transport of lithium batteries. A further important prerequisite for safe shipping is a high safety standard by the manufacturer of the cells and batteries which will have a significant impact on compliance with the UN 38.3 tests. Therefore, all of the dangerous goods regulations require that manufacturers of lithium batteries follow a quality management program that addresses, e.g., quality control, quality assurance, and process operation instructions [5].
11A.1.4.2 Exceptions from fully-regulated dangerous goods shipping The UN Model Regulations, IMDG Code, and European ADR and RID contain a Special Provision 188 that provides an “exception” from the regulations for smaller lithium cells and batteries, which means they are not offered for transport as fully-regulated dangerous goods. The most important point of the exceptions is related to the energy of cells or batteries given in Watt hours (Wh) for lithium-ion and lithium metal content given in gramm for lithium-metal cells/batteries. These Wh and lithium metal content limits enable most consumer-type products with lithium cells and batteries to be shipped under the exceptions and thus under a less onerous regulatory scheme than larger lithium batteries used in industrial applications such as hybrid-electric and electric vehicles. While excepted cells and batteries are provided some relief from the regulations, they generally require some type of hazard mark or label on packages to indicate the presence of the lithium batteries. A new lithium battery mark was incorporated into the dangerous goods regulations in 2017 and will be required on most packages of excepted lithium batteries starting on January 1, 2019. However, the new mark may be used by shippers of lithium batteries starting on January 1, 2017.
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FIGURE 11A.5 Lithium Battery Mark— indicates a place for the applicable UN number (UN 3090, UN 3091, UN 3480 or UN 3481), for phone number. Reproduced from H. Huo, Y. Xing, M. Pecht, B. J. Zu¨ger, N. Khare, A. Vezzini, Energies 2017, 10, 793 [1].
As mentioned in the legend of Fig. 11A.5 this mark requires the entry at “ ” of the applicable UN number (UN 3090, UN 3091, UN 3480 or UN 3481) and at “ ” of the phone number of the responsible shipper or an emergency response company or organization. This new lithium battery mark also will appear in the IMDG Code, ICAO Technical Instructions, IATA Dangerous Goods Regulations, and European ADR and RID. This harmonized approach to marking packages containing excepted lithium batteries will help to facilitate the safe transport of lithium batteries and products packed with them. The Interline (or Interchange) Message Procedure-Code (IMP Code) of IATA shipping excepted lithium cells and batteries is for Li-ion batteries Excepted Lithium-ion—Cargo (ELI); and for Li-metal batteries Excepted Lithium-metal—Cargo (ELM). The dangerous goods regulations that govern shipments of excepted lithium cells and batteries generally do not require employees to be trained in accordance with the regulations. However, for air transport, these employees must receive “adequate instructions” commensurate with their responsibilities.
11A.1.4.3 Packaging requirements Shipments of lithium cells and batteries must comply with very stringent packaging requirements found in all of the dangerous goods regulations. Logically, the air transport regulations in the ICAO Technical Instructions and IATA Dangerous Goods Regulations contain the most restrictive and stringent packaging requirements based on the quantity or net mass of the batteries per package. Under the UN Model Regulations, most packaging must meet or exceed minimum standards of performance before it can be authorized for transporting dangerous goods. Package performance is established by subjecting packaging to the tests described in Chapter 6.1 of the UN Model Regulations. These tests include, but are not limited to, drop, leak proofness, internal pressure, and stacking. If a package design passes the tests, all subsequent packages manufactured to the same specification are marked accordingly to indicate they comply with the applicable tests (Table 11A.1).
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Table 11A.1 Limited Energy Level and Lithium Metal Content for Excepted Li-Ion and Li-Metal Cells and Batteries-related to IATA-DGR [3a] Proper Shipping Name
Limited Energy Level and Lithium Metal Content Per Unit
Lithium-Ion Cells Lithium-Ion Batteries Lithium-Metal Cells Lithium-Metal Batteries
# 20 Wh # 100 Wh # 1 g Li # 2 g Li
Table 11A.2 UN Number, Proper Shipping Name, Packaging Instruction (PI), Energy Limitations of Cells/Batteries, Net Weight and Numerical Limitations Per Packages, Relevant Sections, Subsections, and IMP Codes (related to IATA-DGR [3])
UN Number
Proper Shipping Name
UN3480
Lithium-ion batteries
PI 965
Energy or Li Metal Cont. Limitations, Cell/Battery Section I IMP: RLI
Energy or Li Metal Cont. Limitations, Cell/Battery Section II IMP: ELI
Section IA: C: .20 Wh
C: # 20 Wh B: # 100 Wh
B: .100 Wh
Section IB: C: # 20 Wh
UN3481
Lithium-ion batteries packed with equipment
966
B: # 100 Wh C: .20 Wh
C: # 20 Wh
UN3481
Lithium-ion batteries contained in equipment
967
B: .100 Wh C: .20 Wh
B: # 100 Wh C: # 20 Wh
B: .100 Wh
B: # 100 Wh
Net Weight Limitations, Package Section I IMP: RLI
Energy or Li Metal Content and Numerical Limit., Package Section II IMP: ELI
Section IA: PAX A/C: forb. CAO: 35 kg
Only 1 package, package limits: • # 2.7 Wh/cell 5 max. 2.5 kg • 2.7 Wh— # 20 Wh/ cell 5 max. 8 cells • . 2.7 Wh— # 100 Wh/batt 5 max 2 batt. PAX A/C: forb.
Section IB: PAX A/C: forb. CAO: 10 kg PAX A/C: 5 kg. CAO: 35 kg PAX A/C: 5 kg. CAO: 35 kg
PAX A/C: 5 kg CAO: 5 kg PAX A/C: 5 kg CAO: 5 kg
11A.1 TRANSPORT
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Table 11A.2 UN Number, Proper Shipping Name, Packaging Instruction (PI), Energy Limitations of Cells/Batteries, Net Weight and Numerical Limitations Per Packages, Relevant Sections, Subsections, and IMP Codes (related to IATA-DGR [3]) Continued
UN Number
Proper Shipping Name
UN3090
Lithium-metal batteries
PI 968
Energy or Li Metal Cont. Limitations, Cell/Battery Section I IMP: RLI
Energy or Li Metal Cont. Limitations, Cell/Battery Section II IMP: ELI
Section IA: C: .1 g Li
C: # 1 g Li B: # 2 g Li
B: .2 g Li
Section IB: C: # 1 g Li
UN3091
Lithium-metal batteries packed with equipment
969
B: # 2 g Li C: .1 g Li
C: # 1 g Li
UN3091
Lithium-metal batteries contained in equipment
970
B: .2 g Li C: .1 g Li
B: # 2 g Li C: # 1 g Li
B: .2 g Li
B: # 2 g Li
Net Weight Limitations, Package Section I IMP: RLI
Energy or Li Metal Content and Numerical Limit., Package Section II IMP: ELI
Section IA: PAX A/C: forb. CAO: 35 kg
Only 1 package, package limits: 2 0.3 g Li/ cell 5 max. 2.5 kg 2 0.3 g # 1 g Li/ cell 5 max. 8 cells 2 . 0.3 # 2 g Li/ batt 5 max 2 batteries PAX A/C: forb.
Section IB: PAX A/C: forb. CAO: 2.5 kg PAX A/C: 5 kg. CAO: 35 kg PAX A/C: 5 kg. CAO: 35 kg
PAX A/C: 5 kg. CAO: 5 kg PAX A/C: 5 kg. CAO: 5 kg
Adapted from H. Huo, Y. Xing, M. Pecht, B.J. Zu¨ger, N. Khare, A. Vezzini, Energies 10 (2017) 793 [1].
For each of the lithium battery entries there is a specific packaging instruction (PI) in the IATA DGR (see Table 11A.2). Table 11A.2 gives an overview of the relevant air shipping parameter related to IATA DGR. All shipments in Section I also must be accompanied by a Shipper’s Declaration for Dangerous Goods (DGD) [6]. In addition to the requirements shown in Table 11A.2, shipping regulations published by IATA and ICAO, the flow charts in Fig. 11A.6 (Li-ion) and Fig. 11A.7 (Li-metal) provide guidance for shipping excepted and fully-regulated lithium cells/batteries by air.
FIGURE 11A.6 Requirements for shipping lithium-ion cells/batteries by air based on the IATA DGR. Reproduced from IATA (2017) Lithium Battery Guidance Document [6].
FIGURE 11A.7 Requirements for shipping lithium-metal cells/batteries based on the IATA DGR. Reproduced from IATA (2017) Lithium Battery Guidance Document [6].
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467
As previously noted, lithium cells and batteries in the prototype state and from low production runs (#100 pcs/a) do not require testing according to UN 38.3. These cells and batteries may be shipped by ground or sea as fully-regulated Class 9 dangerous goods in Packing Group I or II packaging depending on the mode of transport used. Shipments by Cargo aircraft are possible but only if approved by the appropriate authority of the State of origin and the requirements in Packing Instruction 910 of the Supplement to the ICAO Technical Instructions are met (see Special Provision A55, A88). Securing air transport approvals from aviation authorities in certain countries may take as long as 6 months.
11A.1.5 APPROVALS FOR SPECIAL SHIPPING OF LITHIUM BATTERIES Often shippers of lithium batteries are unable to comply with certain provisions of the lithium battery dangerous goods regulations or, as noted above, require authorization to ship by air prototype or low production lithium batteries that have not been subject to the required UN lithium battery tests. In these cases, the dangerous goods regulations authorize a “competent authority” to issue approvals to shippers authorizing an alternative method of packaging and shipping their lithium cells/batteries. Over the years, competent authorities have issued many approvals that authorize the transport by air of lithium cells/batteries that exceed the 35 kg cargo aircraft package net mass limit or that authorize shipments of prototype or low production lithium batteries. It is quite common to exceed the upper weight limitation of 35 kg for EV and HEV lithium ion batteries. The weight of these batteries on average range from to 200 500 kg. Because most of the EV manufacturers are shipping their batteries globally, it is necessary for these manufacturers to secure multiple approvals from various countries such as the United States, China, and Germany. Other examples of special shipping are given below.
11A.1.5.1 Shipping damaged or defective lithium batteries The transport of damaged or defective lithium batteries has garnered a significant amount of regulatory attention due to the potential for an incident involving these batteries. Therefore, Special Provisions and Packing Instructions governing the transport of these batteries were incorporated into the various dangerous goods regulations in 2015, which include detailed and stringent packaging requirements. This is also valid for lithium cells and batteries installed inside equipment such as mobile phones, laptops, or tablets where the devices are subject to recall due to manufacturing defects. In all cases, the damaged or defective lithium batteries must be shipped as fully-regulated Class 9 dangerous goods and often are packaged in metal drums or expensive and customized fire-resistant packaging. The transport of damaged or defective lithium cells and batteries by air is strictly prohibited. The inability to ship damaged or defective lithium cells/batteries by air has created significant problems for manufacturers. If a cell or battery has had a thermal event, a manufacturer often wants to conduct a failure analysis as quickly as possible. However, due to the lack of authority to ship by air, conducting a failure analysis in short order is impossible.
11A.1.5.2 Disposal and recycling of lithium batteries Also in 2015, new Special Provisions and Packing Instructions for shipping lithium cells and batteries for disposal or recycling were incorporated into the dangerous goods regulations. These new
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requirements were particularly critical to help facilitate shipments of waste lithium batteries that are being transported internationally by sea from countries that do not have lithium battery recycling facilities. Please see also in this book Chapter 11B, Specific Risks of Lithium Batteries at End of Life.
11A.1.6 LITHIUM BATTERIES PERMITTED FOR PASSENGERS IN AIRCRAFT 11A.1.6.1 Carry-on baggage checked at the gate or planeside allowed in the cabin Passengers can carry most consumer-type lithium batteries and portable electronic devices (PEDs) powered by lithium batteries for their own personal use in carry-on baggage. Spare batteries are prohibited in checked baggage. Spare lithium batteries in carry-on baggage must be protected from damage and short circuit. Battery-powered devices must be protected from damage and accidental activation and heat generation. Damaged, defective, or recalled batteries, including when in a device, must not be carried. Lithium batteries allowed in carry-on baggage include: Lithium-ion batteries: All consumer-sized lithium-ion batteries (up to max. 100 Wh) alone or in an equipment. With airline approval, devices can contain larger lithium-ion batteries (101 160 Wh), but spares of this size are limited to two batteries. Lithium-metal batteries: All consumer-sized lithium-metal batteries up to maximum of 2 g Li/ battery alone or in equipment are authorized.
11A.1.6.2 Checked baggage includes bags checked at the gate or planeside [7] Spare (uninstalled) lithium metal and lithium ion batteries, including power banks, are prohibited in checked baggage. Except for electronic cigarettes and vaporizers, only lithium batteries installed in equipment are allowed in checked baggage. Electronic cigarettes and vaporizers are strictly prohibited in checked baggage and must be placed in carry-on baggage. The summary for batteries allowed on board passenger aircrafts is shown in Table 11A.3. Note that medical devices with up to 8 grams of lithium metal are also authorized in carry-on baggage.
Table 11A.3 Overview About Batteries Permitted for Passengers in Aircrafts (related to IATA-DGR) Li-Ion System # 100 Wh/Batt.
Li-Metal Systems 101 160 Wh/batta
# 2 g Li/Battery
Battery Alone
Batt. in Device
Battery Alone
Batt. in Device
Battery Alone
Batt. in Device
Carry-on
Permitt.
Permitt.
Permitt.a
Permitt.
Permitt.
Checked-in
Banned
Permitt.
Max. 2 pieces Banned
Permitt.a
Banned
Permitt.
a
Only by permission of the airline. Adapted from H. Huo, Y. Xing, M. Pecht, B.J. Zu¨ger, N. Khare, A. Vezzini, Energies 10 (2017) 793 [1].
11A.2 STORAGE (WRITTEN ONLY BY J. GARCHE)
469
11A.2 STORAGE (WRITTEN ONLY BY J. GARCHE) Many transportation regulations are in principal also useable as regulations for storage of lithium ion batteries. During storage of lithium ion batteries, however, one should consider the significantly higher numbers of cells and batteries, higher total energy of the stored batteries (partially . MWh), and often long storage times. The lithium-ion cell and battery manufacturers give various instructions for storage. Thus, it is preferred to store at room temperature of about 25 C and at a state-of-charge (SOC) of about 20% 40%. It is recommended to store the cells in original packaging whose materials are related to fire relevant packaging regulations. Some manufacturers recommend checking the charge level of the battery every three months and recharging if necessary, which is, however, quite time-consuming. Particularly important is the control of cells which have just been formed, because in that post formation time micro shorts could be occurred. Typical risks in storage processes, such as electrical risk, dropping, and damage caused by mechanical influences, are normally not strong risk factors due to existing measures and established processes. The cell and battery storage rooms should be equipped with fire and temperature sensors, preferably with measurements near in the cell and battery batch. For effective risk minimization, protective concepts such as automatic fire extinguish systems, for example, sprinkler, foam, or inter gas flooding are recommended. Due to high fire loads (plastic of the components, packaging) and the high energy content of the cells/batteries, conventional sprinkler systems may be not sufficient. Sprinkler systems with water misting show considerably higher cooling capacities caused by small water drop diameters. Water is currently the recommended extinguishing agent, which, in addition to the cooling effect, also inhibits the fire by limiting the air access to the brand center. For smaller rooms, CO2 can also be used. Large volumes of extinguishing water which are contaminated with higher concentrations of electrolytes should be collected. More on fire extinction can be found in Chapter 12C, Ignition and Extinction of Battery Fires. For fire prevention, lowering the oxygen partial pressure in storage rooms is also used [7]. The combustibility of solids in an atmosphere with # 15.9% O2 and liquids with # 13% O2 can be radically reduced. The storage building construction materials must be in accordance to the relevant building codes, for example in Germany, DIN 4102—Fire behavior of building materials and building components. Of the usual fire resistance classes, at least the class F90—“fireproofed” (function maintenance over 90 minutes)—should be used. When evaluating the fire loads of cells/batteries, the packaging material which is usually first burned during thermal propagation is also to be assessed. The German Insurance Association (GDV) provides specifications for storage of cells and batteries based on the mass of lithium cells and batteries and their energy content in three categories [7]. For all classes there should be no mixed storage with other goods. •
Low energy— # 2 g Li (Li-metal) or # 100 Wh per battery (Li-ion) This includes, among others, (small) batteries and individual cells, which are mainly used in the field of computers, multimedia, small electromechanical devices, and small tools. There are no special safety requirements for the low energy class. If the cell/battery volume is .7 m3 or . six euro-pallets, however, the requirements of the medium energy class are to be considered.
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Medium energy— . 2 g Li (Li-metal), or .100 Wh per battery (Li-ion), and # 12 kg gross per battery This includes medium sized individual cells and batteries, e.g., for E-bikes, E-scooter, lightelectric vehicle, larger gardening tools, various small vehicles. Storage places for the medium energy class require a distance of .5 m to other places if they are not constructed with fireproofed materials at least of the class F90. The storage places must be fitted with a fire alarm system. If, however, the cell/battery storage area is .60 m2 and/or a storage height of .3 m is used the requirements, of the high energy class are to be considered. • High energy— . 2 g Li (Li-metal), .100 Wh per battery (Li-ion), and .12 kg gross per battery. This includes large sized cells and batteries for EVs as well as network-independent large devices. The storage places for the high energy class require also a distance of .5 m to other places if they are not constructed with fireproofed materials at least of the class F90. The GDV requirements in Germany are not “standard” in all countries. Especially the costs of fireproof construction materials as e.g., F90. are, for example, for smaller warehouses, prohibitively expensive. Two fire codes used in the United States - the International Fire Code (IFC) and NFPA 1 - have been considering substantial changes to address the storage of “used” and “off specification” lithium cells and batteries. New requirements for energy storage systems were adopted in the 2018 IFC.
•
ABBREVIATIONS Aircraft European Agreement concerning the International Carriage of Dangerous Goods by Road (ECE) Battery Management System Cargo Aircraft Only Shipper’s Declaration for Dangerous Goods Dangerous Goods Regulations (IATA) Dangerous Goods Panel (ICAO) Sub-Committee on Dangerous Goods, Solid Cargoes and Containers (IMO) United Nations Economic Commission for Europe (also UNECE) Excepted Lithium ion—Cargo IMP-Code for “small” Lithium ion batteries according to Part II of PI ELM Excepted Lithium-metal—Cargo IMP-Code for “small” Lithium-metal batteries according to Part II of PI ECOSOC United Nations Economic and Social Council EV Electric vehicle GDV German Insurance Association IATA International Air Transport Association ICAO International Civil Aviation Organization IMDG International Maritime Dangerous Goods Code (IMO) IMO International Maritime Organization IMP Interline (or Interchange) Message Procedure-Code Code A/C ADR BMS CAO DGD DGR DGP DSC ECE ELI
REFERENCES
LBSG MAG MSC OTIF PAX A/C PI RID RLI RLM SOC TI UN UN 38.3 UNECE
471
IATA Lithium Battery Shipping Guidelines Miscellaneous goods (Class 9, dangerous goods) Maritime Safety Committee (IMO) Intergovernmental Organization for International Carriage by Rail Passenger Aircraft Packing Instruction—IATA DGR Regulations Concerning the International Carriage of Dangerous Goods by Rail (OTIF) Restricted Lithium ion—Cargo IMP-Code for Lithium ion batteries according to Part IB and Part I / IA of PI Restricted Lithium-metal—Cargo IMP-Code for Lithium metal batteries according to Part IB and Part I / IA of PI State of Charge of a cell/battery, normally in % Technical Instructions (ICAO) United Nations Subsection 38.3 of part III of the UN Manual of Tests and Criteria United Nations Economic Commission for Europe (also ECE)
REFERENCES [1] H. Huo, Y. Xing, M. Pecht, B.J. Zu¨ger, N. Khare, A. Vezzini, Energies 10 (2017) 793. [2] https://en.wikipedia.org/wiki/Dangerous_goods. [3] http://www.unece.org/trans/areas-of-work/dangerous-goods/legal-instruments-and-recommendations/unmanual-of-tests-and-criteria/rev6-files.html. [3a] https://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-guidance-document-2017-en.pdf. [4] https://www.lithium-batterie-service.de/app/index.php/?lang5en-gb. [5] J. Schnell, G. Reinhart, Procedia CIRP 57, pp. 568 573, 2016. [6] https://www.iata.org/whatwedo/cargo/dgr/Documents/lithium-battery-guidance-document-2017-en.pdf. [7] GDV, G. d. (VdS 3103: 2016-05 (02)). Lithium-Batterien GDV-Merkblatt zur Schadenverhu¨tung. Publikation der deutschen Versicherer (GDV e. V.). https://vds.de/fileadmin/vds_publikationen/ vds_3103_web.pdf.
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SUBCHAPTER
11B
SPECIFIC RISKS OF LITHIUM BATTERIES AT END OF LIFE
Jean-Pol Wiaux Consultant. Route d’Annecy, Geneva, Switzerland
11B.1 INTRODUCTION At end of service life, the potential hazards developed by waste lithium batteries (WLB) are similar to those of new batteries when placed on the market but the environment in which they may develop is different. The potential hazards are linked to the consequences of a short circuit (inner or outer) and the rapid release of stored electrical energy as well as the possibility of a thermal runaway resulting from exposure to high temperature of flammable components (solvent and additives) contained in lithium batteries. A specific attention needs to be paid also to residual high voltage (above 48 VDC) that may be present in large batteries used, for example, for electric mobility or energy storage. The risk level of an incident may be increased in the case of ignorance by a carrier or a waste storage facility operator about the presence of waste lithium batteries in the transport unit or the waste storage facility. The absence of information about the properties of such batteries in a given waste stream (e.g., lithium batteries in electrical and electronic equipment) is also perceived as a source of concern. Fig. 11B.1 gives a simplified representation of various hazard sources for waste lithium batteries. There are major management options for lithium batteries after their initial service life. As illustrated in Fig. 11B.2, a lithium battery reaching an end of its first service life (EOL) may be returned for repair or remanufacturing for reuse within the same application. When considered as waste, it is transferred to a waste company for final treatment or disposal. It may also undergo repurposing for a different use than the initial one: this represents the “second use” of the battery (Section 11B.6 of this chapter will address specifically this issue). Lithium batteries at end of life, when qualified as waste, may be collected by public or private organizations or taken back by producers, for recycling, as the result of voluntary initiatives or mandatory requirements. This chapter will not review the case of waste lithium batteries sent for disposal. The complexity of the end of life management is increased by the different types of lithium batteries placed on the market (pom) among others: lithium-metal primary and secondary (Li-M), rechargeable batteries with intercalation electrodes (Li-ion) and new rechargeable systems that use metallic Li electrodes.
11B.1 INTRODUCTION
Internal factors
473
External factors Fire Solid particles emissions Liquid & gas releases
Thermal runaway
Thermal stress (e.g. exposure to sunlight)
Temperature increase Mechanical damage Opening a short circuit
Internal short External short
Sudden release of electrical energy or Short circuit
Mechanical damage / damaged battery With Li B and with other waste batteries Storage in humid environment External short Unknown residual voltage
Li batteries at end of life
Lack of info on Li battery composition Non selective storage Non controlled transport Ignorance of the presence of Li batteries In transport unit or storage facility
FIGURE 11B.1 Major hazard sources for waste lithium batteries.
Service life (1st)
End of first service life (EOL) Reuse
Waste
Repair or Remanufacturing
Take back B2B
Repurposing
Collection C2B Second use Recycling
FIGURE 11B.2 Illustration of various management options for lithium batteries at end of first service life (EOL).
As illustrated in Fig. 11B.3, each of these return or collection routes are presenting different potential hazard levels due to their specific environment, the nature of the returned batteries and their residual electrical energy content—from a few Wh per cell (communication applications) to several kWh per module (E-mobility) up to the MWh per battery (energy storage).
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3. WLB separate collection (from dedicated commercial activity (*))
1. WLB mixed with other types of batteries (C2B)
Sorting
2. WLB installed in waste electrical & electronic equipment
Waste lithium batteries (WLB) take back & collection routes
Recycling
(*) e.g. Photo or watches shops, electronic equipment shops, cordless tools (DIY)…
4. WLB separate collection (from specific industrial applications (**)) (B2B) (**) e.g. Flow meters, e-bikes, electric vehicles, stand-by power units (UPS)…
FIGURE 11B.3 Illustration of various take back and collection routes for waste lithium batteries (WLB).
11B.1.1 THE NATURE OF INCIDENTS The large differences which exist in packaging and transport conditions between new and waste lithium batteries are illustrated in Fig. 11B.4. New cells out of works are packed separately in blisters or in trays to prevent short circuits. At the collection stage waste lithium batteries are transported in packaging with limited individual protection and sometimes in bulk conditions. The following circumstances have been at the origin of incidents involving waste lithium batteries: • • • • • • • • • • •
Unsafe storage in open air conditions (e.g., exposure to rain). Unsafe storage due to exposure to sunlight. Storage with other hazardous waste such as volatile organic solvents. Presence of large quantities of charged cells/batteries in noncontrolled storage areas (e.g., temperature control). No separation in storage between batteries of different chemistries. Storage of bare cells with metal housing offering opportunities for short-circuits between cells or batteries. Storage of mixed batteries in damaged conditions in absence of external protection. Handling of waste batteries subject to mechanical shock (e.g., during waste management operations). Presence of large quantities of charged cells in noncontrolled storage areas. Presence of large lithium-ion batteries in lead-acid battery flows entering a lead-acid battery recycling plant. Etc. . . An illustrative representation of lithium batteries-based incidents is reported in Fig. 11B.5.
11B.1 INTRODUCTION
FIGURE 11B.4 Differences in packaging conditions for new and waste lithium metal cells.
FIGURE 11B.5 Illustrative representation of some incidents sources involving lithium batteries.
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1. Lithium batteries at end of life hazard mitigation tools 2. Legislative and regulatory context Waste management legislation Basle convention Transport of dangerous goods 1. Waste lithium batteries 2. Damaged & defective lithium batteries
3. Communication Battery information factsheet Good practice guidance Emergency response guidance
4. Prevention Collection Safe storage Cushioning materials Insurance comp. Express courier Fire brigade connection
5. Control Depowering Recall actions Fire 1st responders Recycling plants 6. Reuse and second use
FIGURE 11B.6 Illustration of the content of this chapter.
11B.1.2 THE APPROACH In order to deliver to the reader some useful information for the handling and storage of waste lithium batteries, the approach taken in this chapter is described below and illustrated in Fig. 11B.6. Section 11B.2 will concentrate on the key legislative and regulatory acts in force to control the flow of waste lithium batteries at the end of service life at EU level as well as at international level. The specific requirements of the International Regulation for the Transport of Dangerous Goods will be summarized; indeed lithium batteries are classified as dangerous goods by the UN Model Regulation for the Transport of Dangerous Goods. In this context, the provisions of the Transport Regulation for Waste and Damaged and Defective batteries will be reviewed in Section 11B.3. In Section 11B.4, importance will be given to various sources of information available about the potential hazards offered by waste lithium batteries. References to major Good Practice Guidance documents will be given in this paragraph on “Prevention through Communication.” The paragraph will also review practical measures recommended or adopted by several commercial actors to mitigate the hazard at the end of life value chain. When waste lithium batteries with unknown residual energy are transported or entering recycling facilities, special procedures need to be implemented to identify and control the hazards that could develop due to the presence of high density electrical power sources in waste streams. This will be considered in Section 11B.5 on “Electrical Hazard Control.”
11B.2 LEGISLATIVE AND REGULATORY FRAMEWORK
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Several technical solutions have been considered to deactivate, depower, or inert the battery before transport or treatment when this is feasible: they will be briefly reviewed. The protection of portable batteries collected and transported in bulk will be addressed separately. In the context of a circular economy, the importance of recycling waste batteries and the recovery of raw materials has been placed as a priority by the EU institutions. In addition, “Reuse and Second use” are options to be considered before recycling. This will be further discussed in a final Section 11B.6 as a complementary regulation needs to be developed to deal with the producer responsibility aspects of a second use and a second placing on the market of rechargeable lithium batteries.
11B.1.3 BATTERY AGING The link between battery aging and safety has not been developed in this chapter as there is not sufficient data available to correlate the aging of waste lithium battery components and the safe handling of these batteries at end of life. But for the general influence of aging on safety please see Chapter 7E, Effect of Electrical Energy and Aging on Cell Safety. The Transport Regulation requires the knowledge of the history of the damaged or defective battery before its shipment. Therefore parameters such as abnormal aging, abuse, excessive temperature elevation during normal conditions of use all have their importance when considering the impact of aging on the safe behavior of lithium batteries at the end of life stage. This aspect of the safety issue will be reviewed in Section 11B.3.
11B.2 LEGISLATIVE AND REGULATORY FRAMEWORK During the last 10 years, the collection of waste batteries in general and waste lithium batteries has gained some momentum on a worldwide basis. In North America, Call2Recycle is operating a voluntary waste rechargeable battery collection program that covers waste lithium batteries and their processing in authorized recycling facilities [1]. The collection program covers North America (United States, Canada, and Mexico). In Japan, the Japan Battery Recycling Center (JBRC) is also operating a voluntary National Waste Rechargeable Battery Recycling and Collection Scheme [2]. In Australia, the voluntary collection of waste batteries is organized via the Australian Battery Recycling Initiative (ABRI) [3]. In Europe, portable batteries [4] that are separately collected from consumers have to be processed in a recycling plant as it is forbidden to landfill or incinerate separately collected waste batteries. Obviously, those batteries that are not collected separately will end up in municipal waste streams and will either be landfilled or incinerated. Waste industrial batteries that are taken back by producers or collected by professional waste management companies have to be processed in a recycling facility in accordance with the EU Batteries Directive. For the definitions of portable, industrial, and automotive batteries the reader is invited to consult the Batteries Directive 2006/66/ EC, Article 3 [4].
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11B.2.1 THE EU WASTE FRAMEWORK DIRECTIVE AND THE DAUGHTER DIRECTIVES ON WASTE The EU waste legislation concentrates at first on the protection of workers and of the environment during the production, the handling, and the processing of (hazardous) waste. When the management of waste batteries is considered, the mother piece of legislation (Waste Framework Directive) is complemented by Daughter Directives such as the End of Life Vehicle Directive and the Directive on Waste Electrical and Electronic Equipment (WEEE) and the Batteries Directive.
11B.2.2 THE WASTE FRAMEWORK DIRECTIVE National environmental authorities secure the implementation of the requirements of the EU Waste Directives regarding specific waste streams management. Directive 2008/98/EC [5] sets the basic concepts and definitions related to waste management, such as definitions of waste, recycling, recovery. It explains when waste ceases to be waste and becomes a secondary raw material (so called end-of-waste criteria), and how to distinguish between waste and by-products. The Directive lays down some basic waste management principles: it requires that waste be managed without endangering human health and harming the environment, and in particular without risk to water, air, soil, plants, or animals. The Directive introduces the “polluter pays principle” and the “extended producer responsibility.” It incorporates provisions on hazardous waste and includes two new recycling and recovery targets to be achieved by 2020: 50% preparing for reuse and recycling of certain waste materials from households and other origins similar to households, and 70% preparing for reuse, recycling, and other recovery of construction and demolition waste. The EU Waste Hierarchy principle is illustrated in Fig. 11B.7.
Product/article Prevention Preparation for reuse Preparation for 2nd use
Recovery Recycling Disposal Waste
FIGURE 11B.7 The EU Waste Hierarchy. Adapted from http://ec.europa.eu/environment/waste/framework/.
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According to the EU Waste Catalogue [6], batteries containing cadmium, mercury, and lead (or mixtures of batteries containing these batteries) are classified as hazardous waste. Currently, in Europe, waste lithium batteries are not classified as hazardous waste by the EU Waste Catalogue (see below for the distinction between hazardous waste and dangerous goods). Nevertheless, there is an exception in Austria where waste lithium batteries are considered by the National Austrian Legislation as hazardous waste. Therefore the lithium batteries collected in Austria are recycled in Austria, avoiding the issue of the transboundary movement of hazardous waste. There are discussions at EU level for classifying waste lithium batteries as hazardous waste. In Europe, changes in WLB classification is still under evaluation on a country basis. The following Daughter Directives have implications for waste lithium batteries.
11B.2.3 THE END OF LIFE VEHICLE DIRECTIVE Every year, end-of-life vehicles (ELV) [7] generate between 7 and 8 million tonnes of waste in the European Union which should be managed correctly. Directive 2000/53/EC on end-of life vehicles aims at making dismantling and recycling of ELVs more environmentally friendly. It sets clear quantified targets for reuse, recycling, and recovery of the ELVs and their components. The ELV Directive covers certain categories of vehicles, including their components, such as batteries. In its Annex 1 y3, the End of Life Vehicles Directive requires the separate removal of batteries contained in vehicles. This has been applied successfully for lead-acid starter batteries and is now implemented for lithium-ion batteries used in HEV, PHEV, or Full Electric vehicles (EV).
11B.2.4 THE WASTE ELECTRICAL AND ELECTRONIC EQUIPMENT DIRECTIVE The first WEEE Directive (Directive 2002/96/EC) entered into force in February 2003. The Directive provided for the creation of collection schemes where consumers return their WEEE free of charge. These schemes aim to increase the recycling of WEEE and/or reuse. In December 2008, the European Commission proposed to revise the Directive in order to tackle the fast increasing waste stream. The new WEEE Directive 2012/19/EU entered into force on 13 August 2012 [8]. In its Annex 7 yI, the WEEE Directive requires the separate removal of batteries contained in WEEE. This mandatory requirement is applied in all Member States through WEEE operators with a variable efficiency.
11B.2.5 THE BATTERIES DIRECTIVE The EU legislation on waste batteries is embodied in the Batteries Directive [4]. It intends to contribute to the protection, preservation, and improvement of the quality of the environment by minimizing the negative impact of batteries and accumulators and waste batteries and accumulators. To achieve these objectives, the Directive prohibits the marketing of batteries containing some hazardous substances, defines measures to establish schemes aiming at high level of collection and recycling, and fixes targets for batteries collection and recycling. The Directive also sets out provisions on labeling of batteries and their removability from equipment.
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It also aims to improve the environmental performance of all operators involved in the life cycle of batteries and accumulators, for example, producers, distributors, and end-users, and, in particular, those operators directly involved in the treatment and recycling of waste batteries and accumulators. Producers of batteries and accumulators and producers of other products incorporating a battery or accumulator are given responsibility for the waste management of batteries and accumulators that they place on the market. In 2008, the European Batteries Directive 2006/66/EC entered into force in all EU Member States [4]. As a result of the EU Batteries Directive implementation, waste lithium batteries were collected and returned to recycling plants via several major routes as illustrated in Fig. 11B.3: 1. in a mix with other nonlithium batteries as a result of the collection of all types of batteries from consumer applications; 2. after sorting, from streams of collected waste electrical and electronic equipment in a B2B operation; 3. in a separate collection stream when collected in specialized commercial entities; 4. from industrial applications where the waste lithium batteries are returned to industrial waste operators for consolidation before shipment to recycling plants. With the recent development of electric mobility, an increasing quantity of batteries are returned to recycling plants after separation from the application and collection, e.g., from electric bike shops or Authorized Treatment Facilities for cars at End of Life. Industrial batteries used for hybrid and full electric vehicles are generally under the controlled logistic of the car manufacturing company or its authorized representative.
11B.2.6 THE BASEL CONVENTION In addition when waste is transferred between countries and has to cross borders, the shipment have to fulfill the requirements of the Basel Convention on the transboundary movement of hazardous waste [9].
11B.2.6.1 Objective The overarching objective of the Basel Convention is to protect human health and the environment against the adverse effects of hazardous wastes. Its scope of application covers a wide range of wastes defined as “hazardous wastes” based on their origin and/or composition and their characteristics, as well as two types of wastes defined as “other wastes”—household waste and incinerator ash.
11B.2.6.2 Aims and provisions The provisions of the Convention are concentrating around the following main objectives: • • •
the reduction of hazardous waste generation and the promotion of environmentally sound management of hazardous wastes, wherever the place of disposal; the restriction of transboundary movements of hazardous wastes except where it is perceived to be in accordance with the principles of environmentally sound management; and a regulatory system applying to cases where transboundary movements are permissible.
In particular such hazardous waste cannot be shipped to a non-OECD country that has not signed the Basel Convention.
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There is a need of Prior consent for the transfer of this hazardous waste (each country involved during the transfer (transport) needs to give its authorization). There is a requirement of financial guarantees to be organized to secure the avoidance of orphan waste or to secure the treatment of orphan waste. The shipment of hazardous waste requires obviously significant administrative work between the shipper and the competent authorities of all countries crossed by the shipment of hazardous waste. Authorization may be granted only after 6 months or one year. . .depending on the number of the transit countries. This administrative work is not necessary for the shipment of nonhazardous waste which is done on a nonregulated free trade basis.
11B.2.7 THE INTERNATIONAL TRANSPORT REGULATION As we shall detail in the next paragraph, lithium batteries are classified as dangerous goods by the UN Model Regulations for the Transport of Dangerous Goods [10,11]. When they are transported to a recycling facility, a disposal center or an incineration facility, the transport of waste lithium batteries is governed by the Special Provision SP377 and its associated packing instruction P909. The transport of Damaged or Defective Lithium Batteries (D&D Lithium Batteries) is regulated independently by SP376 and P908. In Europe, the transport by road is regulated by the ADR [12] (the European Agreement concerning the International Carriage of Dangerous Goods by Road (ADR 2015)). The transport by sea is regulated by IMDG Code [13]. It is forbidden to transport waste batteries by air unless authorized by the National/local competent transport authority (See IATA [14]). These requirements will be reviewed in the next paragraph.
11.B.2.8 NOTE TO THE READER: HAZARDOUS WASTE AND DANGEROUS GOODS In the EU, the Dangerous Goods Transport Regulation is independent from the Waste Management Legislation. The terminology “dangerous goods” is used for the transport of new and waste lithium batteries. It corresponds to an international classification as proposed by the UN Recommendations on the Transport of Dangerous Goods—Model Regulations [10]. Currently dangerous goods such as Li batteries transported for disposal or recycling are not classified as hazardous waste. The terminology “hazardous waste” is used for waste batteries classified as hazardous in accordance with the EU Waste Catalogue [6,15].
11B.3 TRANSPORT OF LITHIUM BATTERIES FOR DISPOSAL OR RECYCLING The United Nations (UN) Model Regulations on the Transport of Dangerous Goods regulates the conditions of transport of Dangerous Goods such as lithium batteries listed under the reference numbers UN3090 and UN3091 (for lithium-metal batteries) and UN3480 and UN3481 (for lithiumion batteries).
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The objective of the UN Transport Regulation for Dangerous Goods is to define the rules/provisions under which the safe transport of dangerous goods is guaranteed. The UN Recommendations for the Transport of Dangerous Goods (Model Regulation—20th Edition) are structured around Special Provisions and associated Packing Instructions [10,11]. In principle the Special Provision defines the scope of application of the transport conditions while the associated Packing Instruction(s) addresses the technical details on the way to transport safely dangerous goods such as waste lithium batteries and damaged and defective lithium batteries. These provisions and instructions are aimed to be applied on a worldwide basis by any consignor to prevent and control the potential hazards that can originate in the mishandling of lithium batteries during transport. In addition, the UN Model Regulation is complemented by the specific Modal Transport Regulation, e.g., the ADR for Road and Rail Transport (ADR 2017) [12]. General for transport regulations see also Chapter 11A, Special Risks During Transport and Storage.
11B.3.1 SPECIAL PROVISIONS SP377 AND SP636 (B) (ADR) FOR LITHIUM BATTERIES TRANSPORTED FOR DISPOSAL OR RECYCLING In the specific case of lithium batteries transported for disposal or recycling, Special Provision SP377 and Packing Instruction P909 apply. NB. The UN Model Regulation does not use the terminology “waste” to characterize the load of lithium batteries when transported for disposal or recycling. Special Provision SP377 defines the scope of application of the Transport Regulation such as the type of lithium batteries as well as the marking requirements; reference is also made to the applicable Packing Instructions P909 that regulates the packing of lithium batteries carried for disposal or recycling. Under certain conditions, P903 for new lithium batteries can also apply to waste lithium batteries transported for disposal or recycling (See P903 (2c) when such batteries are still in compliance with testing requirements). P909 applies to lithium batteries transported for disposal or recycling either packed together with or packed without nonlithium batteries. it also regulates the transport of lithium batteries contained in equipment (see P909 (3)). The application of the UN Recommendations through the various transport modes is summarized in Table 11B.1. When the modal transportation is considered, the ADR Transportation regulation contains a specific Special Provision for the transport of waste lithium batteries (SP636 (b) (ADR 2015)) in relation with Packing Instruction P909. Special Provision SP636b (ADR) provides for some relaxation from the Packing Instruction P909. Indeed SP636 is considering the special conditions under which waste lithium batteries are collected from consumers. In Europe a significant ratio of waste lithium batteries is collected with other non-lithium batteries (e.g., zinc-alkaline batteries). The commercial entity, the private or administrative office, or the civil amenities collecting waste lithium batteries in a mix with other types of batteries do not have the knowledge about the composition of the returned batteries at the collection point. Therefore the Packing Instruction tolerates the return of these mixes of batteries in controlled quantities to the intermediate processing facility under not fully regulated transport conditions. This is illustrated in Fig. 11B.8.
Table 11B.1 Summary of the Transport Regulations for the Various Transport Modes for Waste Lithium Batteries Transported for Disposal or Recycling Specific Regulatory Requirements Waste Lithium Batteries (a)
Transport Modes 1.1.
1.2. 1.3. 1.4.
UN Model Regulation For the Transport of Dangerous Goods (Ref. 11). ADR—Road Transport (Specific in addition to 1.1.) (Ref. 12). IMDG—International Maritime Transport Regulation (Ref. 13). IATA—International Air Transport Association (Ref. 14).
UN SP377 and P909 (with the possibility to use P903 (2) under certain specific conditions) for waste Lithium batteries. In addition to 1.1. above and for Waste Lithium Batteries SP636b—ADR needs to be considered for Road Transport. To be considered: SP377, P909 and SP636b identical to Road Transport. IATA Dangerous Goods Regulations, Special Provision A154. Not allowed except when approved by the National Transport Authority of the State of Origin and the State of the Operator (Recycler—Disposal Facility).
a
Batteries transported for disposal or recycling.
Waste lithium batteries UN3090 & UN3480 and UN3091 & UN3481
SP636b
ADR road transport (specific)
SP377 & P909 or P903
Excepted from full regulation
Subject to full regulation
Modes road transport only
Modes road and maritime (not allowed by air mode)
1. Scope Li-M 20 Wh per cell 1.0 g Li per cell Li-ion 100 Wh per battery 2.0 g Li per battery < 500 g (cells and batteries) Together with or without other non-Li batteries 2. Conditions Up to the intermediate processing facility Quality insurance system in place < 333 kg (cells and batteries) per load P909 applies except add req 1 & 2 May not be protected individually against short circuit May contain not identified D&D Li batteries (see SP377) 3. Packaging Strong outer resistant packaging up to 30 kg gross mass
4. Marking Marking required Class 9 UN numbers
UN model regulation
1. Scope Full range of energy content All sizes (from small to large) Only lithium batteries and lithium batteries contained in equipment 2. Conditions Identified damaged & defective batteries need to follow SP376 For Li cells and batteries in equipment : outer packaging not PGII For Li cells and batteries > 12.0 kg with a strong outer resistant outer casing, a strong outer packaging may be used
3. Packaging Approved packaging of PG II performance level. or up to 30 kg >>> nonapproved packaging (strong outer packaging) Batteries should be secured against movement inside the outer packaging Packed to prevent short circuits and dangerous evolution of heat 4. Marking
Lithium batteries for recycling Not required Not required
Marking Class 9 Un numbers
Lithium batteries for recycling Required Required
In addition WLB may be transported as new batteries under P903 (2c)
FIGURE 11B.8 Summary table of the transport requirements for waste lithium batteries under the UN Model Regulation and ADR.
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11B.3.2 SPECIAL PROVISION SP376 FOR THE TRANSPORT OF DAMAGED AND DEFECTIVE LITHIUM BATTERIES The carriage of damaged and defective lithium batteries is regulated by a dedicated special provision SP376 and a packing instruction P908 (for batteries up to 400 kg net mass). A separate Large Packing Instruction LP904 covers the transport conditions for large batteries that are damaged or defective with a net mass above 400 kg. When a battery has undergone one or more severe mechanical damages leading, for example, to electrolyte spill out or structural damages or in case where it shows evidences of instable thermal behavior, such a battery is considered as damaged and needs to receive a dedicated attention for packaging and marking from the shipper/consignor. Similarly, a battery may be considered as defective when it has lost some of its functional properties that may lead to some instability such as abnormal thermal behavior, even when it has not been through mechanical damages. The International Transport Regulation has adopted a Special Provisions SP376 that considers the cases where a battery needs to receive the appropriate handling due to its defects or damages or its potential thermal instability: Table 11B.2 summarizes these specific regulatory requirements. Packing Instruction P908 allows the return of these damaged and defective batteries in controlled quantities per package to recycling plants under fully regulated transport conditions illustrated in Fig. 11B.9. It is advisable for the reader to refer to reference books prepared by qualified organizations such as “Lithium Batteries Transport and Packaging Instructions (A Multimodal Approach)” that can be also consulted on the referenced website [16]. This book is summarizing the transport regulation for lithium batteries with dedicated chapters on the transport of waste lithium batteries. the practical aspects of the packing instructions and packaging requirements are also described in the publication prepared by Dr. M. Ottaviani [16]. The publication of Label Master on the subject is another reliable source of information [17].
Table 11B.2 Summary of the Transport Regulation for the Various Transport Modes for Damaged and Defective Lithium Batteries Transport Modes 1.1.
UN Model Regulation For the Transport of Dangerous Goods
1.2.
ADR - Road Transport (Specific in addition to 1.1.) IMDG - Road and Maritime Transport. IATA - Air Transport
1.3. 1.4.
Specific Regulatory Requirements Damaged and Defective Lithium Batteries SP376 and P908 and LP904 NB. SP376 Overruled SP377 for identified D&D Batteries. SP376 and P908 and LP904 SP376 and P908 and LP904 IATA Dangerous Goods Regulations, Special Provision A154. Not allowed except when approved by the National Transport Authority of the State of Origin.
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Damaged & defective lithium batteries UN3090 & UN3480 and UN3091 & UN3481
SP376 and P908
(UN model regulation and ADR)
Subject to full regulation Road and maritime (not allowed by air mode) 1. Scope Full range of energy content All sizes (from small to large) Large batteries > 400 kg are covered by LP904 2. Conditions The use of PGII is required. Cell of a net mass > 30 kg: one cell per packaging. 3. Packaging Each D&D battery shall be individually packed in an inner packaging and placed inside an outer packaging Each inner packaging shall be surrounded by non-combustible and nonconductive thermal insulation material Adopt measures to minimize the vibrations effects during transport Absorbent material to be used for leaking batteries
4. Marking Marking Class 9 UN numbers
Damaged/defective Lithium batteries Required Required
FIGURE 11B.9 Summary table of the transport requirements for damaged and defective lithium batteries under the UN Model Regulation and ADR.
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11B.4 COMMUNICATION TOOLS AS PREVENTIVE MEASURES The number of commercial actors dealing with lithium batteries is increasing significantly as the lithium battery technology is under continuous technical development and used in a broader range of applications. Therefore, it is important for battery manufacturers to communicate about the properties of their product down the value chain. In parallel, end of the pipe actors such as collectors and recyclers are also increasing while receiving larger quantities of various types of waste lithium batteries. When waste lithium batteries are reaching an intermediate storage facility, a waste management plant for consolidation or sorting, or a recycling plant before treatment, the local operators need to be informed with the most updated information regarding the lithium battery composition and their physical and chemical properties. In response to this concern, Competent Authorities and Private Organizations have prepared communication tools where good practice guidance, emergency response guidance, or battery information factsheets are made available to professionals.
11B.4.1 THE PREVENTION AND RESPONSE TO INCIDENTS Batteries associations such as RECHARGE and PRBA, supported by their members representing the lithium battery industry, have developed communication tools describing the potential hazards of lithium batteries [18]. This type of information contains also appropriate information regarding the prevention and response to incidents. Good Practice Guidance and Emergency Response Guidance prepared by National Transport Authorities [19] and industry represent key communication tools about the potential hazardous properties of lithium batteries. They describe the basic safety measures to adopt for handling or storing new lithium batteries and waste lithium batteries. The first Emergency Responses Guides were published in the mid-2000s by the US Department of Transport (DOT): the Pipeline and Hazardous Materials Safety Administration (PHMSA) issued an updated version of its Emergency Response Guidebook in 2016 [20]. The Guide N 138 addresses the specific issues of lithium primary batteries while the Guide N 147 is dealing with lithium-ion batteries. The Emergency Response Guidebook is used by emergency services personnel to provide guidance for initial response to hazardous material and dangerous goods incidents. This publication helps to provide consistent emergency response procedures for hazardous materials in North America, and is an essential tool for preparedness, planning and training. The preparation of this Guidebook is a joint effort between the transportation agencies of Mexico, Canada and USA.
More recently, RECHARGE the European Advanced Rechargeable Battery Association has published a Lithium-Ion Battery Information Factsheet [21] that covers the handling of lithium batteries at end of life. In cooperation with CTIF, the Factsheet was used to prepare an appropriate emergency response in case of incident at the attention of first and second fire responders [22]. Call2recycle [23] has published safety tips on how to recycle safely lithium batteries. The organization is also proposing a detailed set of information regarding the packaging of batteries for mail delivery.
11B.4 COMMUNICATION TOOLS AS PREVENTIVE MEASURES
Do • Carry out a risk assessment before you start any activity involving used batteries. • Ensure that appropriate firefighting equipment is available in case of a battery fire. • Ensure that Material Safety Data Sheets (MSDS) are readily accessible. • Comply with all packaging and transport requirements in the Australian Dangerous Goods Code if you are collecting, transporting, or storing a lithium or lithium ion battery consignment. • If lithium batteries are mixed with other nonlithium batteries for recycling, follow the requirements in Dangerous Goods exemption 010/12. A quality assurance system must be in place to ensure that the total amount of lithium batteries per transport unit does not exceed 333kg and the total weight of each container does not exceed 400kg. A copy of the exemption must be carried by the driver. • Ensure that the site where lithium batteries are collected and stored, and the transport vehicle, have a satisfactory level of security to ensure that only trained people have access. • Train employees in spill and emergency response. • During storage and transport ensure that batteries are protected from the weather and excessive humidity, in a well ventilated area, and easily accessible in case of a fire. • Always wear thick gloves and safety glasses if handling batteries. • Wash your hands thoroughly with water should contact be made with leaking or damaged batteries. • Ensure that storage containers are appropriately labeled.
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Don't • Don't store used batteries near any heat source (strong light, sun, oven, machinery). • Don't store used batteries near other chemicals or food. • Don't touch used batteries without protection. • Don't store batteries too close to inhabited buildings. • Don't attempt to lift heavy loads manually. Always seek help or put controls in place (removal trolley or forklift). • Don't handle used batteries if you haven't been trained. • Avoid vibrations and micro-movements caused by transportation, machines, fork-lift, etc. as they increase the risk of short circuits. • Don't transport used handheld batteries with other batteries weighting more than 500g or used lead acid batteries (ULABs). These need to be packaged separately as they have different regulatory requirements. • Don't deliberately break open lithium batteries as lithium is a reactive metal and if exposed to humid air may react and spontaneously catch on fire. Care needs to be taken to avoid physical damage to the batteries. • Don't store batteries for more than 6 months. They should be transported to recyclers regularly.
FIGURE 11B.10 List of recommendations for the handling of waste lithium batteries.
The Australian Battery Recycling Initiative (ABRI) is a not-for-profit association established in 2008 to promote responsible environmental management of batteries at end of life. More information on battery recycling can be found on their website where the organization is proposing safety guidance for the transport and recycling of lithium batteries [24]. A list of recommendations for the storage and handling of lithium batteries as proposed by the Australian Battery Recycling Initiative is reproduced in Fig. 11B.10.
11B.4.2 RESULTS OF TESTS The information gathered by laboratories or institutions that are performing tests on lithium batteries is essential for the professionals that are handling and storing large quantity of waste lithium batteries. The pioneering work of the National Fire Protection Agency (NFPA-USA) [25] and of The Institut National d’Etude des Risques (INERIS-F; [26] ) need to be mentioned as they analyze the consequences of a severe incident and the appropriate measure to be taken by responders [27].
11B.4.3 RECALLED BATTERIES Air carriers such as UPS and DHL are issuing regularly recommendations about the transport of recalled lithium batteries for recycling [28,29]. Their basic recommendation is not to ship by air batteries recalled by the manufacturer for safety reasons, as such shipments are prohibited by regulation (i.e., IATA Dangerous Goods Regulations, Special Provision A154).
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Table 11B.3 Set of Recommendations for the Safe Storage of Waste Lithium Batteries as Published by VDA (Ref. 30) • Compliance with all requirements of the manufacturer regarding safety through its safety data sheet. • Prevention of short circuits by adequate protection of battery terminals. • Prevent internal short circuits, e.g., during mechanical damage. • Prompt disposal wanted for trial products via waste management professionals. • Do not expose to high temperature heat sources or expose directly to sunlight. In the case of Mixed Storage of goods/articles, organize a separate storage area for lithium batteries. Maintain a distance of 2.5 m from other goods storage area. Comply with fire safety equipment or store in separate areas (e.g., dedicated containers). Safety cabinet, hazardous substance containers, . . . Appropriate staff training for handling of lithium batteries (according to similar Dangerous Goods/Hazardous materials). Prepare dedicated fire intervention tools. Maintain contact with local authorities and official fire responders.
As mentioned in Section 11B.3 above, waste lithium batteries collected for recycling are not to be sent via air services as the shipment of waste batteries by air is forbidden unless an authorization is granted specifically by the National Air Transport Authority.
11B.4.4 RECOMMENDATIONS FOR THE SAFE STORAGE OF WASTE LITHIUM BATTERIES The German Insurance Association [30] has issued recommendations for the storage of lithium batteries that applies both to new and waste lithium batteries. Such recommendations can be found in one of their publications where they mainly concentrate on the conditions for storage. Some of their recommendations are listed in Table 11B.3. For safe storage see also Chapter 11A.2, Storage.
11B.4.5 FIRE FIGHTING FIRST RESPONDERS Fire fighting first responders have also considered the new type of hazards developed by electrically powered vehicle, hybrid, plug-in hybrid, or full electric equipped with lithium batteries. Among their concern comes the first response to a fire and, after, the management of the battery when such an incident is under control. At the initiative of CTIF, an IEC Standard on the Information Sheet is in preparation by Fire Fighters Organizations [31]. For fire fighting see also Chapter 12C, Ignition and Extinction of Battery Fires.
11B.4.6 WASTE BATTERIES COLLECTION ORGANIZATION EUCOBAT is the European association of national collection schemes for batteries [32]. The Members of EUCOBAT ensure that all collected waste batteries are recycled in an ecological
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sound way. These advisory notes are based upon the experience and the best practices of the members of EUCOBAT and to the best knowledge of the compliance organizations. They are subject to permanent evaluation and improvement. They have published in 2013 a series of Safety Advisory Notes. Their recommendations should be consulted before collecting and shipping waste lithium batteries collected from end users.
11B.4.7 THE TRAFFIC LIGHT APPROACH In order to minimize the hazards linked to waste lithium batteries storage and transport, the recommendations developed by GRS (Battery Collection and Recycling Foundation (Germany)—one of EUCOBAT’s members) are illustrated by the traffic light approach (Fig. 11B.11) where three different levels of hazards are associated with the collection of waste lithium batteries [33]. The Green level concerns the collection and storage of lithium batteries of low nominal energy content (e.g., less than 100 Wh) in a mix with other nonlithium batteries. This is typical of the collection of waste consumer batteries from sales points. The Yellow/Orange level concerns the collection of mono-fractions of primary and secondary lithium batteries of known composition. The Red level is attributed to the collection of damaged portable or industrial batteries with a high energy content: typically, damaged e-bikes batteries would enter this category.
FIGURE 11B.11 The traffic light approach: basic principles for a differentiated hazard approach when handling, storing, and transporting waste lithium batteries. GRS—http://www.grs-batterien.com/fileadmin/user_upload/Download/Batteriebriefe/GRS-Batteriebrief_EN.pdf.
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As an evaluation tool for their clients, GRS has also developed a questionnaire with recommendations to categorize the batteries in accordance with the traffic light approach and to adopt the appropriate attitude before the transport of such batteries from such collection points. In a similar way some of the members of the German automotive industry have adopted a traffic light approach for the transport of damaged and defective lithium batteries used for E-mobility [34]. It concerns mainly the qualification of lithium batteries that have undergone an accident while installed in an electric vehicle. The following progressive scale of hazards has been retained in order to supply the most appropriate packaging and transport recommendations to the damaged battery. Green: Yellow: Red:
Batteries not damaged, not defective. Batteries may be damaged but not showing any potential evolution of heat. Batteries suspected to be “unstable” that may undergo heat evolution (uncontrolled).
The associated recommendations for packaging and transport can be obtained by contacting directly the referenced authors.
11B.5 ELECTRICAL HAZARD CONTROL: TECHNICAL SOLUTIONS Lithium batteries collectors and recyclers have to deal with primary lithium-metal batteries and rechargeable lithium-ion batteries for processing in their plant. As shown in Fig. 11B.12 there is a wide range of energy content in new lithium-ion batteries that may or may not be present when the waste battery flow reaches the recycling plant. In a similar way in the case of lithium-metal batteries, the recyclers may accept button cells (less than one Ah nominal capacity) as well as large
FIGURE 11B.12 Range of the initial energy content of new lithium ion batteries that may be present in a waste battery stream.
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491
batteries built for industrial applications with energy content up to the kWh and higher. They may also accept manufacturing rejects with more than 80% charge or batteries only partially discharged. This paragraph will elaborate on the control of the electrical risk that may be present in waste lithium batteries due to a residual electrical charge and the way to mitigate it.
11B.5.1 ELECTRICAL HAZARD The processing of waste lithium batteries for recycling requires in most cases their handling in several preliminary steps, in particular when they have been assembled to deliver high energy and power, for example, for electric mobility. When entering a recycling facility, industrial lithium batteries may still contain a significant residual electrical energy. Due to their weight and volume, these batteries are disassembled into smaller components (modules or cells) in order to feed the recycling process. The preliminary treatment steps will secure the protection against two major hazards: the electrical shock from high voltage and high power batteries (e.g., above 48 VDC) and the chemical hazard linked mainly to the presence of organic substances in the battery. For large batteries, the end of life management will generally involve four steps, including: 1. Pretreatment. A pretreatment step for the removal of fluids (such as cooling fluid) or external cleaning. 2. Disassembly. A dismantling step where the battery is disassembled into basic modules and where the various metallic or plastic components (connectors, wiring, etc. . .) are separated. 3. Recycling. A treatment where the battery (or its modules) is entering a process to separate and/ or recover added value materials involving among others, mechanical handling, thermal treatment, chemical processing. 4. Waste Disposal. A final treatment step for residues not recovered under previous step(s). For safety reasons, the battery may be deactivated in order to reduce its voltage and electrical energy content to a minimum value and therefore to prevent electrical shocks. This deactivation may occur before or during step 2 above (disassembly) according to the design of the battery and its technical characteristics. In this chapter, we shall concentrate on references to various methods used for the electrical deactivation of lithium-ion batteries. In the literature, deactivation is synonymous of other terminology such as depowering, inerting, de-energizing, . . . Deactivation targets one objective: the reduction of the residual electrical energy content of the waste battery to a minimum value where the electrical hazard is eliminated. The reported methods apply to industrial batteries well above the 100 Wh range. Typically, deactivation applies to “industrial batteries” used in E-mobility or energy storage applications. The methods of deactivation have also been considered for lower energy containing batteries (,100 Wh), but this practice has not been implemented at industrial scale. It is worth mentioning the recent publication of the United States Advanced Battery Consortium (USABC) on the Recommended Practice for Recycling of xEV Batteries (electrochemical energy storage systems [35]). This set of recommendations shows how important it is to be informed about the battery content and the design of the battery to facilitate a safe end of life processing as well as the recovery of added value materials.
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11B.5.2 DEACTIVATION 11B.5.2.1 Deactivation or de-energizing, depowering, or inerting a Lithium Battery The disassembly of a large EV batteries offering nominal voltages higher than 100 Volts and capacities higher than 10 20 Ah up to 100 Ah requires well informed operators. The deactivation of large EV batteries is an operation that requires trained manpower, special skills and tools, the knowledge of the architecture (design) of the battery, as well as its chemical composition. Generally the E-car manufacturer wants to keep this task inside a circle of qualified and well trained technicians. For safety reasons, it is advisable to inform the “recycler” about the exact design and composition of the battery in order to evaluate the hazards associated to the handling of the chemicals contained in the battery (see Section 11B.4 of this chapter). A well-documented manufacturer’s guide on the safe design of batteries as perceived by a battery manufacturer has been prepared by Jim McDowall [36]: A Guide to Lithium—Ion Battery Safety. In Fig. 11B.13, we have summarized various options considered to deactivate a lithium-ion battery. At end of life, three potential routes have been identified to handle the battery: the example of deactivation of a damaged and defective battery has been selected.
Damaged & defective Batteries (D&D) Objective : secure safety during transport Control the reactivity of the D&D battery 1. UN = SP376
3. Wet process (deactivation)
Discharge
No need for
/external
deactivation
3. Discharge in salt water
2. Dry process (deactivation)
2.2. 2.1. Disassembly
Controlled pyrolysis
2.1.1. Separated D&D module
2.1.2. Separated not D&D modules
2.2.1. Metals & powder
2.3.
load
2.3.1. Low voltage battery
Packaging requirements P908 or LP904
3.1. After drying
3.2. Wet as processed
Safer transport conditions (D&D Batteries Transported for Recycling)
SP 376 &
Like a new
PI908 (See
battery SP 188
Case 1)
P903
Waste battery SP 377 & PI909
Waste or HAZ. waste ?
Waste battery or not?
Waste battery SP 377 & PI909
SP 376 & PI908
Like a new battery SP 188 P903
Waste battery SP 377 & PI909
Use of cushioning materials
Waste or HAZ. waste ?
Waste or HAZ. waste ?
Waste battery or not?
Waste battery or not?
Waste battery
Waste battery
SP 377 & PI909
SP 377 & PI909
FIGURE 11B.13 Various technical alternatives for the deactivation (depowering) of waste lithium batteries.
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493
1. The application of the UN Model Regulation Requirements (SP376 & P908&LP904) and the use of cushioning materials; 2. The application of a dry deactivation based on electrical, thermal, mechanical means; 3. The use of a wet deactivation process in an appropriate water-based electrolyte. Each one of these methods has some advantages and constraints that will be reviewed. In addition, there are many questions raised after the deactivation of a battery. We have also considered the complexity of the handling of the deactivated battery. Indeed some operators are deactivating the battery to classify it as chemical waste and not as a waste battery. The examples illustrated in Fig. 11B.13 show the potential complexity of the problems and the decision processes.
11B.5.3 UN TRANSPORT REGULATION When a damaged and defective battery is transported according to the UN requirements of Special Provision SP376, the importance is placed at the level of the knowledge of the history of the battery (SP376) and at the level of the packing requirements (P908). As mentioned in Section 11B.3, one objective of the UN Transport Regulation is to propose packing instructions that will secure the safe transport of batteries for disposal or recycling. The safety aspects have to be secured by the “consignor,” where the consignor means any person, organization, or government which prepares a consignment for transport, as defined in the UN Model Regulation. One of the requirements of P908 is the use of cushioning materials that will allow to control the abnormal evolution of heat inside a packaging containing lithium batteries (e.g., in the case of thermal runaway). The cushioning material may also be used to absorb any liquid leakage out of the battery.
11B.5.4 USE OF CUSHIONING MATERIAL IN PACKAGING AND STORAGE In order to mitigate the hazard during the transport of lithium batteries for recycling, the regulator requires the use of cushioning materials to prevent among others short circuits during transport and also to avoid the movement of batteries when their packaging is handled and transported (see P908 or P909 of the UN Model Regulation). The technical requirements of the packaging material imposed by the regulator are as follows: Non-combustible, non-conductive (electrically), thermal insulator, chemically inert, cushioning effect and absorbent,. . .
The company ACCUREC GmbH [37] performed recently a study on the use of cushioning materials in transport conditions. The authors have considered that the cushioning materials selected must protect batteries against movements during transport. In addition, the material needs to be handled in a practical way at a realistic cost. In the study, ACCUREC has considered the thermal properties of five cushioning agents: Vermiculite, Sand, SORBIX, Absorbent and Pyro-Bubbles. The various types of cushioning materials are represented in Fig. 11B.14.
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FIGURE 11B.14 Illustration of the various types of cushioning agents studied by accurec gmbh (Ref. [37]).
ACCUREC concludes that thermal conductivity and heat capacity are the important factors in the selection of the cushioning material. As a result of their tests, they identified sand as being the cushioning material that offers the best ratio of technical performances versus cost. Technical performances include control of a thermal runaway and its heat impact to surrounding cells.
11B.5.5 WET DEACTIVATION VIA “IMMERSION” Facing the constraints of the UN Model Regulation, several industrial actors have considered that a “deactivated” battery is safer for transport. The procedure of immersion of the battery in salted water was first developed by battery manufacturing companies and by waste management companies. It consists generally of the immersion of the battery in salted water where the ionic-conductivity of the solution offers slow discharge conditions to the individual elements of the battery by creating an external short via the salted solution. Corrosion occurs with time which allows the salted solution to penetrate deeply into the battery elements, modules, or cells. The discharge of the battery ends when all cells have been exposed to the salted solution and the voltage of the cells or battery is reduced to a minimum value. The method suffers of a few major drawbacks: • • •
The discharge time is strongly dependent of the residual capacity of the battery. The salted electrolyte access to the cells is variable and dependent of the battery design. The end of the discharge is not controlled with accuracy.
11B.5 ELECTRICAL HAZARD CONTROL: TECHNICAL SOLUTIONS
• • • •
495
Lithium-ion batteries that have been discharged by this method have been reported to catch fire when drying. The evolution of hydrogen and other flammable gases during the discharge process requires gas exhaust equipment. The salted solutions need to be handled as hazardous waste at the end of the process. These considerations limit the use and control of a discharge by immersion to qualified employees and to facilities equipped with a waste water treatment unit.
The obvious advantage is the (theoretical) minimum initial investment for equipment (large pool and salted water). The wet deactivation process raises the question: is the deactivated battery still considered as a battery or can it be considered as hazardous waste? The response to this question varies with the level of achievement of the deactivation process. It certainly relies on the type of waste electrolytes produced at the end of the process and the remaining electrical charge in the deactivated battery.
11B.5.6 THE REDOX SHUTTLE APPROACH This approach is an improved version of the immersion process. By adding a selective redox system to the salted electrolyte in which the battery is immersed, the full discharge of the battery is guaranteed, leading to a safer behavior of the waste battery [38]. The advantages of adding such a Redox Shuttle Additive (RSA) in the immersion solution is the avoidance of gas evolution and the possibility to reach a discharged status in a reproducible manner. The methodology was known as early as the 1980s when it was discovered that RSA can be used as reversible overcharge protection of lithium-ion batteries. Details of this approach which is under development have been described by M. Wachtler and al. [39].
11B.5.7 DEACTIVATION THROUGH A CONTROLLED LOAD The use of an external load is a dry method that is attractive for large EV batteries at end of life [40]. In addition, when these batteries are defective and modules need to be replaced the selective discharge through an external load may be applied specifically to the defective module. The removal of energy from the battery or battery sections will make them safer for transportation. Deactivation or depowering can be performed on battery packs and modules most probably when the battery is removed from the vehicle. The dry deactivation generally offers the possibility to transport the deactivated battery under the lighter regime of SP376 as it is less susceptible to develop a dangerous evolution of heat due to a short circuit.
11B.5.8 OTHER MEANS TO DEACTIVATE A BATTERY 11B.5.8.1 Controlled thermal deactivation The principle of thermal deactivation has been recently described by the University of Loeben (Austria). Details can be obtained from the project leader, Mrs. A. Arnberger [41].
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The process consists of heating the battery to a controlled temperature range, below the critical temperature where a thermal runaway can develop. The result of the treatment is the deactivation of the cell from its chemical reactivity (solvent removal) and electrical sensitivity due to the absence of conductivity inside the cell at the end of the process.
11B.5.8.2 De-activation by cooling The handling of lithium-metal batteries under liquid nitrogen is a process used by TOXCO [42]. Recently, some types of lithium-metal rechargeable batteries have been transported at end of life under refrigerated conditions. Low temperatures are used to lower the conductivity of the electrolyte as well as the kinetic of hazard reactions and, therefore, to reduce the hazard of a thermal runaway during transport or batteries processing.
11B.6 REUSE AND SECOND USE The purpose of this paragraph is to define “reuse and second use” of rechargeable lithium batteries, describe the legal context where it can be applied, investigate how the Extended Producer Responsibility Principle applies for their reuse or second use and decide whether minimum requirements are needed to recommend reuse and second use of lithium batteries. With the market development of new rechargeable battery technologies offering longer service life and the possibility to power other applications than the one they were designed for originally, the “reuse” and the “second use” of rechargeable lithium batteries has been proposed to enhance their service life and/or to optimize their cost/performance ratio. It is also a way to reduce their environmental impact while enhancing their usage. The content of this paragraph is based on a report [43] issued recently by RECHARGE where an analysis is proposed of the various issues linked to the reuse or second use of lithium batteries. On December 2, 2015, the European Commission adopted an ambitious new Circular Economy Package [44] to help European businesses and consumers to make the transition to a stronger and more circular economy where resources are used in a more sustainable way. The proposed actions will contribute to “closing the loop” of product life cycles through greater recycling and reuse, and bring benefits for both the environment and the economy. Circular Economy keeps the added value in products as long as possible in order to minimize waste. The objective is also to keep resources within the economy when a product has reached the end of its (first) service life in order to create additional value of this product. The priorities of the legislator evolve into the direction of: 1. Extension of the product’s service life (e.g., by appropriate design, increasing materials performances,. . .). 2. Reuse or second-use (preventing early waste production). 3. Recycling (to recover value added materials or products). These policy options have been presented schematically in Fig. 11B.7.
11B.6 REUSE AND SECOND USE
497
In the Electric Vehicle Regulatory Reference Guide [45] prepared by the UNECE Electric Vehicle and the Environment Informal Working Group, it is mentioned that: As Lithium batteries dominate the cost of electrified vehicles and are typically deemed unusable from a mobility standpoint after degrading to between 70 and 80% of fully-chargeable capacity, there is a compelling reason to take a serious look at re-using these batteries in other applications. Battery re-use post-mobility represents a wide gap that will be challenging to govern given the highly variable nature of battery wear and inherent differences in chemistry, construction, and power management. In order to ensure the success of battery re-use or second use, guidelines and regulations that govern the implementation, as well as ensure the reliability and durability of such systems are crucial. There may also be a need for additional regulation/legislation in this field to prevent misuse or abuse of rechargeable batteries offered for second use.
A number of research initiatives and pilot projects have been developed to evaluate the economics and viability of second use of (mainly industrial) lithium batteries. These projects link the industrial battery used in e-mobility with the household electricity grid in a so-called combined energy storage. As long as the project is run under the responsibility of the battery producer, there does not seem to be an issue with extended producer responsibility principle as the producer controls the first and second placing on the market. A nonexhaustive list of projects evaluating the possibility to have a second use for EV Batteries is presented in Table 11B.4 while Fig. 11B.15 offers an illustration of the various management options of lithium batteries at end of life. Table 11B.4 Nonexhaustive List of Minimum Requirements to be Considered for Allowing Reuse or Second Use of Lithium Batteries (Recharge)
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Life cycle Design
Article
Applications
(Re)Processes Reuse * Application A
New product Application A
Manufacturing assembly
Repurposing Redesigning
Repurposed for a different application
New battery Incorporated or private label
Incorporated or Relabeled
PoM Remanufactured,... same design product, same application (*)
PoM
In use
In use
Used, D&D or from repair...
Used, D&D, Rep.
EoL Waste
EoL Waste
* includes integration of the original battery (component) into the product to obtain same functionalities as before.
** includes changes in electronics, software, communication system (e.g., battery management unit)
Use phase In use
Used defective damaged Repaired
Remanufacturing (2) Rebuilding Refurbishing Reconditioning Repairing
(3) EoW
End-of-Life recycling
EoL Waste
Waste treatment Preparation for recycling
Re-enter life cycle as raw material
Second use ** Application B
End of Waste Recycling Energy recovery landfill
(4)
FIGURE 11B.15 Illustration of various management options for lithium batteries at end of first service life.
In this section, the author will concentrate on definitions issues and on the producer responsibility associated to the additional commercial step where a lithium battery could be commercialized for a second use.
11B.6.1 DEFINITIONS The literature offers a wide variety of terminology to qualify a technical and commercial step where the service life of lithium batteries is enhanced: second hand use, double use, repurposing, refurbishment, remanufacturing, repairing, redesigning, reconditioning, etc. These terms need to be placed in their context to avoid confusion and misunderstanding of the issues [46]. In the Batteries Directive 2006/66/EC, the term “reuse” is not defined. Such a definition is supplied in the Waste Framework Directive and other Daughter Directives such as the WEEE and the ELV Directives (see Section 11B.2 for the reference to the Directives). In contrast, the term
11B.6 REUSE AND SECOND USE
499
“second use” is not defined at all in the various Waste Directives (neither in the Waste Framework Directive nor in other Daughter Directives) that are governing the end of service life of substances, mixtures, equipment or articles. We are proposing the following definitions for reuse and for second use. Reuse. Any operation by which articles (products or components) that are not waste are used again for the same purpose for which they were conceived. This definition is supplied in Article 3 (y13) of the Waste Framework Directive 2008/98/EC (WFD). RECHARGE interprets that reuse is meaning the complete or partial reuse of the battery for the original purpose/application it was designed for (possibly after inspection or remanufacturing or refurbishment) when placed on the market for the 1st time. The definition of reuse is based on the “same/original purpose.” One could argue about the fact that batteries—being a component—in the case of reuse, need to be reused in the original application in order to secure all technical performances and safety aspects. Second use is not mentioned in any of the Directives listed above. RECHARGE interprets second use as any operation by which articles (products or components) that are not waste are used for a different purpose for which they were conceived and placed on the market for the 1st time. The absence of definitions for the “second use” of a battery opens the door to a misunderstanding of the operation of second use and its legal consequences. Therefore some caution is advised to readers as in many documents the terminology “second use” is being utilized to describe either second hand use, or second life, or even to describe reuse. . .
11B.6.2 THE EXTENDED PRODUCER RESPONSIBILITY (EPR) The producer responsibility is at first regulated when a product or article is placed on the market by an identified producer. The producer responsibility has been further extended to the management of waste lithium batteries. When lithium batteries are concerned, the legislation covers the first placing on the market. The absence of a legal background raises the issue of the extended producer responsibility for such batteries that are either reused or offered to the market for a second use. Beyond the need for harmonized definitions across the different waste directives, there is also a need to clarify the minimum requirements under which the legal context could further develop.
11B.6.3 EPR AND DIRECTIVES ON NEW PRODUCTS The producer responsibilities are well defined in the Directive 2001/95/EC on General Product Safety where Article 2 (e) defines the producer and its responsibilities regarding the safety of the products or article sold under its brand name. In addition, Directive 85/374/EEC on liability for defective products in Article 3, producer means the manufacturer of a finished product, the producer of any raw material or the manufacturer of a component part and any person who, by putting his name, trade mark, or other distinguishing feature on the product presents himself as its producer. More precisely, a battery producer will indicate on its battery or in the user’s manual that the battery cannot be used in any other application than the appliance it was placed on the market with.
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This applies evenly to lithium batteries for digital cameras, cordless power tools, lawnmowers, or electric vehicles.
11B.6.4 EPR AND WASTE DIRECTIVES Within the context of the Waste Directives such as WEEE (2012/19/EC), Batteries (2006/66/EC) and ELV (2000/53/EC) Directives, Member States shall ensure that producers set up schemes for the collection and recycling of WEEE, batteries and accumulators and vehicles. EPR is based upon the principle that producers have the greatest control over product design and marketing and that these same companies have the greatest ability and responsibility to reduce waste and improve resource efficiency. EPR may take the form of a reuse, take-back, or recycling program. To encourage manufacturers to design environmentally friendly-conscious products the EPR is holding producers responsible for the costs of managing their products at end of life. The producer may also choose to delegate this responsibility to a third party, a so-called producer responsibility organization (PRO), which is paid by the producer for the management of its own products at end of life. In this way, the producer secures its responsibility for waste management by a third party while fulfilling its obligations versus the local (national) authority. The EPR principle shifts the responsibility for waste management from government to private industry, requesting producers, importers, and/or sellers to internalize waste management costs in their product prices and ensuring the safe management of their products at end of life. The link between EPR and the Batteries Directive 2006/66/EC can be found in the definition of “producer” in Article 3. y12.: “any person in a Member State that, irrespective of the selling technique used, including by means of distance communication. . .places batteries, including those incorporated into appliances or vehicles, on the market for the first time within the territory of that Member State on a professional basis.” The Article 3 y 14 defining the “placing on the market,” is complementary to the definition of the “battery producer.” Two cases are detailed below and illustrated in Fig. 11B.16. Case 1. In the case where the battery is reused (after refurbishment or remanufacturing) for its initial purpose, the producer is still controlling the placing on the market of the battery and the waste management flow of the battery (Case 1). Case 2. In the case where the battery is placed on the market for the second use by the producer (who first placed the battery on the market), this producer will keep the responsibility of the battery offered for the second use (Case 2a). This scenario does not create any concern as the “first producer” will keep the responsibility of the battery through its second use and its end of life. There will be cases where the “second use” will request a transfer of ownership of the battery and a second placing on the market (Case 2b). It is also anticipated that the “second use” will not be known by the first producer. Therefore, the possibility to have a battery offered for a second use is opening the question of the responsibilities of the “second” producer which are not defined in the Batteries Directive. In the case where the battery is offered for a second use by a third party for another application than for which the battery was designed initially (and put on the market for the 1st time), this new
11B.7 CONCLUSIONS
501
Producer 1
Case 1
Case 2 Case 2A POM 1
POM 1
Reuse as USE 1
USE 1
USE 1
(Includes 2nd hand)
EOL
Case 2B
Producer 1
Producer 2
2nd POM
2nd POM
2nd USE
2nd USE
EOL
EOL
(Producer 1)
(Producer 2)
(Producer 1)
Covered by the batteries directive
Not covered by any waste legislation
FIGURE 11B.16 Application of the EPR principle for lithium batteries according to the reuse or second use options.
commercial actor becomes a (second) producer and should take responsibility for the end of life management of the battery. Indeed, the new commercial actor is acting as a second producer placing the battery on the market for a second time. The responsibilities of this operation are not covered by the current definitions of Article 3 y 12 and y 14 of the Batteries Directive.
11B.7 CONCLUSIONS As a result of the development of new batteries technologies opening the road to a wider range of applications and the possibility offered to use a battery in multiple applications during its service life, several additional technical and regulatory issues are raised by the multiple/sequential transfer of ownership and the possibility to use the battery for a different application than the one offered during the first placing on the market. The fact that a second producer is now possible in the value chain of the battery service life requires the development of the legislation to cover their responsibilities. Indeed the battery design must probably be adapted to the new application, including the battery management system. The performances of the batteries and the associated warranty will also be
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adapted. In addition, the UN Model Regulation for the transport of Dangerous Goods applies to lithium batteries. For safety reasons, it requires specific testing requirements in accordance with defined design and technical specifications. This needs to be performed on the new design before the second use of the battery. For reuse, the conditions for EPR of the first producer can be respected. For second use, the conditions for EPR could potentially not be respected because they may be out of control of the initial producer who has placed the battery on the market for the first time. The duties of the EPR for batteries extend to the registration as a producer, reporting of quantities of batteries placed on the market for portable batteries, marking requirements, participation to collection schemes for portable batteries and automotive batteries, as well as take back obligations for industrial batteries. All these requirements should apply to the “second” producer. RECHARGE proposes to define minimum requirements to evaluate the possibility to reuse or to allow a second use of lithium batteries. The most critical factor is to maintain the EPR and the transfer of ownership under a legal framework. These minimum requirements are illustrated in Table 11B.4 below [47]. When the proposed minimum requirements in the table are fulfilled, RECHARGE supports the reuse of rechargeable batteries for their original applications. This requires that quality, performances, and safety standards are observed before placing the lithium battery for a second time on the market. In the presence of legal uncertainties, RECHARGE is not supporting the second use of lithium batteries except when the battery remains under the responsibility of the first producer acting as the legal entity placing the battery on the market for this second use. In the absence of a legal basis and clear minimum requirements, RECHARGE does not support the second use of lithium batteries, when there is a transfer of ownership and a new commercial entity placing the battery for a second time on the market. Indeed, currently, there are too many unknown factors that could impact a product’s reliability and end users’ safety in a nonregulated second use. More precise regulation is needed for a clear application of the EPR, more precise description in case of second use of batteries: the conditions of transfer of the EPR to the “second placing on the market” should be regulated. This is necessary for a level playing field to be developed in the “second life” market. This is critical for the traceability at end of life. This issue has not yet received detailed attention in order to define the boundaries of its implementation. In the case of second use, there is an urgent need to develop an appropriate legal basis to define the EPR and avoid unfair business. Reuse is a practice that can be encouraged, as long as it proposed under professional conditions (see Table 11B.4). Under regulated conditions, the development of a sustainable business in the field of second use of batteries could be a promising objective, allowing for an extended use of batteries for the benefit of all actors of the value chain of a lithium battery.
ACKNOWLEDGMENTS The author is thankful to his colleagues within RECHARGE, Mr. Claude Chanson and Mr. Willy Tomboy for supporting the preparation of this Chapter.
REFERENCES
503
ABBREVIATIONS The European Agreement concerning the International Carriage of Dangerous Goods by Road (Latest Edition 2015) B2B Business to Business C2B Consumer to Business CTIF International Association of Fire and Rescue Services - Comit´e Technique International de Pr´evention and Extinction du Feu DHL Express Delivery Services & International Shipping DOT Department of Transport (USA) EOL End Of Life (or End Of Service Life) EPR Extended Producer Responsibility Principle EU European Union EUCOBAT European Association of National Collection Schemes for Batteries EV Full Electric Vehicle GDV German Insurance Association GRS Battery Collection and Recycling Foundation (Germany) Stiftung Gemeinsames Ru¨cknahmesystem Batterien (GRS Batterien) HEV Hybrid Electric Vehicle IATA International Air Transport Association ICAO International Civil Aviation Organization IMDG International Martitime Dangerous Goods Code NFPA National Fire Protection Agency (USA) PHEV Plug-In Hybrid Electric Vehicle PHMSA Pipeline and Hazardous Materials Safety Agency PRBA The Rechargeable Batteries Association PRO Producer Responsibility Organization RECHARGE The Advanced Rechargeable and Lithium Batteries Association RSA Redox Shuttle Additive SP Special Provisions (UN Model regulations Dangerous Goods Transport) UN United Nations UPS United Parcel Service USABC United States Advanced Battery Consortium WEEE Waste Electrical and Electronic Equipment WLB Waste Lithium Batteries ADR
REFERENCES ,http://www.call2recycle.ca/contact-us/.. ,http://www.baj.or.jp/e/recycle/recycle05.html.. ,http://www.batteryrecycling.org.au/home.. ,http://ec.europa.eu/environment/waste/batteries/legislation.html.. ,http://ec.europa.eu/environment/waste/framework/.. ,http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri 5 CONSLEG:2000D0532:20020101:EN:PDF.. ,http://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri 5 CELEX:02000L005320130611&qid 5 1405610569066&from 5 EN.. [8] ,http://eur-lex.europa.eu/legal-content/EN/TXT/?uri 5 celex%3A32012L0019..
[1] [2] [3] [4] [5] [6] [7]
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CHAPTER 11 LI-SECONDARY BATTERY: SPECIAL RISKS
[9] BASEL CONVENTION : ,http://www.basel.int/TheConvention/Overview/tabid/1271/Default.aspx.. [10] UN Model Regulation. Recommendations for the Transport of Dangerous Goods 19th Revised Edition. ,http://www.unece.org/index.php?id 5 40533&L 5 0.. [11] UN Model Regulation ,http://www.unece.org/index.php?id 5 40533&L 5 0.. [12] ADR ,http://www.unece.org/index.php?id 5 36678&L 5 0.. [13] ,https://en.wikipedia.org/wiki/International_Maritime_Dangerous_Goods_Code.. [14] IATA ,http://www.iata.org/whatwedo/cargo/dgr/Pages/lithium-batteries.aspx.. [15] Waste Catalogue : ,http://ec.europa.eu/environment/waste/framework/list.htm.. [16] ,http://www.hyperedizioni.com/sezioni/213/the-lithium-batteries.. [17] ,http://www.labelmaster.com/lithium-battery-shipping.. [18] ,http://www.rechargebatteries.org/wp-content/uploads/2013/07/Li-ion-safety-July-9-2013-Recharge-. pdf.. [19] ,http://phmsa.dot.gov/pv_obj_cache/pv_obj_id_7410989F4294AE44A2EBF6A80ADB640BCA8E4200/ filename/ERG2012.pdf.. [20] ,http://www.thecompliancecenter.com/publications/erg.htm.. [21] ,http://www.rechargebatteries.org/wp-content/uploads/2013/04/Li_Ion-BIF_EN-May-2013-PART-1-2-34.pdf.. [22] ,http://www.rechargebatteries.org/wp-content/uploads/2015/01/RESCUE-AND-TRAINING-MANUALLITHIUM-BATTERY-IN-STORAGE-2014-12-05.pdf.. [23] ,http://www.call2recycle.org/safety-tips/.. [24] ,http://www.batteryrecycling.org.au/home.. [25] Hazard Assessment of Lithium Ion Energy Storage Systems. Fire Protection Research Foundation February 2016. ,www.nfpa.org/foundation.. [26] Investigation on the fire-induced hazards of Lithium-ion battery cells by fire calorimetry, INERIS. G. Gachot, P. Ribie`re and al. Anal. Chem., 2011, 83 (2), 478 485. [27] P. Ribie`re, S. Grugeon, et al., Energy Environ. Sci. 5 (2012) 5271. [28] ,https://www.ups.com/media/news/fr/ca/intl_lithium_battery_regulations.pdf.. [29] ,http://www.dhl.com/en/express/shipping/shipping_advice/lithium_batteries.html.. [30] Deutschen Insurance Association (GDVl) ,http://www.gdv.de/tag/lithium-batterien/. and ,http:// www.gdv.de/2015/12/lagerung-und-bereitstellung-von-lithium-batterien-aktualisierung/.. [31] Personal communication. Mr Kurt Volmacher: [email protected] ISO 17840 Road vehicles Information for first and second responders. [32] ,http://www.eucobat.eu/system/files/Eucobat%20-%20Safety%20Advisory%20Notes%20v4.1.pdf.. [33] ,http://www.grs-batterien.com/fileadmin/user_upload/Download/Batteriebriefe/GRS-Batteriebrief_EN. pdf.. [34] F.-A. Polonius, S. Spiez, Bescha¨digte lithium batterien in der automobile industrieFachkonferenz Lithium Batterien - Frankfurt/Main, SpringerVerlag, 2016GefahrGut. Available from: www.gefarhtgutonline.de/lithium2016. [35] file:///C: /Users/jpwiaux/Downloads/DisassemblyRP_USABC_2013_finalr1%20(2).pdf. [36] ,http://www.battcon.com/PapersFinal2014/1%20McDowall%20Paper%202014%20Final.pdf.. [37] Accurec Recycling GmbH, D-45472 Mu¨lheim am der Ruhr, Germany. Dr R. Weyhe and al. ,www. accurec.de.. [38] M. Wachtler, B. Emmermacher, M. Wohlfahrt-Mehrens, H. Do¨ring PD-18 Safe Discharge of Damaged Li-Ion Batteries, Battery Conference 2015, Aachen, April 27 29, 2015. [39] Safe Discharge of Damaged Li-Ion Batteries. M. Wachtler and al. ZSW Zentrum fu¨r Sonnenenergie und Wasserstoff-Forschung Helmholtzstrasse, 8 89081 Ulm. Germany. E-Mail. ,[email protected]..
REFERENCES
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[40] ,http://www.midtronics.com/shop/products-1/battery-chargers-and-maintenance-products/diagnosticchargers/gr-series/grx-5100.. [41] Personal communication. Mrs A. Arnberger : [email protected].. [42] ,http://www.toxcommc.com/toxco.html.. [43] ,http://www.rechargebatteries.org/wp-content/uploads/2014/04/RECHARGE-Information-Paper-on-Reuse-and-second-use-October-2014-v.14.pdf.. [44] ,http://europa.eu/rapid/press-release_IP-15-6203_en.htm.. [45] ,http://www.unece.org/fileadmin/DAM/trans/doc/2014/wp29/ECE-TRANS-WP29-2014-81e.pdf.. [46] Extracted from REF. (43) PART I. [47] Extracted from REF. (43) PART II - ANNEXES.