Journal Pre-proof Environmental impact of spent lithium ION batteries and green recycling perspectives by organic acids – A review Pratima Meshram, Abhilash Mishra, Abhilash, Rina Sahu PII:
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Please cite this article as: Meshram, P., Mishra, A., Abhilash, , Sahu, R., Environmental impact of spent lithium ION batteries and green recycling perspectives by organic acids – A review, Chemosphere (2019), doi: https://doi.org/10.1016/j.chemosphere.2019.125291. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier Ltd.
Battery Materials are less prone to affect the food chain, and efficient utilisation might resurrect the metal depletion imbalance
ENVIRONMENTAL IMPACT OF SPENT LITHIUM ION BATTERIES AND GREEN RECYCLING
PERSPECTIVES BY ORGANIC ACIDS – A REVIEW
Pratima Meshram1, Abhilash Mishra2, Abhilash1, Rina Sahu2
CSIR-National Metallurgical Laboratory, Jamshedpur
National Institute of Technology, Jamshedpur
Tel: +91-657-2345274; Fax: +91-657-2345213; Email: [email protected]
Abstract: The huge usage of rechargeable batteries in electronics has added to a recurrent
problem worldwide in generating tonnage of spent lithium-ion batteries (LIBs). The inadequacy
of the resources of the depleting critical metals has also been described in vogue. The
environmental assessment of the life cycle of the LIBs has been elucidated vis-a-vis the effects
of raw material supply, transportation, and recycling. Based on the available work for recycling
technologies, this review also attempts to elicit the various methods practiced in
discharging/dismantling, classification, and separation of components followed by metal
recovery. The authors have reviewed the major developments in the area of recycling of
cathode material by using various acids for extraction of metals from spent LIBs, compared the
merits and demerits of acids used and presented a comprehensive outlook to the processes
formulated vis-à-vis imperative need for using green techniques. The necessity for benign
recycling methods is stressed upon to alleviate the need for high temperature and oxidative
acid leaching conditions. The various green lixiviants (organic acids) attempted to extract
metals from spent LIBs have been discussed in detail with respect to the mechanism, efficacies
as well as the various factors (selectivity, cost, etc.) that govern the use of organic acids in
battery recycling. It was ascertained that the GHG emissions to extract Co using organic acids
stand 1/8 of that using an inorganic acid leaching process. Efforts need to be envisaged in
separating the leached metals from these lixiviants ensuring economics and environmental
Keywords: environmental assessment; spent LIBs; recycling; pretreatment; metal; organic acids 1
Every year the LIBs production increase rapidly and the production of LIBs all over the world has
reached 7.8 billion in 2016, which is grown by 40% as compared to 5.6 billion in 2015 (Zheng et
al., 2018). Lithium-ion batteries (LIBs) have been introduced by Sony Corp. in 1991, after which
it gains more attention as compare to any other available batteries (Zou et al., 2013; Georgi-
Maschler et al., 2012). Spent LIBs recycling gain remarkable attention in the past few years due
to the rapid increase in demand for critical metals and negative impact on environmental from
solid hazardous waste scrapping and disposal. Lithium-ion batteries find their applications
mainly in portable electronic devices such as mobile phones, power banks, laptops and cameras
due to their advantageous features including, large range of operating temperatures, high
energy density, long life cycles, and sensible discharge resistance. LIBs are not only dominating
the portable electronic markets like mobile phone and laptop but also become the first choice
for electronic automobiles in the future. Automakers like Nissan, Toyota, Honda, General
Motors and Volkswagen announced plans to utilize LIBs in upcoming electric and hybrid
vehicles (Ferreira et al, 2009). LIBs technologies are more advanced than other batteries in
terms of energy density and higher voltage per cell, which is a crucial factor for hybrid and
electric vehicles (Zou et al., 2013; Li et al., 2012).
Spent LIBs not only contain significant quantities of valuable materials but also contain
hazardous materials. The release and fate (i.e., transport and transformation) of metals in these
batteries or the batteries as such into the environmental system is a very important issue for
discussion. The uncontrolled disposal of these batteries creates a major risk to health, the
environment, and a significant waste of valuable resources. Although a few organizations, such
as Portable Rechargeable Battery Association (PRBA), Rechargeable Battery Recycling
Corporation (RBRC) and European Portable Battery Association (EPBA) and some more
organizations in the USA and Europe are involved in collection and recycling of batteries but at
present there are no such legislation and regulations of collecting and recycling of batteries in
most of the developing countries. Battery metals such as lithium, nickel, cobalt, and manganese
as well as the electrolytes may have adverse human health and environmental effects. The
amount and the form in which the respective component material is present in the battery can
determine the quantum of risk associated with the batteries. Disposal in landfills or by
incineration is preferred often during the phase-out of technologies, but green recycling is
unanimously the better option as it can diminish the adverse effect (if any) on the environment
LIBs cell is predominantly composed of three different layers that are cathode layer, an
anode layer, a separator (PVC), electrolyte, and polymer enclosed with metallic shells (Gratz et
al., 2014). The composition of different parts of LIBs vis-à-vis its percentage weight distribution
per battery is shown in Table-S1. The cathode material in LIBs is mostly metal oxide in the form
of LixMyOz such as lithium cobalt oxide, lithium manganese oxide and many more coated on
aluminum foil. Among these the recycling of spent batteries comprising LiCoO2 as the electrode
material has many positive aspects since the cobalt and lithium in it can be an alternative
resource for the future. The anode is the negative active material coated with active material
(graphite) on copper foil. The electrolyte salts used include LiPF6 and LiBF4. Lithium hexafluoride
phosphate (LiPF6) is preferably used lithium salt in most of the LIBs (Zeng, et al., 2014). A
separator is mainly used between anode and cathode layers to maintain the space and avoid
contact between them. Separator (a microporous film) is made up of polymers like
polypropylene (PP) or polyethylene. The function of separator is to avoid short circuits between
the electrodes as well as it also used as a safety purpose by sealing the electrodes when the cell
is overheating. Around 85% of the lithium-ion batteries used in worldwide have a size in
between the range of 5 to 25 g and around 15% have sizes between 25 to 75 g. Espinosa, et al.,
(2004) mentioned that every laptop usually consists of four to six cells and the average weight
of single cell is 45 g, whereas mobile phones having a single cell with 22 g of average size. Table-
1 shows the weight of different parts of mobile and laptop LIBs. The differences in composition
matter for the economics of processing of the different types of batteries; but the
environmental effects are mostly similar. In recent years, there have been few comprehensive
reviews on the subject of LIB green recycling. Zhang et al. (2018) emphasized on the various
aspects of recycling and leaching of LIBs including the process steps, and separation of metals
followed by LCA of the process methods. Huang et al (2018) do emphasize similar aspects but
mostly focused on product manufacturing from recycled LIBs. Kim et al. (2018) strictly discuss
end-of-life battery management and material flow analysis in South Korea instead of a global
perspective. Boxall et al. (2018) reviewed the projections of LIB waste generation and potential
for innovation for LIB recycling only for Australia. Zeng et al. (2014) attempt to review the
status of the recycling processes of spent LIBs, introduce the structure and components of the
batteries, and the problems encountered. However, no of these reviews have been able to
assess the environmental impact during raw material production, battery production,
distribution and transportation, usage and green recycling in a collective mode.
2. Environmental Assessment
The life cycle of lithium-ion battery (Fig.1) defines the complexity in disposition of spent LIBs
due to presence of various interim routes like reuse in batteries, use of remanufacturing
material in batteries, and regeneration of cathode before recycling for use as battery grade
material by stoichiometric additions. A detailed environmental assessment for the production
of LIBs as well as their recycling has been put forth with the need to pinpoint the precise unit
operation that contributes maximum towards environmental degradation and emission of
greenhouse gases. The environmental impacts of the production of several different batteries
were presented by McManus (2012), who reported that the materials required in lithium-ion
battery production have the most significant contribution to greenhouse gases and metal
depletion. The energy requirement for the production of these batteries was reported to about
90 MJ per Kg and 12.5 kg of CO2 equivalent emitted for per Kg of LIBs. Ordoñez et al., (2016)
reported that about 1100 t of heavy metals and 200 t of toxic electrolytes were generated from
4000 t of spent LIBs. Apart from this, there are many occupational hazards during disposal and
recycling of LIBs vis-à-vis components, which is depicted in Table-2. The major contributors to
environmental and health impact start from its raw material production followed by battery
production, its distribution, and transportation requirements, uses, charging and maintenance
and finally recycling and waste management (Corbus and Hammel, 1995). Recycling efforts are
mainly focused on cathode materials because of their relative mass and presence of critical
metals (Kim et al., 2018; Song et al., 2019). The cradle to grave pathway via all these stages
needs minimization ensuring a shift to adoption of a circular economy approach to preventing
the environment and health effects.
2.1. Effects of raw material production: The raw material production for batteries have a huge
ramifying effect. Mostly the raw materials used in LIBs are extracted from their respective ores
with mainly focusing on lithium, cobalt, nickel, and manganese as they are used in the
production of cathode materials in the lithium-ion batteries. Cobalt is mainly extracted from its
ores accompanied by nickel or copper along with the little amount of arsenic and silver as well.
The worldwide scenario of cobalt generation mainly includes 44% from the copper industry,
50% from the nickel industry and remaining production are from primary cobalt operations. The
approximate reserve of cobalt is about 7,100,000 MT (USGS, 2018). African countries,
Democratic Republic of Congo (DRC) and Zambia are the main producers of cobalt while Russia,
Australia, China, Cuba, Canada, and Madagascar are the other important producers as shown in
Fig. 2 and the location of reserves are presented in Table-3. Lithium is an important metal as it
shares the largest market in the production of LIBs. Chile, Australia, and Brazil are the main
producers of lithium while other important producers include Argentina, Portugal, the U.S., and
China. The estimated reserves for lithium are about 16,000,000 MT, out of which Chile has
about 53% and Argentina has 14% (USGS, 2018). The estimated reserves for manganese is
about 680,000 MT (USGS, 2018). South Africa (75% of world resources), Ukraine (10%),
Australia, and China are the major producers and suppliers of manganese, while other
important producers include Brazil, India, and Indonesia. Cuba and Australia are the major
producers of nickel across the worldwide while Brazil, Russia, the Philippines, and Indonesia are
also important producers of nickel. The estimated reserve for nickel is about 74,000,000 MT. It
is estimated that cobalt and lithium will be going to face a serious deficiency in the upcoming
years. In the year 2016, the consumption rate of Co for batteries has increased to 13.7% and
will reach 20.3% in 2018 (Lv et al., 2018). According to USGS, 2018 the reserve for valuable
metals like Li and Co is 53 million tons and 5 million tons respectively. Apart from metals, it is
important to consider graphite recycling especially in countries with less primary production
(Song et al., 2019).
Mining, mineral processing, smelting, leaching, and refining are the major processes applied for
the conversion of the metal and components to the specific form of material utilized in the
batteries. Taking into consideration a LIB for EVs, the production of wrought aluminum
consumes 2-3kg CO2 equivalents per kg of battery, surpassing it more than an actual alumina
refinery. The electrode viz., LiMn2O4, production consumes nearly 800-1000 kg CO2 equivalents
per kg of battery. Even the consumption is 100-500 kg CO2 equivalents per kg of battery for
production of electrolytes like DMC, LiFP6, which after discharging of batteries pose high threats
of being emanated into the environment (Kang et al., 2013; Dunn et al., 2016). However,
currently owing to the stringent regulation and environment pollution acts these days, all the
unit operation in the production of raw materials releases fewer emissions.
2.2. Effects during battery production: Water pollution, air emission, and solid wastes may
generate during LIBs manufacturing, which is harmful to health as well as the environment. Due
to the increasing demand for these types of batteries, the Greenhouse gas (GHG) emission
associated with its production has become a major concern. Recently Hao et al., (2017)
reported the GHG emission for the three types of most commonly used cathode materials of
LIBs. According to their report, for the production of a 28 kWh battery of LFP, NMC and LMO
cathode materials, about 3061 KgCO2-eq, 2912 kgCO2-eq, and 2705 kgCO2-eq GHG emissions is 7
generated respectively. A more detailed perspective id shown in Table-4, which describes the
energy consumption vis-à-vis type of cathode chemistry and its share on contribution to GHG
emissions. Though used prevalent and economically suitable, LCO’s contribute 80% to GHG
emissions. The emitted gas contains 40% carbon monoxide (CO), 20% carbon dioxide (CO2) and
30% hydrogen (H2) as well as traces of <3% hydrogen fluoride (HF) and nearly 7% hydrocarbons.
2.3. Effect due to transportation and distribution: Battery waste management is imperatively
affected by sorting, packing, storage and transportation. To avoid fire or incident, the batteries
must be packaged according to stringent requirements. A non-conductive material should be
used to prevent the short-circuiting against each other as well as the sides of metal packaging.
Approved packaging container viz., metal drum, wooden box, fiberboard or other materials are
used for this purpose. Separated packing is required for leakage of vented cells (Miller and Bill
McLaughlin, 2001). The batteries are then placed into an approved packaging group II container
with suitable cushioning (vermiculite) to reduce vibration and shock. The inside of the
packaging should be lined with a heavy plastic/polypropylene liner. The outside of the package
should be labeled with a "Miscellaneous" Class 9 label.
2.4. Effect during battery usage and maintenance: By increasing roundtrip efficiency and,
minimizing the amount of energy that is lost during these charging cycles, the environmental
impacts incurred by the energy used to charge batteries could be reduced.
2.5. Effects during recycling: Numerous companies around the world are licensed and currently
working in the field of battery recycling. The major firms engaged in LIBs recycling are Accurec,
Umicore process, Batrec AG, Sony-Sumitomo, Toxco and many more as mentioned in Table-6.
The primary aim of recycling batteries at the industrial and laboratory is to extract metals like
cobalt, lithium, nickel, and manganese. Recycling of lithium-ion batteries is more common than
Ni-Cd and Ni-MH batteries (Ellis and Mirza, 2011).
The advanced battery chemistries of LIBs offer improved systems because they incorporate less
hazardous materials and may use hydrometallurgical rather than pyrometallurgical or smelting
processes for recycling. In addition to increasing efficiency in the use of resources, recycling
provides direct environmental benefits. For instance, the GHG emissions of an LMO lithium-ion
battery could be reduced by up to 50% over its lifetime if it uses recycled cathode, aluminium,
and copper instead of virgin materials (Dunn et al., 2012). Moreover, recycling LCO batteries
results in a reduction in SOx emissions by almost 100%, largely because it avoids the SOx-
intensive smelting step of virgin cobalt recovery (Dunn et al., 2015). LCA analysis when
compared among the outputs of battery production from pyro-metallurgy and hydrometallurgy
via-a-vis raw material production, pyro-metallurgy exceeding production from raw materials in
electricity consumption and double release of PM2.5 and VOCs than that of hydrometallurgy
(Arambarri et al., 2019).
Another very important parameter that should become an integral part of the life cycle and
environmental impact assessment study for batteries is the form of the material in the battery
system itself. While evaluating the effects of battery materials, the focus presumably shifts to
the toxic nomenclatures of Ni, Co, Cd, Mn, Zn as they translocate easily in the environment. The
battery manufacturers frequently modify their battery chemistries, which makes it difficult to
incorporate recovered materials. For example, the compound normally used in a Ni-Cd battery
is an insoluble cadmium oxide but assumptions are made based on the highly soluble cadmium
chloride existing in the literature on toxicology. The MnO2 and Mn3O4 phase of manganese,
ZnMn2O4 phases of zinc and LiNiO2 phase of nickel in spent LIBs are not so easily soluble in
normal temperature and pressure, and thus must be a decisive factor when assessing their
effects too. This problem is yet to be addressed in life cycle analyses of battery systems, and it
is difficult to state how much it might affect them when it is addressed. The new chemistries
replace the old ones irrespective of geographical locations. Apart from Europe and China, India
has become a prominent destination for e-waste recyclers. Indian mobile manufacturing
industry is expected to touch Rs 160,000 crore by the end of 2019. In 2017, the Indian mobile
manufacturing industry produced 22 million mobile phones and the industry would produce 50
million mobile phones by 2020. The service life of LIBs is generally 3 - 4 years or average life is
1000 cycles (Chen et al., 2018).
217 218 219
3. The necessity of environmentally benign recycling methods
Several methods have been proposed for the extraction of valuable metals from waste/spent
LIBs. These can be categorized into pyrometallurgy, hydrometallurgy, and bio-hydrometallurgy.
Out of these, hydrometallurgy is a superior process in terms of high concentration of recycled
metal, low energy cost, and low emission. Nowadays the use of LIBs tends to increase rapidly
for the upcoming years, hence new recycling techniques should be developed and existing 10
processes should be optimized to treat spent Li-ion batteries to obtain sustainability (Renault et
al., 2014). Numerous researchers have developed techniques for extraction of metals from
waste LIBs by using inorganic acids like HCl (Wang et al., 2009; Shuva and Kurny, 2013; Guzolu
et al., 2017), HNO3 (Lee and Rhee, 2002) and H2SO4 (Meshram et al., 2014; Chen and Ho, 2018).
To diminish the negative impact of inorganic acids, reducing environmental pollution and to
find environmentally friendly treatment, many researchers in recent years use green recycling
tools like organic acids viz., citric acid (C6H8O7) (Zheng et al., 2016; Fan et al., 2016), oxalic acid
(H2C2O4) (Sun and Qui, 2012; Zeng et al., 2015), DL-malic acid (C4H5O6) (Li et al., 2010a; Sun et
al., 2017), L-tartaric acid (C4H6O6) (He et al., 2017; Cheng, 2018). To reduce the hazardous risks
to humans as well as to the environment, in recent times some effort has been made by the
researcher to develop an efficient and eco-friendly technique for extracting valuable metals and
recycle the spent LIBs. The use of organic acid for leaching to dissolve valuable metals like
lithium, cobalt, nickel, and manganese from waste LIBs have to gain more attention.
Nonetheless, this overview also gives a comprehensive record of comparison between
inorganic and organic acid along with, extensive usage of organic acid as green leaching
reagents for recycling and extracting metals from spent of LIBs. Gao et al (2018) compare both
the lixiviants to stress upon the use of inorganic media for higher extraction and organic media
for better selectivity based on the pH and dissociation constant, however the mechanism
missing is evident in this review. Lv et al., (2017) describe the procedure for recycling lithium-
ion is divided into two basic categories of the simple procedure and combination process as
shown in Fig.3.
3.1. Discharging and dismantling and pre-treatment of LIBs: This is an important component in
battery recycling in general. The first basic step before dismantling is to discharge the LIBs
completely to avoid explosion or self-ignition. Different researchers have opted various
methods as described in Table-S2. LIBs can be dismantled manually using a plier and a
screwdriver (generically can be referred as cutting device) and split into components like plastic
shells, metallic shells, polymer, PVC, anodes foil, and cathodes foil. Metallic components, plastic
parts, and separators can be directly recycled. The high purity plastic and metallic crusts and
the organic separators comprise relatively homogeneous components. They can be directly
centrally collected, compacted, and then sent to specialized plants for further reuse in new
products. Most of the researchers preferred a single-stage pretreatment technique for
dismantling of LIBs by directly crushing them into small sizes, followed by magnetic separation
to separate metallic parts. In the end, fine crushing and sieving process was employed to obtain
cathode active material as a feed to the leaching process. The dismantling process vis-à-vis the
components is presented in Fig.4. Many researchers employed different methods for extracting
cathode material from Al foil and concluded that pretreatment methods always play a vital role
which includes solvent dissolution method, ultrasonic separation, thermal treatment method,
and mechanical methods which are shown in Table-S3 along with its merits and demerits. With
the rapid development of mechanization, the mechanical and automatic dismantling of WEEE is
recently becoming a hot spot. Nowadays some new attempts to automatically disassemble
mobile phones are emerging (Zhang et al., 2018). Elaborative dismantling via full automatic
machines is expected to be the desired ideal operation for spent LIB recycling.
After separating cathode active material from Al foils, it is used for subsequent leaching process
as feed. Table-6 shows the composition of different cathode active material used by different
researchers. The literature survey shows that mechanical treatment, hydrometallurgy
(Meshram et al., 2014), pyrometallurgy (Paulino et al., 2008), and biotreatment (Brandl and
Faramarzi, 2006; Kim et al., 2016) are the main available recycling methods for extracting the
valuable metals from waste LIBs. Apart from these methods, metals can also be extracted by
bacteria and fungi (Horeh et al., 2016; Mishra et al., 2008; Xin et al., 2009). Among all the
available recycling approaches, hydrometallurgy method dominates due to being simple, high
recovery and options of closed-loop operations. Biotreatment has also created some attention
due to the selective and green recovery of some metals from the waste lithium-ion batteries.
3.2. Hydrometallurgical Processing of LIBs: Hydrometallurgical processing of spent LIBs is a
simple and efficient method for extracting all valuable metals. In the hydrometallurgical
technique, number of processes are carried out to dissolve and extract metals from an aqueous
medium; i.e., acid leaching (Meshram et al., 2015a; Paulino et al., 2008), chemical precipitation
(Guzolu et al., 2017; Yang et al., 2017), solvent extraction (Yang et al., 2017; Paulino et al.,
2008), and electrochemical separation (Chagnes and Pospiech, 2013; Garcia et al., 2017; Xu et
al., 2008; Zhang et al., 2013). The first basic step is to dissolve Co, Li, Ni, and Mn by acid
leaching, and then these metals are extracted from the solution (leach liquor) by a suitable
method. Fig.5 shows the typical flowchart for the recycling of waste lithium-ion batteries
through the hydrometallurgical process.
hydrometallurgical treatments to extract valuable metals from solution as they are more
flexible and reliable, eco- friendly, energy consumption is less, good rate of reaction, high purity
and extract all the metals present in spent LIBs (Garcia et al., 2017; Sun and Qiu, 2011; Sun et
al., 2017). The most widely used method to extract valuable metals from waste LIBs is acid
leaching. There are different parameters on which the leaching rate of different metals like
cobalt, lithium, nickel, and manganese depends on lixiviant concentration, pulp density,
reaction temperature, time.
The lixiviants are mainly classified as inorganic and organic acids; merits and demerits of which
are described in Table-7. The use of inorganic acids can lead to high consumption of water,
chemicals, and in long term adding to the corrosion of equipment and generation of secondary
wastes (Tesfaye et al., 2017; Innocenzi et al., 2017). Rocchetti et al., (2013) also explained the
gas emission from the inorganic acid to recycle waste LIBs, and conclude that the gas like CO2,
Cl2, SO2, ethane, and phosphorus will be emitted. Another disadvantage of using inorganic acid
is the pH of the solution (leach liquor) is very low and metals cannot be extracted directly from
the solution hence the process becomes more complicated (Yao et al., 2018). With inorganic
acids, disposal of water containing acid,
problems leading to economic and energy losses.
Whereas organic acids termed as “GREEN LIXIVIANTS” are easy to manage, as they are
biodegradable, do not emits harmful gases to the atmosphere (He et al., 2017; Li et al., 2018).
Chen et al., (2015); Horeh et al., (2016); explain about the advantage of organic acid and the
use of organic acids as eco-friendly and efficient lixiviant, more to that there are no harmful
gases emitted, delayed the corrosion of equipment as well as it is for the operators, and few
organic acids gives selective leaching of valuable metals present in waste LIBs. A most
hazardous fumes, acidic leachates are the main
important factor associated with organic acids is, they can be recycled after leaching processes
(Chen et al., 2015). Golmohammadzadeh et al., (2017) and Rocchetti et al., (2013) reported that
organic acids are costlier than the inorganic acids, still it's usage is cost-effective as it avoids
negative impact on the environment which is mostly associated with inorganic acids.
Numerous researchers used inorganic acid like sulfuric acid (Meshram et al., 2015b; Chen and
Ho, 2018), hydrochloric acid (Guzolu et al., 2017; Wang et al., 2009; Shuva and Kurny, 2013),
nitric acid (Lee and Rhee, 2003; ), Phosphoric acid (Pinna et al., 2017) and hydrofluoric acid
(Suarez et al., 2017) as a leaching reagent and showed very high recovery of metals from spent
lithium-ion batteries. Some selected work is listed in Table-8 using inorganic acid as a lixiviant
for spent LIBs, and Fig.6 shows the schematic recovery process by using different inorganic acid
as the lixiviant.
Hydrochloric acid has an excellent leaching efficiency as compared to another inorganic acid
(Joulie et al., 2014), but Cl2 was produced and leads to a potential environmental problem as
shown in Eq. (1).
2LiCoO2 + 8HCl 2CoCl2 + Cl2 + 2LiCl + 4H2O
Sulfuric acid is mostly used in the presence of hydrogen peroxide (H2O2) as a reducing agent as
it enhances the leaching efficiency. Eq. (2) shows the chemical reaction of cathode active
material with hydrogen peroxide:
2LiCoO2 + 3H2SO4+ 3H2O2 2CoSO4 + Li2SO4
In spite of the fact inorganic acids are stronger oxidants than organic ones; the latter is
thermally stable, leaves no negative impact on the environment, and usually form strong
chelates (Deng et al., 2015). Different organic acids, including oxalic acid (Sun and Qui, 2012;
Zeng et al., 2015), DL-malic acid (Sun et al., 2018; Li et al., 2013), tartaric acid (Chen et al., 2018;
Cheng, 2018; He et al., 2017) and citric acid (Li et al., 2010b; Fan et al., 2016; Chen et al., 2015;
Zheng et al., 2016) shows similar leaching performance as with inorganic acids, which signifies
that these eco-friendly lixiviants can efficiently recover metals from spent LIBs. Few reviews
(Zhang et al. 2018, Huang et al. 2018, Zeng et al., 2014) have emphasized the merits of selected
work on the use of organic acids in recycling of spent LIBs; however, the following section
attempts to discuss and deliberate all such work carried out and their mechanism using organic
3.2.1. Citric Acid: Some of the research that used citric acid for leaching of LIBs vis-à-vis
conditions is summarized in Table-9. A hydrometallurgical process to recover metals by using
citric acid and H2O2 based on leaching was introduced by Li et al., (2010b). Citric acid can leach
90% of cobalt and 100% of lithium by using 1% H2O2, citric acid of 1.25M at 90 oC with 20 g/L
pulp density in 30 min. The extraction of Li and Co from waste LIBs in presence of C6H8O7·H2O
and H2O2 can be presented by Eq. (3)
352 353 354
6H3Cit (aq) + 2LiCoO2 (s) + H2O2 (aq) 2Li+ (aq) + 6H2Cit- (aq) + 2Co2+ (aq) + 4H2O + O2 (g)
Comparison of citric acid with two different organic acid namely aspartic and malic is reported
by Li et al. (2013) by using hydrogen peroxide as a reducing reagents and reported that 100 % Li
and > 90% Co were recovered using malic and citric acids whereas by using aspartic acid the
recovery is very low because of its low acidity. Golmohammadzadeh et al. (2017) reported by
comparing four different organic acids (DL-malic, oxalic, citric and acetic acid) finds the best
sequence is citric acid > DL-malic > acetic > oxalic acid, in terms of their efficiency to recover
cobalt and lithium from spent LIBs.
Extraction of valuable metals by hydrometallurgical process from cathode active material
(LiNi1/3Co1/3Mn1/3O2) of spent LIBs using citric acid was investigated by Chen and Zhou, (2014). It
was observed that about 98% Ni, and Mn, 89% Li and 97% Co was recovered by using 2 M citric
acid in presence of 2% H2O2 and 50 g/L pulp density in 80 min at 70 oC. For the recovery
process, a combined method of selective precipitation and solvent extraction was performed to
separate and recover each metal from the leach solution. Firstly, cobalt and nickel were
selectively precipitated by ammonium oxalate ((NH4)2C2O4) and dimethylglyoxime (C4H8N2O2)
sequentially Fig. 7. Then manganese was extracted by Na-D2EHPA and stripping was carried out
with sulfuric acid. The manganese was recovered as MnSO4 in the aqueous phase and D2EHPA
could be reused after saponification. Finally, lithium was precipitated by 0.5 M Na3PO4 and
about 89% of the lithium was recovered as Li3PO4.
Several researchers work on citric acid and proposed that 90 °C is the optimum temperature for
extraction of cobalt and lithium (Fan et al., 2016; Li et al., 2010b; Li et al., 2013; Zheng et al.,
2016). To avoid the negative influence related to high-temperature, several researchers
reported that 60-80 oC as the preferred temperature range for extraction of valuable metals
like cobalt and lithium (Chen et al., 2015; Golmohammadzadeh et al., 2017). While Aaltonen et
al., (2017) investigated that at room temperature (25 oC) citric acid is able to leach 97% of
cobalt, 89% of lithium along with 98%, and 93% of manganese and nickel respectively by using 1
% H2O2, with 50 g/L pulp density in 24 h. Recently, Ma et al., (2017) reported that the citric acid
is beneficial for the selective dissolution of metals in the mixed battery waste as compared to
the sulfuric acid as leaching reagent. They reported that citric acid with hydrogen peroxide as
oxidant favored valuable metals dissolution (Co and Ni) but not promoted the dissolution of
Mn, Fe, Zn, and the other metals. They also showed with thermodynamic calculations that
metals precipitate more easily in a sulfuric acid system than in the citric acid system. Recently,
Musariri et al (2019) used citric acid to evaluate their effect on metal leaching rate from spent
LIBs. They concluded that with the increase in the acid concentration of citric acid from 1M to
1.5M at 95 °C, an increase in metal leaching rate was observed. Maximum recovery of 95% Co,
97% Li and 99% Ni recoveries within 30 min were obtained in 1.5M citric acid.
3.2.2. Tartaric Acid: Tartaric acid acts as a good buffer in a wide pH range 2.1-7.4
(Golmohammadzadeh et al., 2018). The acid has been reported as an efficient chelating agent.
Very few researchers have been worked on tartaric acid in the recovery of metals from waste
lithium-ion batteries as mentioned in Table-10.
396 397 398
The leaching reaction of tartaric acid with LiCoO2 in presence of H2O2 can be represented in Eq.
2LiCoO2 (s) +3C4H6O6 (aq) + H2O2 (aq)
C4H4O6Li2 (aq) + 2C4H4O6Co (aq) + 4H2O (l) + O2 (g)
For increasing the rate of dissolution, the addition of reducing reagent (H2O2) was essential.
H2O2 helps in the dissolution of cobalt and lithium as two metals are contained in the same
oxide compound. In the absence of H2O2, the aforementioned recoveries were about less than
31%, while with 4 % H2O2 at 70 o C in 30 min and 17 g/L pulp density, the recoveries of all the
metals (Co, Mn, Ni, and Li) increased to > 98% (He et al., 2017). Results also showed that
tartaric acid produces a solution environment with lower pH as compared to ascorbic acid, DL-
malic acid, succinic acid, and L-aspartic acid.
Nayaka et al., (2016) dissolve more than 95% of LiCoO2 in presence of tartaric and ascorbic acid
by employing a reductive complexing mechanism. Eq. (5) shows the dissolution process of
LiCoO2 with C4H4O6 and confirms the reduction of Co(III)-tartrate (CoC4H5NO4) to form Co(II)-
tartrate (CoC4H2O4), followed by cobalt precipitation as cobalt oxalate.
4LiCoO2 + 12C4H4O6 4LiC4H3O6+ 4 Co(C4H3O6)2+ 6 H2O
The effect of different reductants (glucose, ascorbic acid, and hydrogen peroxide) on leaching
of lithium and cobalt from LIBs in tartaric acid solution was reported by Cheng et al (2018). The
group reported that among these three reducing agents, hydrogen peroxide exhibits a higher
ability to convert Co3+ of the cathode active materials to soluble Co2+. The recovery rate of Li
and Co was 98% and 97% respectively in the presence of 0.6 M tartaric acid with 3 % H2O2 at 80
°C in 30 min.
3.2.3. Malic Acid: An environmental friendly recycling technique for recovery of lithium and
cobalt from waste LIBs by using malic acid was reported by Li et al., (2010a) and results showed
that 93% Co and 94% Li can be leached using 1.5 M DL-malic acid in presence of 2.0 % H2O2, 20
g/L pulp density in 40 min at 90
recovery by using malic acid. Result also showed that the leaching efficiency of Li and Co
increases with an increase in reaction time and temperature. The leaching reaction of waste
LiCoO2 with malic acid can be represented in Eq. (6) as follows:
C. Table-11 summaries the optimal condition for metal
4LiCoO2(s) + 12C4H6O5 (as) 4LiC4H5O5 (aq) + 4CoC4H5O5 (aq) + 6H2O (l) + O2 (g)
Li et al., (2010a) also confirmed that for increasing the rate of dissolution, the addition of
reducing reagent (H2O2) was essential because the two metals were present in the same oxide
phase. Eq. (7) shows the reaction of waste cathode powder in the presence H2O2:
439 440 441
2LiCoO2(s) + 6C4H6O5 (aq) +H2O2 4LiC4H5O5 (aq) + 2CoC4H5O5 (aq) + 4H2O (l) + O2 (g)
Under similar conditions by just decreasing the reaction time from 40 min to 30 min, Li et al
(2013) reported the extraction of Li and Co from waste LIBs with DL-malic acid as leaching
reagent. With pure malic acid, ~54% Li and 37% Co could be extracted. However, by adding 2 %
H2O2, the recovery rate increased drastically to 99% Li and 90% Co adding to the embodied
energy of the process. The presence of two carboxyl functional groups and its higher solubility
in water improved the metal solubilization from spent LIBs (Li et al., 2010a).
Sustainable extraction of metals from spent LIBs in the presence of malic acid was investigated
by Sun et al (2017). At 40g/L pulp density, 80 oC in 30 min, 98.9 % Li and 94.3 % Co were
extracted using 1.2 M acid concentration. Golmohammadzadeh et al (2017) used room
temperature to extract 90.9 % Li and 80% Co and elucidated the two-step mechanism of
leaching in Eq. (8) and Eq. (9), where two moles of H+ released from DL-malic acid plays a vital
role to enhance the efficiency of leaching (Li et al., 2014).
H2C4H4O5 HC4H4O5- + H+
HC4H4O5- C4H4O52- + H+
457 458 459 460
Musariri et al (2019) used malic acid to evaluate their effect on metal leaching rate from spent
LIBs. Malic acid concentration did not affect leaching, and 1M concentration was most
appropriate to achieve 98% Co, 96% Li and 99% recoveries in 30min.
3.2.4. Oxalic Acid: Oxalic acid has been a widely used leaching agent for extraction and
chelation of metals from various secondary wastes, especially WEEE. Oxalic acid acts as an
agent for leaching as well as precipitation in hydrometallurgical studies. In this view, Zeng et al
(2015) attempted to extract Li and Co from waste LIBs by synchronous leaching and
precipitation using 2 M oxalic acid with 15 g/L pulp density at 95 °C for 150 min, achieving a
high recovery rate of 98% Li and 97% Co. Similarly, combined oxalate leaching and vacuum
pyrolysis for recovery of Li and Co from the waste LIBs were reported by Sun and Qiu (2012).
They used oxalate ion as a leaching agent to achieve 98% leaching efficiency using 1M oxalic
acid with 15% H2O2 (Eqs. 10 and 11) and 25 g/L pulp density at 80 °C for 120 min. The
separation was aided by differences in the solubility properties of lithium oxalates and cobalt
oxalates; as latter was insoluble in acid and thus precipitated, whereas the former being soluble
could be separately precipitated at high pH. Table-12 summaries the examples of various work
done to use oxalic acid for metal recovery from LIBs.
4H2C2O4 +2LiCoO2 LiHC2O4 +2CoC2O4 (s) +4H2O + 2CO2 (g)
3H2C2O4 +2LiCoO2 (s) +H2O2 Li2C2O4 +2CoC2O4 (s) +4H2O+O2 (g)
479 480 481 482
Recently, Aaltonen et al (2017) reported leaching of metals at room temperature using 1M
oxalic acid along with 1% H2O2 and found that oxalic acid can selectively recover lithium. This
value falsifies the claims of many researchers (Sun and Qiu, 2012, Zeng et al., 2015).
3.2.5. Other organic acids: Some other commonly used acids, though significantly less applied
to leach of spent LIBs, are succinic acid, ascorbic acid, aspartic acid, lactic acid, formic acid.
Table-13 mentions the optimized conditions for metal extraction from spent LIBs by using
different organic acids.
Li et al (2012) developed a hydrometallurgical process using ascorbic acid for the extraction of
lithium and cobalt from waste LIBs, where ascorbic acid worked as a leaching as well as the
reducing agent. Ascorbate ion with high reducing potential can avoid the use of deleterious
hydrogen peroxide to enhance leaching efficiency. Nearly 98.5% Li and 94.8% Co was recovered
as respective metal ascorbates using 1.25 M ascorbic acid with 25 g/L pulp density at 75 °C in 20
min. The leaching reaction is represented in Eq. (12) as follows:
4C6H8O6 + 2LiCoO2 C6H6O6 + C6H6O6Li2 + 2C6H6O6Co + 4H2O
Succinic acid was also used as a leaching reagent for cathode active material of LIBs. Li et al
(2015) reported nearly 100% Co and 96% Li extraction in presence of 1.5 M succinic acid, 4%
H2O2 and 15 g/L pulp density at 70 oC in 40 min. However, in the absence of reducing agent
(H2O2), only 41.98% Li and 19.72% Co were recovered in similar conditions.
Li et al. (2013) reported that due to the weak acidity and low solubility of aspartic acid in the
water, it is an inefficient agent for recovery of lithium and cobalt from spent LIBs and recovered
only 60 % lithium and cobalt. A closed-loop process for recovery of lithium carbonate from
cathode scrap of spent LIBs by using formic acid and it can be used as leachate and reductant
(Gao et al., 2017). The recovery rates of Li, Ni, Co, and Mn were found to be 95.46%, 98.22%,
99.96%, 99.96%, and 99.95% respectively. The chemical reactions during the leaching process
can be described in Eq. (13)
+6CHLiO2(aq)+3CO2 (g)+12H2O(aq) (13)
513 514 515
Recently, in a few studies, the leaching of LIBs with an acetic acid solution in the presence of
H2O2 is also reported (Natarajan et al., 2018; Gao et al., 2018). The reaction of the LCM type of
cathode material in acetic acid in the presence of H2O2 can be represented by equation (14) as
Li2CoMn3O8(s) + 10CH3COOH(aq) + 10H2O2(aq) 2CH3COOLi(aq)+ Co(CH3COO)2(aq) +
3Mn(CH3COO)2 (aq) + 8 H2O + 3O2
Natarajan et al. (2018) used acetic acid as lixiviant and H2O2 as a reductant for leaching of
mobile phone batteries. It was found that with 3 M Acetic acid and 7.5 vol % H2O2 as reducing
agent 99.9% Li, 98.7% Co, and 99.5% Mn were leached out from cathode material in 40 min at
70 oC and a pulp density of 20 g/L. Finally, Cobalt was recovered as cobalt sulfide with 99.2%
purity, and, MnCO3 and Li2CO3 being 98.7% and 99.4% pure respectively. Similarly, Gao et al.,
(2018) also use acetic acid as a lixiviant for selective recovery of valuable metals from spent
lithium-ion batteries and reported that the introduction of reductant accelerates the leaching
speed but decreases the influence of the acid concentration and S/L ratio. About 93.62% Co,
99.97% Li, 96.32% Mn and 92.67% Ni were recovered using 3.5 M acetic acid and 4% H2O2 in 1 h
at 60 oC with S/L ratio of 40 g/L. Li2CO3 was precipitated by adding a saturated Na2CO3 solution.
Lactic acid, which is widely distributed in nature and miscible with water, is also chosen for the
leaching of LIBs. The industrial production of lactic acid is also a green process, mainly through
fermentation. Given this, a green process was developed for the recycling of cathode material
of spent lithium-ion batteries using lactic acid (Li et al., 2017). The results showed that the
leaching efficiencies of Li, Ni, Co, and Mn reached >97% using 1.5 M lactic acid in presence of
0.5% H2O2 at 20 g/L pulp density in 20 min at 70 °C.
The examples of proven work on the use of green reagents in leaching of spent LIBs highlight
the organic acids as effective lixiviants and they have the potential to replace inorganic acids
owing to environmentally benign for processing of spent LIBs. The most important reason for
recycling batteries is to reduce environmental burden apart from meeting critical metal
demand. Thus, environmental impact assessment of the recycling process must be clearly
understood before choosing a process for it to be less energy-intensive as compared to virgin
processes to get the raw materials. The energy consumption is mainly affected by the choice of
leachant used. Inorganic leaching uses a reductant along with oxidizing acids, which increases
the embodied energy of the process as their production sustains environmental encumbrances.
As reported by Li et al., 2013, the energy consumption in producing citric acid is 35MJ/kg which
is 1/10 of the energy required to produce same concentration of sulfuric acid or butane. Apart
from this, the need for high temperatures is very less using organic acids. It is also possible to
recover the acid for recycling by decreasing the solution pH, causing the metals to precipitate
and reviving the acid by filtration. The waste organic acid would not pose a serious
environmental threat because it is a relatively benign substance used in foods, beverages, and
detergents. The use of inorganic acids with high concentration and temperature would result in
process emissions like sulfur, chloride, and nitrous oxides. The energy consumption of the
process of recycling with organic acids (Fig.7) vis-à-vis inorganic acid (sulfuric) was calculated as
9.3 and 14 MJ/kg (Li et al., 2013). There are possibilities to increase process energy efficiency by
further optimizing acid concentrations, and maximizing acid recycling.
The energy intensity of NMC cathode material manufacturing from virgin materials is 132
MJ/kg, which is nearly 25% less by organic acid-based recycling. Finally, using organic acid
enables this process to be competitive with producing virgin cobalt on an energy consumption
basis. The GHG emissions to extract 90% Co using a process with organic acids stands to be
close to 500 g/CO2
The selectivity for leaching Li over Co by oxalic acid is an additional advantage for processing
LiCoO2 cathodes. There lies another advantage of acids like citric and aspartic, which can avoid
oxidants and their effects during downstream processing. The onus now lies on developing
optimized process flow sheets to recover the extracted metals from the leach solutions as
4. Future Directions of Research
With the rise in the application of LIBs in electronics, the number of spent LIBs generated also
surmounts which need a recycling process to conserve the sustainable resource and save the
environment. Based on the above assessment, it can be ascertained that the being hazardous
per kg Co, which is nearly 4000g/CO2eq per kg Co using an inorganic acid
term with batteries, if handled and processed properly, can't be generically applied. The various
portals of battery processing ranging from raw material extraction to recycling in a closed-loop
cycle have its merits and demerits; but with the advent of technological changes and processing
options, battery recycling by safe mode is not a hard task to accomplish. Each cathode material
will be processed by a definite route, which governs its economics, energy consumption and
impact. We cannot recycle all LIBs by one technique, which ultimately leads to complications in
downstream processing and thus paves way for proper segregation of its type and properties.
Owing to large scale discarding of used LIBs, few successful examples worldwide can be a good
reference point for waste battery management for the developing world. By targeting a
complete waste battery collection system, improving EPR and promoting consumers to submit
spent batteries to assigned collection points; the uncontrolled collection issue can be sorted.
Battery dismantling must employ mechanized ways to separate crusts from cathode material.
The available literature survey related to recycling of spent LIBs highlights that mechanical
treatment, pyro-metallurgy, hydrometallurgy, and bio-treatment are the main major routes for
recycling of the waste lithium-ion batteries, hydrometallurgy dominates as compare to other
recycling technique as it an exploitable technology for the extraction of precious metals from
waste LIBs. Organic acids (effective and environmentally green leaching agents) have been
demonstrated to play a vital role in the extraction of lithium, nickel, cobalt, and manganese
from spent LIBs. Though they are weaker than inorganic ones, still organic acids have been
examined to a greater extent for leaching of spent LIBs thus helping to avoid oxidizing agents,
lowering complexity of managing the pregnant liquor and thus diminishing the energy loss. The
GHG emissions to extract 90% Co using a process with organic acids stands to be close to 500
process. Efforts need to be envisaged in separating the leached metals from these organic acid
media, to create a win-win situation of economics and environmental benefits.
per kg Co, which is nearly 4000g/CO2eq per kg Co using an inorganic acid leaching
599 600 601 602
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Figure Captions Fig.1: Life cycle assessment of lithium ion battery Fig.2: World map showing the reserves of Li, Co, Mn, Ni, and Graphite Fig.3: Different processes for recycling of spent LIBs Fig.4: Dismantling process for spent lithium-ion batteries Fig.5: Hydrometallurgical processing of spent LIBs Fig.6: Schematic recovery process by using different inorganic acid as lixiviant (Pinna et al., 2017; Qadir and Gulshan, 2018; Suarez et al., 2017; Shuva and Kurny, 2013; Guzolu et al., 2017; Chen and Ho, 2018; Chen et al., 2017) Fig.7: Schematic recovery process by using citric acid as lixiviant Table Captions Table-1: Weight of the component of the lithium-ion battery Table-2: Occupational standards for materials present in LIBs Table-3: Location of reserves of Li, Ni, Co, Mn and graphite globally Table-4: Energy consumption for various cathode chemistries in LIB production (Modified from Dunn et al., 2014) Table-5: Commercial process and companies engaged in recycling of batteries Table-6: Composition of different cathode active material used (Li et al., 2010b; Chen et al., 2011; Li et al., 2013; Jha et al., 2013; Meshram et al., 2015b; Khan et al., 2016; Fan et al., 2016; He et al., 2016; Sun et al., 2017; Gao et al., 2018; Golmohammadzadeh et al., 2018; Chen and Ho, 2018; Meshram et al., 2018) Table-7: Salient differences among processing parameters among organic and inorganic acid Table-8: Selected literature work on different inorganic acids as a lixiviant for LIBs Table-9: Summary of various published work on metal recovery from LiBs using citric acid Table-11: Summary of selective work on metal recovery from LIBs using tartaric acid Table-11: Summary of selective work on metal recovery from LIBs using malic acid Table-12: Summary of selective work on metal recovery from LIBs using oxalic acid Table-13: Summary of selective work on metal recovery from LIBs using other organic acids Supplementary Table Captions Table-S1: Parts and Composition of LIBs (Zhu et al., 2012; Gratz et al., 2014; Zeng et al., 2014; Younesi et al.,2015; Rojas and Zea, 2016; Toma et al., 2017; Horeh et al., 2017; Zhang et al., 2018; Qadir and Gulshan, 2018) Table-S2: Different discharging processes of LIBs Table-S3: Different pre-treatment process and their merits and demerits.
Table-1: Weight of the component of the lithium-ion battery Component
Total Battery assembly Plastic shell Metallic shell Cu electrode Al electrode Cathode material Polymer electrolyte
Weight of component Mobiles Laptops (Rojas and Zea, 2016) (Qadir and Gulshan, 2018) g % g % 17.8 316 1.8 5.2 50 15.8 4.3 12.2 51 16.1 3.5 9.8 17.2 5.4 7.5 2.4 5.4 15.1 130.9 41.4 0.6 1.8 6.8 2.2 1.8 5 20.9 6.6
Table-2: Occupational standards for materials present in LIBs Component Anode
Gastrointestinal issues in form of dust and mist irritate the eyes and mucous membranes Lung damaged by inhalation Respiratory effects, congestion, edema, and hemorrhage of the lung. Lung damage
Aluminium foil Cobalt oxide
Manganese (VI) oxide
Nickel oxide Lithium
Limits/Standard/Permissible Exposure Limits 0.1 mg/m3 as fume 1.0 mg/m3 as a dust or mist
Vimmerstedt et al., 1995
15 mg/m3 total particulates
15 mg/m3 as dust 5 mg/m3 as metal 1.0 * 104 TO 1.7 * 106 ng/m3
0.1 mg /m3 (TWA) 5 mg/m3 for manganese compounds as Mn 0.2 mg/m3 for manganese (TWA) 1 mg/m3 (TWA)
Skin carcinogenesis Non-hazardous if ingested with food or water
Toxic fume while heating/burning, (HF, PF5) Decomposes to irritating fumes when burnt Mild toxic when inhaled; Toxic fume while heating/burning (HF, PF5)
2.5 mg/m3 as F (long-term value) 15 mg/m3
2.5-5 TWA mg/m3
IARC, 1991; Barceloux, 1999; IARC, 2006
Vimmerstedt et al., 1995
Nordberg et al., 2011 Aral and VecchioSadus, 2008 Kang et al., 2013
Table-3: Location of reserves of Li, Ni, Co,Mn and graphite globally S. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37
Location Greenbushes, AUS Mt Marion, AUS Mt Cattlin, AUS Euriowie, AUS Finniss, AUS Zhabuye, China Qinghai, China DXC, China Jaijika, China Yichun, China Clayton, USA Searles lake, USA Great salt lake, USA Fox Creek, USA Bernic Lake, Canada Fox creek, Canada Wekusko, Canada La Motte, Canada La Corne, Canada H’ Muerto, Argentina Rincon, Argentina Olaroz, Argentina Cauchari, Argentina Bikita, Zimbabwe Atacama, Chile Maricunga, Chile Ethiudna, AUS Mount Gunson, AUS Akkarga, Russia Kola Peninsula, Russia Norilsk, Russia Kolwezi, DRC Kakanda, DRC Kamoya, DRC Konkola, Zambia Nchanga, Zambia Mufulira, Zambia
S. No. 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74
Location S. No. Nkana, Zambia 75 Keely-Frontier, Canada 76 TemagamiLorrain, 77 Canada Blackbird mine, USA 78 Ldaho mine, USA 79 Miramar, Cuba 80 La vega de Taco, Cuba 81 Palawan, Phillipines 82 Surigao, Phillipines 83 Ambatovy , Madagascar 84 Sudbury, Canada 85 Manitoba, Canada 86 Montreal, Canada 87 Québec, Canada 88 Kola Peninsula, Russia 89 Norilsk , Russia 90 Rio Tuba, Phillipines 91 Palawan, Phillipines 92 Toamasina, Madagascar 93 Ambatovy, Madagascar 94 Taolagnaro, Madagascar 95 Vale, Indonesia 96 Halmahera, Indonesia 97 Kidd Creek, S.A 98 Sudbury, S.A 99 Nkomati mine, S.A 100 Queensland, Aus 101 Tasmania, Aus 102 Yilgarn Craton, AUS 103 Taco bay, Cuba 104 Goiás, Brazil 105 Bahia, Brazil 106 Carajás , Brazil 107 Jinchang, China 108 Altay, China 109 Sundergarh, India 110 Balaghat, India 111
Location Ratnagiri, India Durg, India Saldanha Bay, S.A Hotazel, S.A Sishen mine, S.A Richards Bay, S.A Tarkwa Banso, Ghana Franceville, Gabon Nikopol, Ukraine Ushkatyn, Kazakhastan Jezkazgan, Kazakhastan Azul mine, Brazil Espigão d’Oesto, Brazil Corumbá, Brazil Pará, Brazil Port Hedland, AUS Woodie Woodie, AUS Bootu Creek mine, AUS Guiyang, China Wafangzi mine, China Jammu and Kashmir, India Jharkhand, India Kerala, India Tamil Nadu, India Liumao mine, China Pingdu mine, China Bahia, Brazil Tanga, Tanzania Merelani Hills, Tanzania Epanko, Tanzania Sonora, Mexico BalІkesir, Turkey Yozgat, Turkey Konya, Turkey Muğla, Turkey Graphmada, Madagascar Andapa, Madgascar
Table-4: Energy consumption for various cathode chemistries in LIB production (Modified from Dunn et al., 2014) Cathode Structure Weight Energy Preaparation Step Major Chemistry of consumption Energy Contribution contributor to battery (mmBtu/ton) energy consumption of total pack consumption (mmBtu/ton) (%) (kg) NMC Planar/layered 180 135 4.5 3 NiO LMR-NMC
LCO (Solid state) LCO (Hydrothermal) LFP (Hydrothermal) LFP (Solid state) LMO
170 Planar/layered Olivine 230 Olivine Spinel
Table-5: Commercial process and companies engaged in recycling of batteries Process Hydrometallurgy
Company (Name and Location) IPGNA Ent. (Recupyl), France
LiCoO2 and Co(OH)2
Sumitomo-Sony, Japan Toxco, Canada
LIBs Li, Ni-based battery
Eurodieuze, France Zimaval, France
Ni, Cd and steel Zn and Mn
Dowa, Japan Batrec AG, Switzerland
All Zn, Mn, Hg based battery All Batteries Li, Hg based battery
LIBs and Ni-MH
Co and Ni
Nippon Recycling center, Japan Accurec GmbH, Germany
Ni-Cd, Ni-MH, LIBs
Ni, Co, Cd, Al, Cu
Ni, Cd, Fe, LiCO3
Cd, Ni, Zn
Glencore Plc., Switzerland
LIBs and EV
Cu, Ni, Zn, Li
Ni, Co -
References Saloojee and Lloyd, 2015 Ellis and Mirza, 2011 Kushnir, 2015 Saloojee and Lloyd, 2015 Saloojee and Lloyd, 2015 Zhang et al., 2013 Kushnir, 2015 Ellis and Mirza, 2011 Ellis and Mirza, 2011 Zhang et al., 2013. Ellis and Mirza, 2011 Saloojee and Lloyd, 2015 Zhang et al., 2013 Kushnir, 2015 Ellis and Mirza, 2011 Ellis and Mirza, 2011 Kushnir, 2015 Saloojee and Lloyd, 2015 Zhang et al., 2013 Saloojee and Lloyd, 2015 Zhang et al., 2013 Ellis and Mirza, 2011
Table-6: Composition of different cathode active material used (Li et al., 2010b; Chen et al., 2011; Li et al., 2013; Jha et al., 2013; Meshram et al., 2015b; Khan et al., 2016; Fan et al., 2016; He et al., 2016; Sun et al., 2017; Gao et al., 2018; Golmohammadzadeh et al., 2018; Chen and Ho, 2018; Meshram et al., 2018) Metals (wt. %) Cathode Material LiCoO2 LiCoO2 LiCoO2 LiCoO2 LiCoO2 LiCoO2 NCM LiNi1/3Co1/3Mn1/3O2 LiNi1/3Co1/3Mn1/3O2 LiCoO2 LiCoO2 NCM
Co 53.8 26.77 57.94 23.67 74.6 58.76 35.52 20.26 18.65 58.11 25.83 35.8
Li 4.48 3.34 6.76 2.87 4.09 6.78 6.28 7.08 6.15 6.69 8.31 6.5
Ni 0.80 0.34 0.76 0.26 0.58 11.85 20.19 18.32 0.39 26.29 10.6
Mn 0.97 1.1 0.91 0.76 8.15 18.89 17.57 0.14 14.41 11.6
Table-7: Salient differences among processing parameters among organic and inorganic acid Parameters Selectivity Emission of gas Corrosion of equipment’s Separation/ Recovery Free energy (∆ Go) Flammable Overall Cost Example
Inorganic Acid No selectivity can be seen Cl2, Co, CO2 Possible Easy Low Highly flammable Low as compare to organic acid HNO3, HCl, H2SO4, etc.
Organic Acid Selectivity is possible No No Difficult High Non flammable High Citric acid, oxalic acid, etc.
Table-8: Selected literature work on different inorganic acids as lixiviant for LIBs Composition (Wt. %)
1 M HNO3
4 M HCl
Co=20.56 Li=3.43 Mn=12.3 Ni=0.72 Co=35.8 Li=6.5 Mn=11.6 Ni=10.06 Co=6.43 Li=4.37
5 M HCl
Leaching Parameter Time Temp S/L o (min) C (g/L) 75 1020 60 80 20
Recovery % Li Mn
1.5 M H2SO4 + 15% H2O2
Li=4.8, Co=41.5, Mn=2.1 LiCoO2
Co=25.83 Li=8.31 Mn=26.2 Ni=14.41
2 M H2SO4 +10% H2O2
93.4 50.2 96.3
Lee and Rhee, 2003 Wang et al., 2009 Guzolu et al., 2017
Meshram et al., 2015b
Latif and Ahmed, 2016
Pinna, et al., 2017 Suarez et al., 2017 Chen and Ho, 2018
99.8 98.6 98.6
Table-9: Summary of various published work on metal recovery from LiBs using citric acid Composition (Wt. %)
Li-4.48 Co-53.8 Mn-0.97 Ni-0.80 LiCoO2
1.25M Acid + 1% H2O2
Li et al., 2010b
1.25M Acid+ 2%H2O2 1.25M Acid+ 1% H2O2
30 min 35 min
Li et al., 2013
Fan et al., 2016
2M Acid+ 2% H2O2
Chen and Zhou, 2014
Co=97, Ni=93, Mn=98, Li=89
Chen et al., 2015
2.5M Acid+ 5%H2O2
Ma et al., 2017
1M Acid+ 1% H2O2
Co=85.1 Ni=100 Mn=28.3 Co=97, Ni=93, Mn=98, Li=89
Co=97, Ni=93, Mn=98, Li=89
Zheng et al., 2016
2M Acid+ 1% H2O2 1.5M citric acid
Li=97 Co=95 Ni=99
Golmohammadzadeh et al., 2017 Musariri et al., 2019
Li-6.78 Co-58.76 Mn-0.76 Ni-0.58 Li-4.48 Co-53.8 Mn-0.97 Ni-0.80 Li-6.81 Co-58.79 Mn-0.76 Ni-0.58 Co-0.24 Ni=1.01 Mn-35 Co-23 Li-3 Ni,Mn-5
Li-9.73 Co-28.82 Mn-24.39 Ni-33.91 Cu-0.11 Al-1.48
Parameters Temp. Pulp (oC) density (g/L) 90 20
Aaltonen et al., 2017
Table-10: Summary of selective work on metal recovery from LIBs using tartaric acid Composition (Wt. %)
Li-6.28 Co-35.52 Ni-11.85 Mn-8.15 LiCoO2
20 g/L Glucose
Li-6.69 Co-58.11 Ni -0.39 Mn-0.14
Parameters Time Temp. S/L (min) (o C) ratio(g/L) 30 70 17
0.6M Acid + 3 H2O2%
Co=98.64 Li=99.07 Ni=99.31 Mn=99.3 Co>95
He et al., 2017
30 g/L Ascorbic
Li=82.4 Co=53.2 Co=98 Li=97
Nayaka et al., 2016 Cheng, 2018
Chen et al., 2018
Table-11: Summary of selective work on metal recovery from LIBs using malic acid Composition (Wt. %)
Li 7.08 Co 20.26 Mn 18.89 Ni 20.19
Lixiviant Time (min)
Parameters Temp. Pulp (o C) density (g/L) 80 40
Sun et al., 2017
1.2M Acid + 1.5% H2O2
Li 4.48 Co 53.8
1.5M Acid +2% H2O2
Li et al., 2010a
1.5M Acid + 2% H2O2
Li et al., 2013
Li-9.73 Co-28.82 Mn-24.39 Ni-33.91 Cu-0.11 Al-1.48
Li=96 Co=98 Ni=99
Golmohammadzadeh et al., 2017 Musariri et al., 2019
Table-12: Summary of selective work on metal recovery from LIBs using oxalic acid Composition (Wt. %)
Parameters Temp. Pulp (oC) density (g/L) 120 80 50 min
1M Acid + 15%, H2O2
Co- 24.5 Li-3.52
1 M Acid
Co-23 Li-3 Ni and Mn-5
1M Acid +1% H2O2
Sun and Qui., 2012
Zeng et al., 2015
Aaltonen et al., 2017
Table-13: Summary of selective work on metal recovery from LIBs using other organic acids Composition (Wt. %)
1.25M Ascorbic acid
Parameters Temp. Pulp (oC) density (g/L) 70 25
Li=6.76, Co=57.94, Ni=0.76, Mn=0.91 LiCoO2
1.5 M Succinic Acid + 4% H2O2
1.5M Aspartic Acid + 2%H2O2
Li=6.79, Co=17.68, Mn=16.46, Ni=17.58
1.5M Lactic acid + 0.5 % H2O2
Li=6.15, Co=18.65, Mn=17.57, Ni=18.32 Li=6.15, Co=18.65, Mn=17.57, Ni=18.32
Li et al., 2012
Li et al., 2015
Li =60 Co=60
Li et al., 2013
Li= 97.7 Co=98.9 Mn=98.4 Ni=98.2
Li et al., 2017
2M Formic Acid + 2% H2O2
Gao et al., 2017
3.5M Acetic Acid + 4% H2O2
Li= 99.97 Co=93.97 Mn=96.32 Ni=92.67 Li= 99.97 Co=93.97 Mn=96.32 Ni=92.67
Gao et al., 2018
Fig.1: Life cycle assessment of lithium ion battery
Fig. 2: World map showing the reserves of Li, Co, Mn, Ni, and Graphite
Fig 3: Different processes for recycling of spent LIBs
Fig.4: Dismantling process for spent lithium ion batteries
Fig 5: Hydrometallurgical processing of spent LIBs
Fig. 6: Schematic recovery process by using different inorganic acid as lixiviant (Pinna et al., 2017; Qadir and Gulshan, 2018; Suarez et al., 2017; Shuva and Kurny, 2013; Guzolu et al., 2017; Chen and Ho, 2018; Chen et al., 2017)
Fig 7: Schematic recovery process by using citric acid as lixiviant
Research Highlights •
Global distribution of Li, Ni, Co, Mn and graphite depicted
Major ongoing processes vis-à-vis strategies described
Discussed about various organic acids used and mechanism of leaching
An overview on green processing perspective of LIBs recycling is presented.
To, The Co-Editor-in-Chief(s) Chemosphere
Dated: 24th Sep 2019
Subject: Declaration of No-Conflict of Interest (CHEM63222) Dear Sir, I am glad to submit the revision to the review article entitled “ASSESSMENT OF ENVIRONMENTAL IMPACT OF SPENT LITHIUM ION BATTERIES AND GREEN RECYCLING PERSPECTIVES BY ORGANIC ACIDS”, authored by Pratima Meshram, Abhilash Mishra, Abhilash, and Rina Sahu, for consideration to publication in “Chemosphere” Journal. We declare to have no conflict of interest and certify that the manuscript has been revised and submitted with our concurrence. Thanking You, Yours faithfully, (Pratima Meshram) (Abhilash Mishra) (Abhilash) (Rina Sahu)