Recovery and recycling of lithium: A review

Accepted Manuscript Recovery and Recycling of Lithium: A Review Basudev Swain PII: DOI: Reference:

S1383-5866(16)30565-2 http://dx.doi.org/10.1016/j.seppur.2016.08.031 SEPPUR 13203

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Separation and Purification Technology

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Please cite this article as: B. Swain, Recovery and Recycling of Lithium: A Review, Separation and Purification Technology (2016), doi: http://dx.doi.org/10.1016/j.seppur.2016.08.031

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Recovery and Recycling of Lithium: A Review Basudev Swain* Institute for Advanced Engineering, Advanced Materials & Processing Center, Yongin-Si, 449-863, Korea Abstract Projected demands for lithium as LIB for the plug-in hybrid electric (PHEV), electric (EV) and hybrid electric (HEV) vehicle in the recent future is huge and estimated to reach $221 billion by 2024. Currently, 35% of global lithium production being used for LIBs and consumption for estimated LIB demand could be 66% (out of global lithium production) by 2025. During last five (2011-2015) years, global lithium production is almost constant. At present, up to 3% of LIBs are recycled with the only focus of valuable metal recovery, but motivation on lithium recovery almost nonexistence. The global rate of lithium recycling is only < 1%. Considering the current global lithium production with respect to projected demand, environment and regulation, green energy and energy security, cradle-to-cradle technology management and circular economy of critical metal and minimization of waste crime and maximization of the urban mining, recovery and recycling status of lithium should be well understood. In this review recovery of lithium from various resources such as different ores, clay, brine, seawater and recycling of battery by different technique are reviewed. Lithium recovery from various primary resources and its separation purification by different routes such as hydrometallurgy, pyro-metallurgy, chemical metallurgy, and bioleaching are discussed. Lithium recovery through chemical leaching, bioleaching, and floatation of different ores also thoroughly reviewed. The extraction of lithium from seawater by co-precipitation and extraction, ion-exchange and sorption by using various organic, inorganic and composite polymer sorbents has been discussed thoroughly. Although, several industries recovering lithium from primary resources, but lithium recovery from secondary resources almost non-existence. The non-existence of lithium recovery process from LIB or techno-economically inefficient process is a greater challenge for the projected lithium demand. As the cradle-to-grave technology is a sustainability challenge, cradle-to-cradle technology management could be achieved through efficient recycling. Hence, technoeconomically feasible, environment-friendly and sustainable process needs to be developed and recommended. Considering technological advantages of hydrometallurgy process like; smaller scale, minimal energy investment, minimal CO2 emission, and the plant can be designed based on available waste, lithium recovery by hydrometallurgy should be focused. Keywords: Recovery; Recycling; Lithium extraction; separation and purification *

To whom correspondences should be addressed, Fax: +82-31-330-7116 E-mail: [email protected], [email protected] 1

1. Introduction Lithium is electrochemically active, having the highest redox potential value and it has the highest specific heat capacity of any solid element make it the hottest commodity for modern life and a key element for modern electric vehicle revolution. Due to their favorable characteristics, primary LIBs are widely being used for powering sophisticated electronics, while secondary LIBs dominate the cellular phones and laptop computer areas. Currently, LIBs are effective and affordable having few substitutes. The number of these consumer products is constantly expanding at a very fast rate. Today lithium and LIBs represent about 37% of the rechargeable battery world market and their use is increasing.

Particularly

demand for small rechargeable cells for the four sectors such as cellular, computers, video cameras and cordless are constantly growing [1]. Batteries consume 39% of total lithium[2]. In the near future market share of internal-combustion-powered vehicles expected to share with electric-powered vehicles. Large LIBs are and will continue to be needed for all hybrid and electric vehicles powering also for load leveling within solar- and wind-powered electric generation systems. Future light vehicles will potentially be powered by electric motors with large, lightweight LIBs, where lithium is unsubstituted metal for use in these batteries because of its high charge-to-weight ratio [3] [4, 5]. It is estimated that the penetration of plug-in hybrid electric (PHEV), electric (EV) and hybrid electric (HEV) vehicle into the market in 2020 will be at 20% [6, 7].

Lithium compounds are used in ceramics and special glass industry, in the primary aluminum production industry, rocket propellants industry, nuclear industry, pharmaceutical industry, in the manufacture of lubricants and greases, synthesis of vitamin A, synthesis of organic compounds, silver solders, underwater buoyancy devices, and batteries. Lithium is alloyed with aluminum and magnesium like light metals to form stronger and lightweight alloys. When lithium is an option and used in the thermonuclear plant

to control

thermonuclear fusion reactor the lithium requisite is 5,00,000-1,200,00 t [8]. LiCl is one of the most hygroscopic materials known and is used in industrial drying and air conditioning. Lithium is used in making synthetic rubber, greases and other lubricants. Global end-user market size of lithium for various sectors estimated by USGS is appended in Figure 1[9]. The Figure indicates the distribution of global lithium end-use markets as follows: batteries, 2

ceramics and glass, lubricating greases, air treatment, continuous casting mold flux powders, polymer production, primary aluminum production, and other uses, respectively, are 35%, 32%, 9%, 5%, 5%, 4%, 1%, and 9%. Lithium consumption for batteries is the highest among all end-uses and it has increased significantly in recent years. Because rechargeable lithium batteries are used widely in the portable electronic devices and increasingly are used in electric tools, vehicles, and grid storage applications, the market for the same is growing steadily. Lithium stearate is used as a high-temperature and all-purpose lubricant. Recent diversifying applications in metallurgical and chemical industries have been rapidly expanding. Global markets for lithium products has been discussed elsewhere[2, 7]. Highly purified lithium compound is used for biomedical application. Important biomedical application of Li2CO3 includes chemotherapeutic treatment of inflammation of joints, manic depression, and serious mental illness.

Lithium is industrially produced mainly as lithium carbonate, lithium hydroxide, lithium chloride, lithium bromide, and butyl lithium. From the energy security to carbon footprint, from daily life to industrial growth, from environmental safety to mental health, the lithium is a very important commodity. Thus, it is essential to determine the rapid and accurate methods for separation, purification and recovery of lithium from both primary and secondary resources, which ultimately receiving a great attention of scientists, engineers, and industrialist in the present years [10-12]. Worldwide lithium production during last five years, estimated global market for lithium in various sectors for the year 2013 has been discussed elsewhere in our earlier publication [7]. Furthermore, it must be considered that industrial and electric vehicles applications are gaining emergent interest [3]. So the lithium resources are very important taking into consideration the great role of that lithium plays in the industrial, energy, pharmaceutical and economic sectors [4].

The growths of portable electronic equipment use greatly increase the

LIB

consumption and demand, hence, the amount of LIB introduced in the global market is also growing, consequently, increases the production as well as end-of-life (EOL) waste. Lithium hexafluorophosphate (LiPF6) and Lithium cobalt oxide (LiCoO2) are the commonly used electrolytes for commercial LIB. LiCoO2 and LiPF6 can easily dissolve into the water in the 3

natural environment from waste LIB [13]. Kang et al. have reported the high rate of LIB disposal without recycling or treatment can adversely affect human health due to potentially toxic materials and substantially contribute to environmental pollution[14]. Though cobalt is not considered as a toxic metal, but excess deposition cobalt or metals in the nervous system can lead to metallosis. Mao et al., and Curtis et al., have reported cobalt toxicity, although reported cobalt toxicity is from different resources but cobalt is the cause of toxicity[15, 16]. Fatal and acute cases of cobalt toxicity have been reported in various medical journals[15-19]. Liu et al. have reported cobalt toxicity in the mung beans[20]. If LIB not disposed or treated properly, the Fluoride can also enter to the natural environment. Fluoride causes fluorosis, and acute toxicity can be fatal[21, 22]. Hence, their correct disposal is a crucial environmental issue. The storage capacities of special waste dump sites are limited, growing last cost and disposal costs and disposal related cost further worsen the disposal issue. Hence, from waste management, resources conservation, to meet the industrial need, reduce carbon footprint, energy security and to future demand

perspective, recycling of the major

components of spent cells/scrap is a feasible beneficial approach to support the circular economy, handle the energy security, and prevent environmental pollution[23-25]. Treating the scrap LIBs to reduce them for safe/suitable disposal, and environmentally compatible operations are essential both from an environmental and an economic perspective[25, 26]. For the battery industries, it could be very attractive to recover Li, Co materials to recycle in the production of new one [27-29]. Taking into account the expected overall world market evolution of the LIB products and that the average life of the secondary LIBs (Maximum life cycle of LiCoO2 cathode material is 1000 cycles[30]), we can reasonably conclude how the correct disposal of spent LIBs may soon become a serious problem. Consequently, for the sustainable management of natural resources, environment and per capita energy consumption,

researcher, engineers, and

environmentalist are interested in the recovery of all the valuables contained, in the form of pure compounds that can be used in the manufacture of new LIBs, thus achieving a quantitative recycling of these materials and close the loop for a circular economy [31, 32]. Considering the environment and regulation, green energy and energy security, cradle-tocradle technology management and circular economy of critical metal, and minimization of waste crime and maximization of the urban mining recovery, recycling of lithium should be 4

understood. Recovery and recycling of lithium from various primary resources such as different ores, clay, brine, seawater and secondary resources like the recycling of battery by different technique have been reviewed.

2. Lithium Resources In contrast to, important uses of lithium the accountability for occurrences of lithium from various resources need to be discussed. Economic concentrations of lithium are found in brines, minerals and clays in various parts of the world. Brines and high-grade lithium ores are the present sources for all commercial lithium production. Figure 2(a) shows the distribution of lithium spread over various resources. The figure shows continental brine is the biggest resource (59%) for lithium occurrence, followed by hard rock (25%). Figure 2(b) shows the distribution of lithium wealth over various countries. The largest known deposits of lithium are in Bolivia and Chile [33]. Figure 2(c) shows the distribution of lithium production over various countries. The leading producers and exporters of lithium ore materials are Australia and Chile. China and Chile have significant lithium ore resources. Canada, Congo (Kinshasa), Russia, and Serbia have lithium resources of approximately 1 million t each and the same reserve for Brazil is total 180,000 t [34]. The average lithium content of the earth's crust has been estimated at about 0.007%. Lithium does not occur free in nature but is found combined with small amounts in nearly all igneous rocks and in the waters of many mineral springs, sea water, in the ocean. Out of about 20 minerals known to contain lithium, only four, i.e., Lepidolite (KLi1.5Al1.5[Si3O10][F,OH]2), Spodumene

(LiO2.Al2O3.4SiO2),

Petalite

(LiO2.Al2O3.8SiO2),

and

Amblygonite

(LiAl[PO4][OH,F]) are known to occur in quantities sufficient for commercial interest as well industrial importance[35-38]. The mineral spodumene (LiAlSi2O6) is the most important commercial ore mineral of lithium. The lithium minerals also exist as cookeite as (LiAl4(Si3 Al)O10(OH)8) in small hydrothermal quartz veins. Taeniolite (KLiMg2 Si4O10F2) is present in smoky quartz veins in the recrystallized novaculite, Lithiophorite ((Al, Li) Mn4+O2(OH)) occurrence has been reported in the manganese deposits. Pegmatites, Cookeite, Taeniolite, and Lithiophorite minerals are considered non-economical sources of lithium [3941]. Most of the lithium is recovered from brine, or seawater is of high concentration of lithium carbonate. Brine occurs in the Earth’s crust is called continental brine/subsurface 5

brines are the major source for lithium production (lithium carbonate). In the literature, it is reported that in seawater also lithium present about 0.17 mg/L. Lithium occurs in significant amounts in geothermal waters, and oil-well brines. These seawater and brine sources are considered to be less expensive than to mine from the rock like; lepidolite, spodumene, petalite, and amblygonite lithium-bearing minerals.

3. Recovery of lithium from various resources 3.1. Lithium recovery process from ores 3.1.1. Recovery of lithium from ore/clay by hydro and pyro-metallurgy The important commercial hybrid lithium recovery process from lithium rich minerals is presented in Figure 3. Figure 3 shows the lithium recovery from ore broadly consist of mineral beneficiation and extractive metallurgy. The Figure 3 shows lithium-bearing minerals are initially subjected to mineral beneficiation through physical separation to produce concentrate followed by extractive metallurgy being implemented. In extractive metallurgy lithium being recovered purely by a chemical metallurgy process or a combination of chemical metallurgy and pyrometallurgy process [42, 43]. Mainly, two different hybrid process like; roasting/calcinations or a chlorination process being reported in the literature. Both the processes are represented in Figure 4 and 5 below. Figure 4 shows a hybrid process where, after concentration of lithium ore, either it is calcinated or roasted followed by leached to dissolve lithium to the aqueous phase. In the roasting process, limestone gypsum and hectorite mixed by the kiln, after that the mixture heated 750 0C. Then the solid are leached and separated. The lithium salt is leached out along with some sodium, potassium, and calcium. After the leaching the leach solution being purified. Finally, Li2CO3 being produced through carbocation. The lithium recovery efficiency reported being above 85%. The easiest method of lithium recovery from leach liquor is to concentrate solution prior to precipitation by carbonation of Li2CO3 on the addition of soda ash [37, 44-46]. In chlorination technique as shown in Figure 5, the ore is mixed with limonite, heated to 700 0C in a furnace, after volatizing the ore is leached with 20% HCl. Then water is introduced with the HCl, which is necessary for selective chlorination of lithium and eliminates by chlorination of undesirable components. Finally, the Li2 CO3 is precipitated out through carbonation by adding soda ash, which yields up to 80%. After precipitation, the precipitated Li2CO3 separated through solid6

liquid separation, followed by pure Li2 CO3 recovered by drying [42, 43]. Decades before, the process was considered as non-economical because of (i) energy needed to be volatilizing, (ii) the acid invested, and (iii) the cost of limestone added to the ore prior to heating [37, 44-46]. Extraction of lithium from different ores using various techniques reported by various authors has been discussed individually.

Various processes like, water disaggregation extraction process, hydrothermal treatment process, acid leaching, alkaline roast-water leaching, sulfate roast water leaching and chloride roast water leaching has been discussed by Crocker et al [47], May et al [43]. In our current review, recent processes reported in the literature has been discussed and reviewed.

3.1.2. Recovery of lithium from ore/clay by pressure leaching Applicability of the pressure leaching for the recovery of lithium from beta-spodumene mineral has been investigated using NaCl in the alkaline medium by Gabra et al. [48]. Effect of different parameters like; concentration sodium chloride, calcium hydroxide, the temperature, the pulp density, particle size and reaction time has been investigated. Gabra et al. have been reported that the rate and extent of lithium dissolution in pressure leaching process depend on upon various factors such as the concentration of sodium chloride, calcium hydroxide, the temperature, the pulp density, particle size and reaction time. It has been reported that the kinetics of the reaction are controlled by diffusion phenomenon. In above leaching in the range of 2 to 8 stoichiometric percentages, the rate of extraction increases, but beyond that the rate of extraction decreases. The effect of hydroxide also very significant is depicted Table 1. The reported investigation indicated that as the temperature increases the extraction also increases. From the energy calculation, relatively lower activation energy signifies that the rate of reaction is controlled by diffusion phenomenon. When the pulp density is concerned the rate of extraction, independent of pulp density up to 30% after that the rate of extraction decreases at the pulp density increases. As the leaching time increases the lithium extraction efficiency also increases. The combination of particle size with a time of operation has also a very significant effect on extraction Lithium. As the particle size increases the extraction efficiency of lithium decreases for first 60 minutes whereas after one 60 minutes it was independent of parcel size[48]. 7

3.1.3. Recovery of lithium from ore/clay by bioleaching The spodumene (LiO2.Al2O3.4SiO2), is a potential recourse for Li but it is considered as a very resistive mineral in the industry for industrial lithium recovery. The mineral beneficiation of spodumene and lithium extraction from spodumene is high energy intensive process. Considering energy expenditure in from the heat (calcination, roasting, and chlorination), adds significant disadvantage for the lithium recovery process. Hence, the role of micro-organisms extraction of lithium is very attractive from energy, economic and environmental perspective, although the process is encountered with a very slow kinetic problem. The weathering of this mineral has been demonstrated by Karavaiko et.al [49]. Vandeviver et al. have investigated the role of organic acid and extracellular polymers produced by micro-organism in silicate weathering [50]. The intensive investigation for the recovery of lithium from spodumene by bioleaching was investigated by Rezza et al. [51]. Rezza et al. have utilized heterotrophic micro-organisms, like; Penicillium purpurogenum, Aspergillus niger, and Rhodotorula rubra those were isolated from the mineral, separately. Two different media has been used for bioleaching are given in Table 2 (Medium1(M1), Medium 2(M2)). One of them (M2 medium) was highly limited in Mg(II), Fe(II) and K(I). With Penicillium purpurogenum 1·06 mg/L and 1·26 mg/L of lithium was leached into the M1 medium and in M2 medium, respectively in 30 days of bioleaching. The same report indicates 0·5 mg/L and 1·53 mg/L of lithium was leached in the M1 medium in M2 medium with Rhodotorula rubra in 30 days of leaching. Similarly, Aspergillus niger was able to leach 0·37 mg/L of lithium in M1 medium and 0·75 mg/L of lithium in M2 medium [51]. Marcinčáková et al. reported bioleaching of lithium from lepidolite using the yeast rhodotorula rubra. During the bioleaching of lepidolite using rhodotorula rubra, 412.6 μg/g of Li was extracted and 181.2 μg/g was accumulated in the biomass and salt-limited medium, respectively. Into the leach liquor 25 μg/l of lithium was leached[52].

3.2. Recovery of lithium from brine Brine is one of the important potential recourse for lithium recovery. From economical and scientific perspective following points are important to consider the recovery of lithium from brine, i.e., (i) availability of the pond ground and suitability of locality for solar 8

evaporation, (ii) concentration of lithium in brine, (iii) ratio of alkaline earth and alkali metals to lithium, and (iv) complexity of phase chemistry. The brine resources containing lithium can be characterized into three types, i.e., (i) evaporative, (ii) geothermal, and (iii) oil field brines. During the brine evaporation about 50% of the initial natural brine, lithium remains in the residual brine. This phenomenon has been attributed due to the retention of lithium by the precipitated salts. The residual brine is heavily loaded with Mg 2+ in comparison to Na+ and K+, makes the lithium recovery from this residual brine is more difficult[4]. Recovery of lithium from brine does not follow any general scheme because each process is specific according to the brine field composition. In contrast to ores and clay, an important advantage of brine is that it is already available in the solution. Figure 6 shows a typical lithium production technology used for lithium recovery by Outotec ®, where various techniques like solvent extraction, precipitation and flotation has been used. For recovery of lithium by Outotec® lithium carbocation is the process for lithium production[53].

In

literature various technique has been reported for separation and purification of lithium are reviewed below. Recently, Chagnes et al. have proposed general flow sheet for production of lithium from brine and seawater[11]. In the proposed process ion-exchange, liquid–liquid extraction, adsorption, and electrodialysis are the important hydrometallurgy process needed for concentrating the lithium prior to production has been proposed[11].

Recovery of

lithium from both brine and synthetic brine through the various process has been reviewed bellow and summarized in Table 3.

3.2.1. Recovery of lithium from brine by precipitation Recovery of lithium as lithium aluminate precipitation from dead sea brine and end brine (after potash production) has been reported by Pelly et al., Epstein et al., and Kalpan et al. [54-56]. Pelly et al. have reported, to attain 90% extraction efficiency the end brine and the dead sea brine need to controlled the pH of brine through the dilution[54]. As reported, the optimum pH should be ranged between 6.8-7.0 for end brine and between 6.6-7.2 for dead sea brine. The optimum reaction time should be 3 h at room temperature. The optimum amount of AlCl3.6H2O (30-40 gL-1) was added to the brine. Higher temperature have an adverse effect, the best yields was obtained at room temperature and the yield was decreased with increasing temperature [54]. Epstein et al. have reported the importance of lithium extraction from the dead sea by precipitation as lithium aluminate followed by liquid-liquid 9

extraction to separate the lithium from aluminum. An economic evaluation of the method has been reported [55]. Kaplan et al. reported lithium recovery process through lithium aluminate precipitation from dead sea brine[56]. A trace amount of lithium which mainly present as LiCl was precipitated using aluminum salt and ammonia at room temperature as lithium aluminate precipitate. Though subsequent recovery process like by dissolving lithium in sulfuric acid and followed by precipitation with calcium chloride lithium was recovered as alum[56]. An et al. reported a process for recover lithium from a brine collected from Salar de Uyuni, Bolivia. From the brine, Mg and Ca were recovered as Mg(OH)2 and gypsum (CaSO4.2H2O) using lime and sulfate. The residual Ca and Mg were recovered as CaO and MgO using oxalic acid followed by roasting. Finally, lithium was recovered as Li2 CO3 by heating at 80-90 oC. A high pure (99.55%) and crystalline Li2CO3 were recovered by the precipitation process[57].

3.2.2. Recovery of lithium from brine by chromatography The quantitative separation of lithium from other same group metals (alkali metals) and alkaline metal ions can be facilitated by a chromatography. Rona et al. have reported separation of lithium from dead sea brine by gel permeation chromatography. Lithium has been separated from brine by gel permeation chromatography using polyacrylamide gel, BioGel P-2 and Blue Dextran 2000 from dead seawater and end brine of dead seawater[58]. Both dead seawater and end brine on column chromatography on a Bio-Gel P-2, and the cations were eluted with water, the distribution of Li found to be 0.59 and 0.49, respectively. In both above cases, the order of appearance in eluents fraction was K+, Na+, Li+, Mg2+, and Ca2+. The chromatography clearly indicates that LiCl recovery is possible along with a trace of NaCl and KCl, but totally free from Mg and Ca [58]. Lee has reported separation of lithium from other alkali metal ions by reversed phase chromatography. As reported, in the reversed phase chromatography a column of polytetrafluoroethylene supported the organic solution of the extracting agent as the stationary phase. The organic solutions used as the stationary phase were Tributyl phosphate (TBP), Dibenzoylmethane (DBM) and trioctylephosphine oxide (TOPO). Efficient separation of lithium from other metals (alkali and alkaline metal) was achieved by Lee using reversed phase chromatography[59]. Abe et al. have reported that titanium (IV) antimonate cation exchanger (TiSbA) can adsorb lithium up to 66% in seawater and, 25% from hydrothermal water. Abe et al. reported in column chromatographic separation

10

method using titanium (IV) antimonate cation exchanger (TiSbA), lithium can be enriched with 20-fold which can be eluted using HNO3 up to 98% [60].

3.2.3. Recovery of lithium from brine by ion-exchange By employing the specially prepared resin/aluminates composite/inorganic ion exchanger, lithium can be recover efficiently from brine. Bukowsky et al. reported recovery of pure LiCl from brines containing higher contents of CaCl2 and MgCl2 through carbocation and ion exchange process [61]. Bukowsky et al. have studied 3 different ion exchange resin (MC50 resin, (Chemie AG Bitterfeld-Wolfen), TP207 resin (Bayer AG), Y80 -N Chemie AG (Chemie AG Bitterfeld-Wolfen)) for recovery of lithium from synthetic brine. The investigation resulted that purification of LiCl solutions with the resin Y 80 at room temperature and with the resin TP 207 at 50 ° C is feasible[61]. Hui et al. have reported the synthesis of H2TiO3 ion exchanger and recovery of lithium from the brine of natural gas wells[62]. Hui et al. have synthesized the H2TiO3 ion exchanger from TiO2 and Li2 CO3 or TiO2 and LiOH precipitation followed by calcination at 400-800 ℃. The H2TiO3 ion exchanger resulted high selectivity for Li+ with an exchange capacity for Li+ was 25.34 mg/g in mixtures of alkali metal and alkaline earth metal. The H2TiO3 ion exchanger exhibited 97% exchange rate and 98% elution rate for Li+ from the brine (local natural gas well)[62]. Chitrakar et al. have reported lithium recovery from Salt Lake brine using the same H2TiO3 ion exchanger. Chitrakar et al. have reported lithium adsorption ions by H2TiO3 ion exchanger follow the Langmuir model having an exchange capacity for Li+ was 25.34 32.6 mg/g) at pH 6.5 from the brine. The pH of brine was controlled using NaHCO 3[63].

3.2.4. Recovery of lithium from brine by liquid-liquid extraction Traditional liquid-liquid extraction and liquid-liquid extraction by ionic liquids (ILs) has been reported for extraction lithium from brine by various authors is reviewed below. Gabra et al. have developed a laboratory scale LiCl extraction process with n-butanol using synthetic solutions include different quantities of lithium, sodium chloride, potassium, and calcium chloride. A lithium recovery process has been proposed for separation and recovery of LiCl derived from distribution coefficients, separation factors and McCabe-Thiele representation of the results. The process can recover LiCl product with 99.6% purity [64]. Bukowsky et al.

11

reported liquid-liquid extraction of lithium from brines by alcohol such as isoamyl alcohol and n-butanol in combination with precipitation of lithium aluminum complex. Amount of extraction of LiCl from brine at pH 5.4 with various alcohol follow the order; 2-ethyle-1,3hexanediol > isoamyl alcohol > di-isopropyl ether > diethyl ether and can extract 32.8%, 25.2%, 11.4%, 9.1% lithium, respectively along with Na, Mg, and Ca. Including above the extraction lithium also studied using a binary mixture of above compounds with 1:1 ratio at pH 5.4. The 2-ethyle-1,3-hexanediol mixed with isoamyl alcohol is suitable for 90% LiCl recovery as well as suppression of the co-extracted metals is suppressed [65]. Extraction of lithium from brine sources with tributyl phosphate (TBP) in three different diluents has been reported by Zhou et al[66]. Feasibility of extracting lithium metal from brine sources with three salt solutions, (ZnCl2, CrCl3, and FeCl3) were selected as coextracting agents, were investigated for analysis extraction equilibrium of lithium. The liquid-liquid extraction equilibrium of lithium was analyzed with tributyl phosphate (TBP) in methyl isobutyl ketone (MIBK), TBP in kerosene and TBP in 2-octanol. During liquid-liquid extraction equilibrium of lithium investigation FeCl3 (solution) as the coextracting agent. The results indicated that the extraction efficiency followed the sequence: TBP/2-octanol < TBP/kerosene < TBP/MIBK. Lithium recovery with the TBP/MIBK and TBP/kerosene systems was much larger than that for TBP/2-octanol [66]. Badwin et al. have patented process for extraction of lithium from neutral brines using beta-diketone and trioctylphosphine oxide in benzene. The beta-diketone

used

were,

Peniafluorodimeihylhepiunedione

(i)

HeptofIuorodimethyloctunedione,

(ii)

(iii)

Trifluorodimethylhexanedione,

(iv)

Dibenzoylmethane, and (v) Tetrameihylheptonedione[67]. Detail extraction mechanism has been discussed elsewhere[7].

3.2.5. Recovery of lithium from brine by liquid-liquid extraction using ionic liquid In contrast to traditional liquid-liquid extraction the ionic liquid extraction regarded as not only as the solvent but also as the co-extraction reagent. Extraction of lithium from salt lake brine with tri-isobutyl phosphate in ionic liquid and kerosene have reported by Gao et al[68]. Gao et al. have reported three ionic liquids(ILs), i.e., 1-ethyl-3-methyl-imidazolium 12

bis[(trifluoromethyl)-sulfonyl]-imide,

1-butyl-3-methylimidazolium

bis[(trifluoromethyl)-

sulfonyl]-imide, and 1-butyl-3-methylimidazolium hexa-fluorophosphate with the tri-isobutyl phosphate(TIBP) and kerosene to extract lithium ion from Salt Lake brine. Results indicate that the best selective lithium extraction was obtained with IL 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)-sulfonyl] imide. The single-step extraction efficiency of lithium ion was 83.71% under the optimal extraction conditions, and the single-step stripping efficiency was 85.61% with a 1.0 mol/L HCl in 1.0 mol/L NaCl medium as stripping agent at (O/A)=2[68]. Gao et al. also reported extraction of lithium from brine using imidazolium-based ionic liquids with varying alkyl chain lengths in a series of 1-alkyl-3-methylimidazolium-based ionic liquids (ILs), in which the alkyl chain lengths were 4-butyl (C4), 5-pentyl (C5), 6-hexyl (C6), 7-heptyl (C7), 8-octyl (C8) or 9-nonyl (C9), in the presence of tri-isobutyl phosphate (TIBP) and kerosene systems [69]. The results indicated the shorter alkyl chain length of imidazolium-based ILs (enhances the lithium extraction) the better extraction efficiency of lithium. The optimum lithium extraction could be achieved using n-butyl (C4) based 1-alkyl3-methylimidazolium-based ionic liquids (ILs). In a single contact of the extraction and stripping the lithium extraction efficiency was 74.14% and 86.37%, respectively, under the optimal conditions. The optimum condition was n-butyl-3-methylimidazolium-based ionic liquids :TIBP : kerosene=1 : 8 : 1 (vol/vol), pH=5.0, O/A=2.0 in the extraction stage using 1 mol/L HCl at O/A=3 at stripping stage[69]. Chenglong et al. have reported separation of lithium and magnesium from Salt Lake brine by liquid-liquid extraction using ILs containing tributyl phosphate[70, 71]. ILs, 1-octyl-3methyl-imidazolium hexafluorophosphate, and tributyl phosphate (TBP) were used as extraction medium and extractant, respectively, for extraction of lithium from Salt Lake brine. Optimal extraction conditions of this system where the ratio of TBP/ILs at 9/1(vol), O/A at 2:1. The pH of Salt Lake brines kept (unaltered) constant. Under the optimum conditions, the single stage extraction efficiency of lithium and magnesium were 80.64% and 5.30%, respectively. Total 99.42% extraction efficiency was achieved by a three-stage countercurrent extraction. The single stage lithium and magnesium stripping efficiencies were 98.78% and 99.15%, respectively, at 80℃ when the A/O phase ratio was 2. Preliminary results indicated that the ILs had the potential to replace the volatile organic solvents in the liquid-liquid extraction of lithium cations[70]. Elsewhere Chenglong et al. have reported solvent extraction 13

of lithium cations by TBP using a room temperature ionic liquid. In that study, they have used TBP against commonly used ILs bis(trifluoromethyl sulfonyl) imide and quantitative lithium recovery achieved[71].

3.2.6. Recovery of lithium from brine by membrane process Recovery of lithium from brine by membrane process is relatively modern and novel technology has been reported by various authors, which are reviewed below. Jiang et al. have reported production of lithium hydroxide from brines through electro–electrodialysis with bipolar membranes[72]. In a lab-scale process, electro–electrodialysis with the bipolar membrane was installed with a repeated arrangement of conventional electrodialysis stack which is configured in series.

Conventional electrodialysis stacks were configured with

repeated arrangement, using five cation exchange membranes and four anion exchange membranes.

Through

preconcentrating

and

precipitating

brine

with

conventional

electrodialysis and Na2CO3, respectively 98% pure Li2CO3 powder can be recovered. In a 2014 report, the influence of current density and feed concentration on the production of lithium hydroxide (LiOH) was investigated. Electro–electrodialysis with bipolar membranes was cost effective at a current density of 30 mA/cm2 and feed concentration of 0.18 M. Jiang at al. has claimed the process is a cost-effective and environment-friendly process[72]. Liu et al. has reported extraction of lithium from salt lake brine by membrane electrolysis[73]. Various process parameters like; initial lithium concentration of an analyte, the distance between anode–cathode, temperature of the electrolyte, the surface density of active substrate, and time of electrolysis operation were optimized. The electrode exhibits a remarkable Li+ exchange capacity of 38.9 mg/g and the pH value of analyte under 8.00 at the optimal conditions, [73]. Grodzinski et al. reported recovery of lithium from dead sea brine by a membrane separation with ion-exchange hybrid process[74]. Solvent-polymeric membranes selectively permeate lithium cations. Membranes with (2-ethylhexyl)-diphenyl phosphate gave the best selectivity of Li+ transport over Mg2+ and Ca2+. During six months of operation, no significant change in membrane permeability and selectivity were observed. Grodzinski et al. have reported lithium preconcentration and, subsequently selective separation of lithium by a

14

membrane and ion-exchange fusion process. Grodzinski et al. have reported the feasibility of lithium separation by a combination of ion-exchange process and membrane[74]. Reverse osmosis (RO), nanofiltration (NF) processes have been applied for preconcentration/separation of lithium from brine. Separation of lithium and magnesium from brine using a desalination nanofiltration membrane has been reported by Sun et al[75]. Rejection rates of magnesium over lithium was estimated through optimization of various operational parameters like; pressure, inflow water temperature, pH, and Mg2+ to Li+ ratio. Also, extractions of lithium from Salt Lake brines by RO, and NF processes were investigated. The results indicate magnesium and lithium separation was highly dependent on the pH, operating pressure, and Mg2+/Li+ ratio. The competitive coefficient was susceptible to the Mg2+/Li+ ratio, whence the Mg2+/Li+ ratio was < 20, [75]. Somrani et al. have reported lithium recovery from salt lake brine by NF and low-pressure RO membrane[76]. Lithium selective by NF90 membrane compared with XLE a low-pressure reverse osmosis membrane. The NF90 membrane is more efficient for Li+ extraction compared with XLE at low-pressure RO membrane due to its higher permeability (hydraulic permeability) to pure water and 0.1 M NaCl solution. Lower critical pressure (Pc = 0), and higher selectivity between monovalent cations (40%) was obtained at low operating transmembrane pressure (< 15 bars). The NF90 membrane exhibited 100% rejection of magnesium in the first step separation from diluted brine (ten times dilution, 15% for Li+). A final 85% separation between Mg2 +/Li+ was achieved. Retained Li+ can be separated through dialysis[76].

3.3. Recovery of lithium from sea water The ocean considered being the most important as well as promising resources of the lithium for the near future to meet the demand of lithium of world community [38]. The amount of overall inventory of lithium in the world’s ocean is reported to be approximately 2.6 x 1011 t [77]. Recovery of lithium from hydro-mineral sources is carried out on a semiindustrial scale and industrial scale in United states of America from salt lakes [38, 78-80], in Japan from thermal water [81, 82], in Israel from the Dead Sea [38, 54]. Recovery of lithium metal from hydromineral source (geothermal and brine) also investigated in Russia, Bulgaria, Germany, Korea [83]. Conventionally, the lithium recovered from seawater by these two processes, (i) Co-precipitation and Extraction process and (ii) Ion-Exchange and sorption 15

process. With the development of technologies different techniques like liquid-liquid extraction, membrane process being employed for extraction lithium from sea water. Recovery of lithium from both brine and synthetic brine through the various process like liquid-liquid extraction, ion exchange and sorption, co-precipitation, and membrane processes has been reviewed bellow and summarized in Table 4.

3.3.1. Recovery of lithium from seawater by co-precipitation Lithium recovery and extraction by co-precipitation process have not as wide use as other techniques. The existence of higher concentration of alkali and alkaline metals in the sea water possess important challenge for recovery of lithium. Alkali group metals have very similar characteristics adds challenges for lithium recovery. The challenges encountered with lithium recovery from seawater and land-based hydro-mineral resources are very similar[38]. For recovery of lithium from seawater various reagents such as; aluminum hydroxides [38, 81], potassium, and iron periodates have been successfully applied for co-precipitation of lithium. Dissolution of the co-precipitate after ion exchange process is used to concentrate lithium. Um et al. reported a hydrometallurgical process to recover lithium from seawater using an adsorption process with manganese oxide adsorbent followed by a precipitation process[84]. In that process, CaCl2, MgCl2, and MgCl2 from seawater were precipitated as Ca(OH) 2, Mg(OH)2, and Mn(OH)2 by NaOH at the temperature (25–90 °C). Using the NaOH, pH was managed between 7–14 with an initial concentration of CaCl2, MgCl2, and MnCl2 (10 and 100 mmol/dm3). Followed by the second stage Li2CO3 was recovered through carbonation using Na2CO3 by neutralization using HCl[84].

3.3.2. Recovery of lithium from seawater by ion exchange and sorption Though current decade different mega industries are interested in recovery of lithium from seawater, but lithium recovery from seawater has increasingly attractive for researchers for several years through ion-exchange and sorption. Several alternative methods also proposed for lithium recovery from seawater using ion exchange after solar evaporation and fractional crystallization of NaCl, CaSO4, KCl. By this method organic and inorganic sorbets analogous to compounds used for lithium extraction. The reports explaining such method are reviewed below. Lithium selective aluminum contained resin, prepared by treating the microporous 16

anion exchanger Dowex-1 type with saturated AlCl3 solution, ammonia, and finally, with lithium halide solution before heating to obtain a composite of LiX.2Al(OH) 3 microcrystalline includes the resin matrix are examples of such products that have been patented in the United State of America [38, 85, 86]. The Sorbents based on tin, antimony, di-oxides based on titanium and Zirconium [87], mixed oxides of titanium and iron, titanium and chromium, titanium and magnesium and thorium arsenate, having high selectivity for extraction of lithium has been synthesized [38]. In the wide spectrum of lithium-selective ion–exchange materials only the cations exchange based on manganese oxides shows efficient results for lithium recovery from seawater. Originated from Russia, manganese oxide and manganese and aluminum mixed oxides know as ISM-1 and ISMA-1 respectively, are used for recovery of lithium [38, 88]. The H2TiO3 ion exchanger resulted in high selectivity for Li+ in mixtures of alkali metal and alkaline metal ions. The exchange capacity for Li+ was 25 34 mg/g. Abe et al. have reported synthetic inorganic ion-exchange materials titanium (IV) antimonate cation exchanger (TiSbA) have high selectivity for lithium cations. It can be successfully applied to the recovery of lithium cations from hydrothermal water as well as seawater. Abe et al. have also investigated the effects of K+, Mg2+ and Ca2+ cations on the adsorption of lithium cations on TiSbA by a batch technique. They have observation the lithium adsorption decreased significantly with increasing of K+, Mg2+, and Ca2+ cation concentrations. The lithium was enriched from seawater and hydrothermal water on TiSbA columns. The TiSbA exchanger can potentially be used repeatedly for the separation of lithium cations from seawater and hydrothermal water. Adsorbed lithium can be eluted with HNO3 solution as eluent [60]. Nishihama et al. have reported selective recovery of lithium from seawater using two successive processes of ion exchange[89]. Primarily lithium was concentrated from seawater using the bench-scale chromatographic operation with λ-MnO2 adsorbent (granule), which has 33% efficiency for the recovery of lithium. The purification of lithium from concentrated liquor of the benchmark plant was then conducted by a combination of ion exchange using resin and solvent impregnated resin. The purification process consists of the removal of divalent metal ions by strongly acidic cation exchange resin followed by the removal of Na+ and K+ with the β-diketone/TOPO impregnated resin; and finally the recovery of Li+ as precipitates of Li2CO3 using a saturated solution of (NH4)2CO3. By the process, the yield was 17

56% and purity was 99.9%[89]. A new method for recovery of lithium from seawater also propped by Takeuchi [90].This method is based on the high selectivity of the Al(OH) 3 layer for lithium ion at the efficient temperature is 50 0C and almost 70% recovery achieved under batch condition. The selectivity coefficient of Li+, K+, Ca2+, and Mg+ equal 990, 90, 45, and 11, respectively [90]. Lithium recovery from seawater by sorption/desorption fairly common process has been reported by several authors, which is reviewed below [91]. Commonly manganese oxide based sorbate are used for sorption/desorption recovery of lithium from seawater. Sorbet based on hydrated γ-oxides of manganese and a mixed oxide of manganese and magnesium have been developed by Japanese scientist [92, 93]. Recovery of lithium from seawater by manganese oxide (HMnO) ion-sieve (microporous) was investigated by Ooi et al. The maximum (7.8 mg/g) lithium uptake by the HMnO from seawater was achieved[92]. Investigation using ISMA-1 sorbents for recovery of lithium from seawater reveals the following information; (i) distribution coefficient of Li+ cation distribution is 4x104 (ii) the sorbents are easily regenerated with nitric acid (iii) they exhibit a high capacity for lithium cations of about 20 mg/m (iv) lithium concentrates contain up to 1 g/L of lithium can be reached under optimal condition. Using this information pilot plant, the capacity of 3 m3 of seawater per hour, a two-stage scheme for the production Li2CO3 from seawater designed and reported [38]. Although ISMA-1 sorbents provide higher chemical stability, the degradation manganese oxide associated with the ion exchange remains the most serious drawback for their scaled up application in the lithium recovery process. For improvement of the kinetic prosperities of manganese oxide sorbents, Japanese investigator has developed a composite material through the inclusion of λ-MnO2, a fine powder, with spinel structure in poly-vinyl chloride [94]. ISM and ISM-1 sorbents synthesized in Russia are also composite material obtained by applying polymeric binding material [38, 88]. The recovery of lithium from seawater using ion exchange type manganese oxide adsorbent has also been reported in Korea. In their technique specially prepared, high-performance ion-exchange adsorbent was prepared to recover dissolved lithium in seawater. By the solid state reaction of Li2CO3 and MgCO3 a high-performance ion exchange type adsorbate was synthesized. After treatment of seawater with the adsorbate the ion-sieve formed which recovered by acid treatment. The Li-ion sieve was obtained by 3 cycles of 0.5 M HCl treatment with 24 h/Cycle stringing, which shows 18

25.7 mg/L of lithium uptake from artificial seawater[83]. Liu et al. have reported lithium extraction from seawater by manganese oxide ion-sieve. Lithium extraction from seawater by adsorption using manganese oxide ion sieves was considered as the most promising process for industrial application[95]. Park et al. studied lithium sorption properties of HMnO in seawater and wastewater, and demonstrated that HMnO could be effectively used for recovery of lithium from seawater with good selectivity[96]. Zandevakili et al have reported Recovery of lithium from Urmia lake by MnO2 ion-sieve (nanostructure), where more than 90 % lithium recovery could be achieved[97]. Lithium adsorption behavior from seawater using manganese oxide adsorbent studied by Wajima et al[98]. Higher adsorption kinetics for lithium cations in seawater using was observed using a pseudo-second-order kinetic model[98]. Chitrakar et al. studied the recovery of lithium from seawater using manganese oxide adsorbent which is synthesized from the precursor of Li1.6Mn1.6O4. Manganese oxide adsorbent LiMnO2 was synthesized from H1.6Mn1.6O4 at 400 °C by hydrothermal and reflux method. H1.6Mn1.6O4 was synthesized from precursor Li1.6Mn1.6O4. The adsorbent can uptake the lithium up to 40 mg/g from seawater which was fairly an efficient adsorbent [99].

3.3.3. Recovery of lithium from seawater by liquid-liquid extraction Several authors have been reported liquid-liquid extraction of lithium from seawater and liquid-liquid extraction considered to be a potential recovery process for lithium from seawater. Separation, purification and recovery of lithium by liquid-liquid extraction has been reviewed elsewhere, but the application of liquid–liquid extraction for recovery of lithium from seawater is very limited[7]. Based on available reference liquid–liquid extraction of lithium from seawater has been discussed below. Although several extractants such as C3-C5 primary alcohol, and C6-C8 aliphatic alcohol tried for recovery of lithium from seawater, the isobutanol is the most effective and promising. The most interesting extraction method was developed by Japanese scientist and in fact, it represents the most updated technology [100, 101]. In these techniques, lithium is first extracted with cyclohexane and tri-octyloxyphosphine, after the back reaction of lithium with hydrochloric acid followed by precipitation of lithium with potassium phosphate. In this technique, purity of the product obtained from it more than 95%. Harvianto et al have reported synergistic extraction of lithium from seawater using TTA–TOPO mixture [102]. 19

Using TTA–TOPO 93% of lithium could be extracted. Lithium ion could be easily stripped by acidic solutions, the stripping efficiency decreases with pH of acidic solutions. Kind of acid does not affect the stripping efficiency. By the same process, 65% of lithium can be extracted from seawater by liquid-liquid extraction, unless magnesium ion is precipitated prior to the liquid-liquid extraction process. Other metallic ions in seawater negate the extraction efficiency of lithium ion [102].

3.3.4. Recovery of lithium from seawater by membrane processes Recent years recovery of lithium using various types of the membrane has been studied by several authors. Membrane process for recovery lithium fairly advanced process gaining the attention of various researchers around the globe. Recovery of lithium from seawater by membrane processes has been discussed thoroughly below and summarized in Table 4. Park et al. have developed a polysulfone (PSf)-based mixed matrix nanofiber dispersed with particulate lithium ion sieves as a flow-through membrane Li+ absorber. The mixed matrix nanofiber was prepared via electrospinning, thermal annealing, where lithium ion sieves were activated by acid pickling as Li0.67H0.96Mn1.58O4 or MO. The PSf matrix effectively improved the Li+ selectivity. The mixed matrix nanofibers membranes were highly permeable to water under minimal trans-membrane pressure. By maintaining a dynamic Li+ adsorption capacity of the mixed matrix nanofibers, by continuous flow-through operations a shorter adsorption–desorption cycle time (24h) were successfully controlled. Enrichment of Li+ was successfully achieved by repeated Li+ desorption in a small volume of the acid solution[103]. Chung et al. have reported lithium recovery from seawater by inorganic adsorbent containing polymeric membrane reservoir system. Chung et al. have applied three different membranes, i.e., non-woven fabric PSf membrane, PSf non-woven fabric composite membrane, and Kimtex® for recovery of lithium from seawater. The proposed system has the advantage of direct application in the seawater eliminates the use of pressurized flow system[104]. Similarly, Umeno et al. also reported lithium recovery from seawater using inorganic adsorbent containing polymeric membrane. Park et al have reported lithium recovery from seawater desalination retentate using composite poly(acrylonitrile) (PAN) nanofibers with H1.6Mn1.6O4 (HMO) lithium ion-sieves [105]. HMO/PAN dope solutions in N,N-dimethylformamide (DMF) with varied HMO loadings was used for 20

nanofibers preparation and nanofibers were prepared by electrospinning. Park et al. consider the material can be a potential membrane for effective recovery of lithium from seawater desalination retentate.[105] Umeno et al. have prepared a membrane-type adsorbent from spinel-type manganese oxide by a solvent exchange method using poly(vinyl chloride) (PVC). The PVC was used as a binder. PVC was dissolved in DMF solution, followed by lithium manganese oxide (spinel-type) was mixed with the DMF to make a suspension. Solidified the PVC film was prepared by spreading the suspension over a thin film and immersed in water. The membrane was treated with an HCl solution to extract lithium result was membrane-type adsorbent. As reported the lithium extraction highly depends on upon the method of preparation[106]. Hoshino has reported lithium recovery from seawater both by dialysis and electrodialysis[107-109]. Selective recovery of lithium from seawater by electrodialysis using ionic liquid (PP13-TFSI) impregnated membrane has been studied in laboratory scale. Followed by a membrane recovery process has been developed for recovery of lithium[107, 108]. In the dialysis process using a lithium ionic superconductor membrane selectively, lithium recovery from seawater was achieved. The dialysis process can be energy efficient and is easily scalable for suitable industrialized mass production of lithium[109]. Recently, Jensen et al. have reported recovery of lithium by membrane desalination followed by crystallization[110]. Membrane crystallization in direct contact, vacuum, and osmotic configurations have been carried out to recover lithium chloride and compared. Among them by the vacuum membrane distillation required supersaturation for crystallization was achieved, which is used for simultaneously clean water and lithium production[110].

3.4. Lithium extraction from lithium ion battery recycling To justify and realize the importance of LIB recycling as prime secondary resource, the global demand, market, trend and forecasts are reviewed and analyzed. Navigant Consulting, Inc. has forecasted global LIB demand for vehicles is expected to total $221 billion by 2024[111]. Investorintel reported and Avicenne Energy has forecasted global lithium metal demand for battery industry will increase from 9,760 t (2015) to 12,160 t by 2020 and 21,520 t by 2025, which are 30%, 37 % and 66% of the total lithium being produced currently (32,500 t) for the year 2015, 2020 and 2025, respectively[112, 113] . Sonoc et al. have reported only LIBs, based on lithium chemistries will satisfy the demand for electric 21

vehicle[114]. Although LIB being recycled by various industries but most of the process focused on Co, Ni or other metals value recovery than lithium. A UNEP status report on recycling rates of metals reported hardly <1% of lithium being recycled[115]. The present production capacity of lithium from the rock, clay, and brine resources is at bottlenecked to meet the steadily growing lithium demand by the conventional lithium industries [116]. Sonoc et al. have reported considering the future demand of lithium for LIBs at the most optimistic supply scenario could not meet in 2023[114]. The future supply crisis only can be prevented through 100% LIB recycling with minimum 90% lithium recovery[114]. Currently, up to 3% of LIB are recycled with the focus of valuable metal recovery with a minimal focus on lithium recovery[114, 117, 118]. Progressive lithium demand for LIB and the controlled thermonuclear fusion reactor may exceed the current availability of the mineral and brine reserves in the next few decades. Thus, it is far-sighted to search for new alternatives to satisfy these and other lithium applications in the future. Considering overall LIB world market evolution, projected future market evolution, average life and end-of-life(EOL) scrap and projected future scarcity

recovery of lithium through recycling of LIBs are very

important for the environment and lithium metal economy [119]. Extraction of lithium from LIB recycling and another metal values is multi-dimensional beneficial such as; to keeps all the hazardous metals in one place, the metals reclaimed are reused, bring back the recovered lithium to manufacturing process, the cost of landfilling the batteries can be saved, good environmental policy, saves natural resources, protects the future, and conserves resources for future generations[25]. It is not only very important for lithium metal economy but also environment-friendly. By recycling waste batteries helps to keep in compliance with various environmental regulations such as waste electrical and electronic equipment (WEEE) directive, and restriction of the use of hazardous substances in the EEE (RoHS) directive. Through recycling UNEP e-waste management strategy, extended producer responsibility (EPR) waste management strategy, and e-waste crime can be addressed. Most of the proposed processes basically are (i) Hydrometallurgy, (ii) Pyro-metallurgy, (iii) Hybrid processes, and (iv) Biological process. A detailed classification of LIB recycling process is provided in Figure 7. Different industries recycling battery associated with lithium are summarized in Table 5, but the focus of lithium recovery is very limited[120, 121]. Various LIB recycling processes reviewed below. 22

3.4.1. Lithium recovery from LIB by pyro-metallurgy process Though various industries like; Toxco Inc. (now retriev technology Inc.), USA, BDC Inc, Canada, Sony Corp., Japan, SNAM, France, Umicore, Belgium, and AEA technology, UK recycle either LIB or batteries, but focus on lithium recovery are very limited [23, 33, 121, 122]. As reported in the literature because of the high reactivity of lithium in air or moisture, LIBs are industrially processed by Toxco Inc. (now retriev technology Inc.) and BDC Inc. using low-temperature process recycling plants only in Canada and USA [23]. The Toxco process can recycle most types and sizes of waste batteries which include alkaline, lithium ion battery, mercury, NiCd, lead. Toxco process recycles lithium bearing waste batteries through a combination of cyromilling and pyrometallurgy processes [120-122]. In Toxco process the waste LIBs are stored underground followed by residual electrical energy is discharged. In the cyromilling process, the lithium bearing waste batteries is cooled in liquid nitrogen at -325°F followed by shredded mechanically[123]. After shredding materials are separated. The powder material then mixed with water, where lithium dissolved as lithium hydroxide and evolves hydrogen. The evolved hydrogen burns above the reaction liquid. By this process main product is lithium hydroxide is produced followed by cobalt, nickel or other metals are also recovered. As the review is limited to lithium recovery, the process for recovery of the metals has not been addressed here. The lithium hydroxide recovery chemistry partially can be explained using Equation 1 given below.

Lithium-ion batteries are reprocessed in France (SNAM) or in the UK (AEA technology batteries) [23] mainly with the aim to recover electrolyte and valuable metals from the anode. In AEA batteries recycling technology, the electrolyte can be extracted by immersing in a suitable solvent for a few hours. After residual solids separation, by evaporation at reduced pressure the solvent can be recovered through condensation and left over pure electrolyte can be collected without further purification. Several liquids are used as the extraction solvent. The main requirements are: (i) the boiling point of the solvent at reduced pressure should be below the lithium salt decomposition temperature (~80°C), and (ii) the solvent should be in an anhydrous state. The electrodes immersed in the solvent, which is stirred, heated to around 23

50°C to separate electrolytes from the residual copper, aluminum, steel and plastic-based components. The electrode particles are filtered from the binder solution. The residual electrode particles are lithium cobalt oxide and different types of carbon. To avoid adding any chemicals to the system it was electrochemically reduced. As the cobalt(III) is reduced to cobalt(II), lithium is freed from the solid structure. Oxygen is generated at the counter electrode, giving a (simplified) overall chemical Equation (2) as follow: LiCoO2(s) + H2O ⇌ 2 CoO(s) + 2 LiOH(aq) + ½ O2(g)

(2)

During the electrochemical reaction, the carbon particles increase the electronic conductivity. Hydrogen evolution is an unwanted side reaction. Therefore, aqueous lithium hydroxide is used as an electrolyte [23, 122].

Although industrial lithium recovery from batteries is limited, but, several authors have reported recovery of lithium from battery recycling. Hydrothermal treatment of LiCoO2 a spent cathode electrode and recovery of lithium from LiCoO2 has been reported by Kim et.al. LiCoO2 cathode material is renovated and simultaneously separated from spent LiCoO2 electrodes, Al current collector, electron-conducting carbon, binder, and separator in a single synthetic step using the hydrothermal method in a concentrated LiOH solution at 200 oC without any scraping procedures[124]. Träger et al. reported a recycling process for automotive lithium-ion batteries[125]. Two metallurgical treatment technologies are reported: direct vacuum evaporation of Li followed by recovery of metallic Li by distillation, and a selective entraining gas evaporation of Li followed by recovery of lithium oxide[125].

3.4.2. Lithium recovery from LIB by hydrometallurgy process Zhang et al. have reported the separation and recovery of cobalt and lithium from spent secondary LIBs by hydrometallurgy technique [126]. The cobalt was recovered through leaching followed by the liquid-liquid extraction process. After the cobalt recovery, the raffinate was concentrated and treated with a saturated solution of sodium carbonate to precipitate lithium carbonate. The Li2CO3 was recovered after filtration. By this precipitation, 80% of the lithium could be

recovered as a precipitate [126]. A laboratory-scale LIB 24

recycling process has been proposed by Contestabile et al.. Contestabile et.al. have reported after the mechanical separation of the active electrode materials of the samples materials were inserted into an isobutyl alcohol/water, i-BuOH/H2O, biphasic system, which allowed for achieving a mild oxidation of lithium metal. The direct reaction of lithium metal in water, represented by Equation (3) given below. 2Li+2H2O→2LiOH+H2 ↑

(3)

The dissolved LiOH can be precipitated as Li2CO3 by bubbling CO2 gas through the solution for few minutes. By heating the solution, equilibrium shifted to the formation of the carbonate ion (CO3−) which precipitate lithium as Li2CO3 . Second stage precipitation of the same process recovers lithium quantitatively [31]. Nguyen et al. have reported lithium recovery from the sulfate leach liquor of spent LIB using PC-88A. In their process followed by Ni, recovery lithium was recovered as Li2 CO3 from scrubbing solution using saturated solution of Li2CO3 at 100 oC[127]. Our literature investigated leads to the fact that though numerous investigations have been reported in the literature, but report regarding lithium recovery is very limited. Hence, lithium recovery from LIB by hydrometallurgy should be focused to address the environment, circular economy, and urban mining issues. The same can be exploited as a prime secondary resource for the lithium. Chemical extraction of lithium from LiCoO2 using oxalic acid has also been investigated by Lee et al [128]. Lee et al. have reported mineral acid, like sulfuric acid and nitric acid leaching of LiCoO2 lack of selectivity. In acidic leaching usually, both lithium and cobalt leached add complexity for recovery of pure lithium. Hence, a week oxalic acid lixiviant could selectively leach lithium efficiently as a low pH range. In the oxalic acid leaching, qualitative leaching was achieved along with less than 1% of cobalt leaching. The oxalic acid leaching has added advantages, the less that 1% of cobalt leached could be precipitated as an insoluble CoC2O4. The process is efficient to recover 90% lithium from cathodic battery materials at the optimum condition. After precipitation of cobalt by oxalate, the remaining Li ions in solution can be converted into a carbonate compound by the addition of Na2CO3 [128].

3.4.3. Recovery of lithium by hybrid metallurgy process 25

Several industries recover lithium from LIB by the hybrid process. Xstrata, Canada and Umicore, Belgium uses a combination of pyrometallurgy and electrowinning to process all kind of batteries including LIB. But, focus on the recovery of lithium is limited. Literature investigation indicates that report regarding recovery of lithium by hybrid metallurgy process are extremely rare for such an important metal[120, 121]. Maschler et al. have reported lithium recovery from LIB through ACCUREC Recycling and UVR-FIA a recycling with (hybrid process) combining a mechanical pretreatment with hydro-and pyro-metallurgical process. Unlikely other studies not only the cobalt recovery only but also lithium recovery was the interest of the reported process[129].

3.4.4. Recovery of lithium by chemical extraction process Chemical extraction of lithium from LiCoO2 has been investigated with various oxidizing agents—Cl2, Br2, and I2 by Gupta et al [130]. Gupta et al reported a considerable amount of lithium could be extracted with both chlorine and acid. The combination of the stronger oxidizing power of Cl2 and the relative instability associated with the lithium can dissolve lithium during chlorine oxidation to a considerable extent. A deeper lithium extraction with chlorine also leads to the occurrence of oxygen vacancies in Li1-x CoO1-δ. Lithium extraction with acid proceeds mainly by an inconsistent of Co3+ to Co2+ and Co4+, similarly the LiMn2O4 spinel works to ion exchange of Li+ by H+. Gupta et al. have observed extraction behavior depend on upon the nature of the initial material. Extraction of Co from Li planes by this process might be useful to obtain improved electrode materials for lithium batteries. The lithium extraction efficiency of

different oxidizing agents depends on their oxidation

potential [130].

3.5. Lithium recovery from lithium ion metal oxide battery Lithium recovery from the lithium ion metal oxide (LIMO) battery has not been widely investigated. Venkatraman et al. and Endres et al. have reported chemical extraction of lithium from the layered LiNi1−y−zCoyMnzO2

and

Li1+xMn2−xO4−δ, which are the battery

electrode material for LIMO. The rate of chemical extraction of lithium from the layered LiNi1−y−zCoyMnzO2 has been investigated by Venkatraman et al. with the oxidizer NO2BF4 in acetonitrile medium [131]. As Venkatraman et al. reported, chemical extraction of lithium 26

was carried out by stirring the LiMO2 (LiNi1−y−zCoyMnzO2) powders in an acetonitrile solution of NO2BF4 for various reaction times under argon atm in a Schlenk line. The overall leaching reaction can be explained using Equation (4). LiMO2 + NO2BF4 → Li1−xMO2 + xNO2 + xLiBF4

(4)

The molar ratio of LiMO2:NO2BF4 was kept constant at 1:2 in acetonitrile for the various samples in order to keep the driving force for chemical lithiation the same. After a specific reaction time, the formed products were washed several times with acetonitrile under argon to remove LiBF4. Then dried under vacuum at ambient temperature, and stored in an argon-filled glove box. The respective observations are reported in Table 6 gives the time required to extract all lithium. From the cobalt-rich LiNi1−yCoyO2 (0.5≤ y ≤1), lithium could be extracted quantitative in 0.5 h, while the extraction time was longer (6–48 h) for quantitative recovery of

lithium

from

the

nickel-rich

LiNi1−yCoyO2

(0≤

y

<

0.5)

materials.

The

LiNi0.5−0.5yMn0.5−0.5yCoyO2 electrode material the time required for efficient recovery of lithium decreases with increasing Co content. The slow lithium extraction rate in the cobaltpoor LiNi0.5−0.5yMn0.5−0.5yCoyO2 and nickel-rich LiNi1−yCoyO2, LiNi1−zMnzO2 material is due to considerable cation disorder [131]. The lithium content in the electrode material decreases as a function of reaction time.

With increasing nickel content needed longer time for a

quantitative extract of lithium [131]. Endres et al. have reported extraction of lithium from spinel phases of the system Li1+xMn2−xO4−δ, though acidic leaching [132]. Chemical extraction of lithium from the spinel phase Li1+xMn2−xO4−

δ

was studied for 0 ≤ x ≤ 0.33 in acidic

medium (H2SO4/H2O) and proton-free medium (Br2/CH3CN) extracting solvent. Endres et al. reported lithium recovery is possible with Li+ ↔ H+ exchange [132].

4. Conclusion Along with per capita energy consumption from battery resources, the requirement of lithium in various industries, like; glass industry, electronic and electrical industry and pharmaceutical industry increases rapidly. Projected demands for lithium as LIB for the vehicles is huge, estimated to consume 66% lithium metal by 2025 of total lithium produced currently and global market size for LIB for vehicles will be $221 billion by 2024. Currently, only 3% of waste LIB being recycled and rate of lithium recycling is only < 1%. Taking future lithium demand for LIBs into account under the most optimistic circumstances of 27

supply could hardly meet the demand after 2023[114]. The future supply crisis only can be prevented through 100% LIB recycling with minimum 90% lithium recovery[114] or by the techno-economical, environment-friendly, and efficient recovery of lithium from low-grade primary resources. To meet lithium requirement, it is essential to find the alternative for efficient recovery of lithium from low-grade primary and secondary resources such as from ores, clays, brine, seawater and scrap LIB. In comparison to low-grade primary resources, recycling of LIB should be preferable as it eliminates several processes (beneficiation and recovery process from primary resources to Li salt/metals) and could be easily available through urban mining. Also, in the favor of the clean environment, to support environmental regulation and urban mining, address the lithium metal economy and green energy security, it is also essential to recover the metal values from the waste LIBs. Several industries recovering lithium from primary resources, but lithium recovery from secondary resources almost non-existence. The non-existence of lithium recovery process from LIB or technoeconomically inefficient process is a greater challenge for the projected lithium supply crisis, needs attention for development of techno-economically efficient processes. Technology for industrial recovery of lithium from LIBs should be focused and an essential requirement for the environment and regulation, green energy, and energy security, cradle-to-cradle technology management and circular economy of lithium, minimization of waste crime and maximization of the urban mining recovery, and to keep the green energy policy on track. In above discussion each of the reported research paper has its own potentiality to support the environment and the economy as well as for extraction, separation, purification and recycling of lithium. Whence, the process involved in lithium recovery all over the world are limited and needs proportionately development to meet the lithium requirement at present and future. Literature investigation shows that to recover high pure Li2CO3 for pharmaceutical interest also very limited, in contrast, which is considered to be very important. Need for development of efficient and feasible technology for pure lithium recovery from low-lithium bearing sources recommended and secondary resources like LIBs is also recommended. The urgency for the alternative recycling technologies/processes to recover the lithium in particular from LIB needs an attention to avert the projected crisis in the near future. As the Cradle-to-Grave technology is a sustainability challenge, Cradle-to-Cradle technology management could be achieved through efficient recycling. Recovery of lithium through 28

recycling from LIB can be an alternative feasible option to meet future demand (turn away the supply chain crisis if any existed), sustainability of energy, environment, and circular economy. Techno-economically feasible, environment-friendly and sustainable process needs to be developed and recommended. Since pyrometallurgical processes are technoeconomically feasible mostly under mega scale which requires a high volume of investment simultaneously an environmental challenge and requires higher energy, the pyro process hardly can be an option to recover values. Considering technological advantages of hydrometallurgy like; smaller scale, minimal energy investment, minimal CO2 emission and the plant can be designed based on available waste, lithium recovery by hydrometallurgy should be focused.

Acknowledgements Lovingly dedicated to my most loving mother, Mrs. Ahalya Swain On her II death anniversary 16th May 2016. ‘May God grant her a place in the heaven'.

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Fig. 1: Distribution of global lithium end-uses at various sectors for various applications.

37

Fig. 2: Distribution of lithium (a) at various natural resources, (b) wealth across the globe, (c) production across the globe and

38

Fig. 3: Lithium recovery process from the Li-bearing ore.

39

Fig. 4: Lithium recovery process from the Li-bearing clay through roasting[7].

40

Fig. 5: Lithium recovery process from the Li-bearing clay through chlorination[7].

41

Fig. 6: Outotec lithium production technology from brine. Reproduced with permission from Outotec. (Reproduced with permission)

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Fig. 7: Lithium-ion battery recycling process classification.

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Table 1: Effect of different alkali hydroxide on the yield of lithium extraction, Gabra et al. [48]. Hydroxide

[Hydroxide], g/L

Yield of lithium Extraction (%)

Ca(OH)2

1.25

98

NaOH

1.25

92

KOH

1.50

92

LiOH

1.50

90

NH4OH

175mL

90

Table 2: Composition of media was used for bioleaching by Rezza et al. [51]. Composition

Medium1(M1)

Medium2 (M2)

Glucose

5 g/l

5 g/L

(NH4)2SO4

0.5 g/l

0.5 g/L

Fe2+

0.048 mol/L

0.048 mol/L

Mg+

1.5 m mol/L

< 0.01 m mol/L

K+

1.8 mol/L

0.3 mol/L

44

Table 3: Recovery of lithium from Brine by various process Resources

Process

Reagent

Mechanism

Refer ence

End brine and

Precipitation

Lithium aluminate

Precipitation

[54]

Dead Sea brine

Precipitation

Lithium aluminate

Precipitation

[55]

Dead Sea brine

Precipitation

Lithium aluminate

Precipitation

[56]

Salar de Uyuni,

Precipitation

Precipitation

[57]

[58]

Dead Sea brine

Bolivia, Dead sea brine

Gel permeation

Polyacrymidegel, Bio-Gel

Column

chromatography

P-2 and Blue Dextran

Chromatography

2000 From other alkali

Reversed phase

Polytetrafluroethylene

Column

metal

chromatography

Tribytyle phosphase

Chromatography

[59]

(TBP), Dibenzoylmethane (DBM) and trioctylephosphine oxide (TOPO) Seawater,

Column

Titanium (IV) antimonate

Column

[60]

hydrothermal

Chromatography

cation exchanger (TiSbA)

chromatography

Chelating resins

MC50 resin,

Ion exchange

[61]

H2TiO3 ion exchanger

Ion exchange

[62]

H2TiO3 ion exchanger

Ion exchange

[63]

water Synthetic brine

TP207 resin, Y80 -N Chemie AG Brine of natural

Inorganic ion

gas wells

Exchanger

Salt Lake brine

Inorganic ion Exchanger

Synthetic brine

Liquid-liquid

n-butanol

extraction

45

[64]

Synthetic brine

Liquid-liquid

2-ethyle-1,3-hexanediol,

extraction

isoamyle alcohol, di-

[65]

isopropyl ether, diethyl ether Brine

Brine

Liquid-liquid

with tributyl phosphate

extraction

(TBP)

Liquid-liquid

HeptofIuorodimethyloctun

extraction

edione,

[66]

[67]

Peniafluorodimeihylhepiu nedione, Trifluorodimethylhexaned ione, Dibenzoylmethane, and Tetrameihylheptonedione Salt Lake brine

Ionic liquid

-butyl-3-

liquid-liquid

methylimidazolium

extraction

bis[(trifluoromethyl)-

[68]

sulfonyl]-imide, 1-ethyl-3methyl-imidazolium bis[(trifluoromethyl)sulfonyl]-imide, and 1butyl-3methylimidazolium hexafluorophosphate Brine

Ionic liquid

1-alkyl-3-

liquid-liquid

methylimidazolium-based

extraction

ionic liquids (ILs), in which the alkyl chain lengths were 4-butyl (C4), 5-pentyl (C5), 6hexyl (C6), 7-heptyl 46

[69]

(C7), 8-octyl (C8) or 9nonyl (C9), Salt Lake brine

Ionic liquid

1-octyl-3-methyl-

liquid-liquid

imidazolium

extraction

hexafluorophosphate, and

[70]

tributyl phosphate (TBP) Salt Lake brine

Ionic liquid

Bis(trifluoromethylsulfon

liquid-liquid

yl) imide in TBP

[71]

extraction Brine

electro–

Bipolar membranes

[72]

Bipolar membranes

[73].

Solvent

Solvent-polymeric

[74]

impregnated

membranes

membrane

(2-ethylhexyl)-diphenyl

electrodialysis Salt Lake brine

membrane electrolysis

Dead Sea brine

phosphate Brine

Desalination

Nanofiltration membrane

[75]

Salt Lake brine

Desalination

Nanofiltration (NF90

[76]

membrane XLE membrane)

47

Table 4: Recovery of lithium from seawater by various process Resources

Process

Reagent

Mechanism

Reference

Seawater

Precipitation

Na2CO3 + HCl

Precipitation

[84]

Seawater

Ion-exchange

Titanium (IV)

Ion-exchange

[60]

antimonate cation exchanger (TiSbA) Seawater

Adsorption

λ-MnO2 adsorbent

Sorption

[89]

Seawater

Adsorption

Al(OH)3 layer

Sorption

[90]

Seawater

Adsorption

(HMnO)ion-sieve

Sorption

[92]

(microporous) Seawater

Adsorption

λ-MnO2

Sorption

[94]

Seawater

Adsorption

MnO2

Sorption

[95]

Seawater

Adsorption

HMnO

Sorption

[96]

Seawater

Adsorption

nanostructure MnO2

Sorption

[97]

ion-sieve Seawater

Adsorption

MnO2 adsorbent

Sorption

[98]

Seawater

Adsorption

H1.6Mn1.6O4

Sorption

[99]

Seawater

Liquid-liquid

cyclohexane and tri-

extraction

octyloxyphosphine

Liquid-liquid

Thenoyltrifluoroacetone

extraction

(TTA) and TOPO

Membrane

Mixed matrix nanofiber

process

as a flow-through

Seawater

Seawater

[100, 101]

[102]

Adsorption

[103]

Adsorption

[104]

Adsorption

[106]

membrane Seawater

Membrane

Inorganic adsorbent

process

containing polymeric membrane

Seawater

Membrane

Inorganic adsorbent

process

containing polymeric membrane 48

Seawater

Seawater

Membrane

Recyclable composite

Adsorption

[105]

process

nanofiber adsorbent

Membrane

Li ionic superconductor

Dialysis

[109]

process

functioning as a Li

Ionic liquid membrane

Electrodialysis

[107, 108]

Membrane

Membrane distillation

Osmotic and

[110]

process

and crystallization

vacuum

separation membrane Seawater

Membrane process

Seawater

configuration Seawater

Membrane

Mixed matrix nanofiber

process

as a flow-through membrane

49

Adsorption

[103]

Table 5: Summary of battery recycling process by various company all over the world [120, 121] Company

Battery Types

Process

Location

Toxco

Ni, Li-Based

Cyromilling (Li),

Trail, BC, Canada

Pyrometallurgy (Ni)

Baltimore OH, USA

Salesco Systems

All type battery

Pyrometallurgy

Phoenix, AZ, USA

OnTo Technology

Li-Based

Liquid-liquid

Bend OR, USA

extraction AERC

All type battery

Pyrometallurgy

Allentown PA, USA Hayward CA, USA West Melbourne FL, USA

Dowa

All type battery

Pyrometallurgy

Japan

Japan Recycle

All type battery

Pyrometallurgy

Osaka, Japan

Sony Corp. &

All type battery

Pyrometallurgy

Japan

All type battery

Pyrometallurgy+

Horne Que, Nikkelverk

Electrowinning

Nor, Sudbury Ont, Canada

Sumitomo Metals and Mining Co. XStrata

Accurec

All type battery

Pyrometallurgy

Mulhiem Grenada

DK

All type battery

Pyrometallurgy

Duisburg, Greece

AEA Technology

Li-Based

Batrec AG

Li-Based, Hg

Pyrometallurgy

Wimmis, CH, Switzerland

AFE Group (Valdi)

All type battery

Pyrometallurgy

Zurich CH, Switzerland

Sutherland, Scotland

Rogerville, France Citron

All type battery

Pyrometallurgy

Zurich CH, Switzerland Rogerville, France

Euro Dieuze/SARP

All type battery

Hydrometallurgy

Lorraine, France

SNAM

Cd, Ni, MH, Li

Pyrometallurgy

Saint Quentin Fallavier, France

IPGNA Ent.

All type battery

Hydrometallurgy 50

Grenoble, France

(Recupyl) Umicore

All type battery

Pyrometallurgy+ Electrowinning

51

Hooboken, Belgium

Table

6.

The

time

required

to

extract

all

the

lithium

LiNi1−y−zCoyMnzO2 Venkatraman et al. [131]. Cathode

Time required for quantitative extraction of the lithium

LiCoO2

<15 min

LiCo0.9Ni0.1O2

30 min

LiCo0.8Ni0.2O2

30 min

LiCo0.7Ni0.3O2

30 min

LiCo0.5Ni0.5O2

30 min

LiCo0.3Ni0.7O2

6 h

LiCo0.15Ni0.85O2

12 h

LiNiO2

48 h

LiNi0.75Co0.25MnzO2

36 h

LiNi0.5Co0.5MnzO2

36 h

LiNi0.33Co0.33Mn0.33O2

1 h

LiNi0.425Co0.15Mn0.425O2

18 h

52

from

Highlights    

Recovery and recycling of lithium are reviewed. Need for Li recovery technology development from low-grade sources recommended. Urgency for the alternative recycling method from secondary resources recommended. Considering the benefits, hydrometallurgical recycling of LIB should be focused.

53