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Recycling of Lithium from Li-ion Batteries
Bhuvaneshwari Balasubramaniama, Narendra Singha, Swati Vermaa, Raju Kumar Guptaa,b*
a Department of Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016,
UP, India
b Center for Environmental Science and Engineering, Indian Institute of Technology Kanpur,
Kanpur-208016, UP, India
*Corresponding author. Tel: +91-5122596972; Fax: +91-5122590104.
E-mail address: guptark@iitk.ac.in
Abstract
Battery recycling is one of the important fields in terms of providing second life to the energy
materials through recycling and reuse them for future applications. Lithium ion batteries (LIBs)
are used mainly in almost all the portable electronic devices such as mobile phones, camera,
laptops and electric vehicles etc. It is important to have green recycling process for effectively
utilizing the full potential of the spent LIBs. This will also reduce disposal of the dangerous heavy
metals and toxic chemicals in the environment. There are many recycling processes developed by
researchers while keeping in mind the importance of economic and environmental benefits. As a
result, many novel and ecofriendly business models are developed based on the recycling
processes. However, enormous efforts are required to reach the zero-by-product concept and
efficient recycling. In this chapter, we mainly focus on the process development,
economic/environmental benefits and future requirement towards recycling of LIBs. Spent LIBs
are classified under the category of a new kind of waste, different from other sections of solid
waste. Mainly the advantage of recycling spent LIBs is to eradicate the potential environment
impacts and to promote the sustainable development of the LIB industry and process upgrade at
industrial level through valuable metal recycling of resources.
Keywords: Batteries; Recycling; Reuse; Energy storage; Li-ion Batteries
Introduction
Batteries are used in many different applications including cars, radios, laptops, mobile phones,
and watches. Batteries are classified as primary batteries and secondary batteries. The former one
is known as alkaline batteries made up of zinc and manganese as primary source and mainly used
for household purposes, which convert automatically chemical energy into electrical energy. The
later one is usually made up of nickel (Ni), cadmium, nickel metal hydride or lithium ion and are
mainly used in mobile phones, electronic items, cameras, etc. Primary batteries are not
rechargeable, while the secondary batteries are rechargeable. The main concern of using batteries
is the threat to the environment at the end of its usage. Among all type of batteries, Lithium ion
batteries (LIBs) are gaining world-wide interest owing to use in almost all the modern life
applications. Experimentation were started by Gilbert Newton Lewis in 1912 over the use of LIBs.
After that disposable (primary) LIBs were developed in 1950s. Panasonic is the first company,
which produced commercial primary LIBs in 1970. LIBs, a rechargeable secondary battery was
first explored in 1970s by M.S. Whittingham at Exxon, which was made of titanium disulfide
cathode and a lithium-aluminum anode. Since the instability of metallic lithium presented in that
batteries caused safety risk, focus was primarily concentrated on the use of LiCoO2 and carbon as
the cathode and anode materials, respectively (Fey and Huang, 1999). Then, the LIBs were
commercially rolled out by Sony at Japan in 1991. The significant role of electrical energy storage
technologies demand for green and sustainable energy (Liu et al., 2016). The chemical reactions
that take place inside LIB during charging are shown in Equations 1-2. Further, the reverse
reactions occur during discharge.
Cathode: 6+++−→6 [1]
Anode: 2→(1−) 2+++− [2]
LIBs are generally used in portable electronic devices and electric vehicles (EV) due to their high
energy density, low self-discharge efficiency, long storage life, light weight, non-memory effect,
having wide range of application temperatures, small volume, and advantages in environmentally
compatible operations (Zheng et al., 2018, Li et al., 2016, Guo et al., 2016, Wang et al., 2016,
Santana et al., 2017, Yao et al., 2016, Xu et al., 2008). The major advantage of these batteries is
that they possess higher energy density (W/kg) compared to other battery chemistries being used
currently. LIBs presence in the market is from the year 1990 onwards, since the demand of LIBs
in electrochemical power sources such as portable electronics and electric vehicles are
unavoidable, it is extremely important to come out with the proper recycling methods as it also
avoids the environmental pollution due to dumping of heavy metals and toxic chemicals of spent
LIBs (Zheng et al., 2018). Also, it saves the energy by giving them second life until their potential
is completely utilized. Nowadays, hazardous mixing is a major threat for all the living species as
the exposure to pollutants are highly assured due to less care on the environment. Due to this,
severe health problems are witnessed, which consequently reduces the life span of people, animals,
etc. Hence, recycling of batteries is very much required to protect environment and human health.
In the modern era, an efficient harvest, management and storage are three essential segments to
energy consumption. Figure 1 explains about the life history of Li in the battery applications
(Winter et al., 2018).
Figure 1. Life history of Lithium in the battery applications (Reprinted with permission from
Winter et al., Copyright©2018, American Chemical Society)
Serious environmental pollution such as the infiltration of toxic heavy metals would occur in the
underground waterbodies due to the disposal of spent LIBs. On the other side, considerable
amount of poisonous gases, such as hydrogen fluoride (HF) will be produced to the atmosphere.
This will pollute the atmosphere while burning the spent LIBs. Hence, it is required to come out
with a green treatment method which should also bring economic benefits for the recycling of
spent LIBs. Due to the presence of larger amount of valuable metals, spent LIBs receive greater
attention on commercial aspect (Dorella and Mansur, 2007). The composition of spent LIBs
generally are in the range of cobalt (Co) 5%–20%, nickel (Ni) 5%–10%, lithium (Li) 5%–7% ,
other metals such as copper (Cu), aluminum (Al), iron (Fe), etc. (5%–10%), and the rest are 15%
organic compounds and 7% plastic (Ordoñez et al., 2016). However, spent LIBs compositions vary
from different sources depending on the manufacturer. The company ZSW has come out with the
data of stock and new registrations of battery-electric vehicles. Data reveals that globally, USA
and China are in forefront for the development of EV (Huang et al., 2018, Anderson, 2011). The
estimated global demand for LIBs is forecasted as per Table 1.
Table 1. Estimated global forecast for requirement of LIBs
Structure of LIBs and Spent LIBs
LIBs are defined as greener and cleaner energy storage devices compared to other batteries due to
their higher voltage, high energy density, low self-discharge efficiency, and less harmfulness to
the environment. The constituents of LIBs are generally cathode and anode materials, separator,
electrolyte, etc. Among these, the cathode assembly usually contains Al foil (collector), carbon
black, Polyvinylidene fluoride (PVDF) as binder, and the anode mainly contains Cu foil
(collector), graphite and PVDF binder. The challenge is mainly on recovering the maximum
number of valuables out of the minimum number of reagents used. Data shows that 4000 tonnes
(t) of spent LIBs contain 1100 t of heavy metals and more than 200 t of toxic electrolyte (Ordoñez
et al., 2016). Figure 2 illustrates the schematic diagram of the Li intercalation–de-intercalation
Estimated Year
Product
Estimate (t/year)
Reference
2015
Li2CO3 with the
battery grade
111700
(Mohr et al., 2012)
2050
Lithium exclusively
for EV batteries
400000
(Mohr et al., 2012)
2020
Lithium ion batteries
21000
(Anderson, 2011)
2020
Lithium carbonate
40000 – 95000
(Haber, 2008)
reaction mechanism in a rechargeable LIB containing solid electrodes and a liquid electrolyte (Roy
and Srivastava, 2015).
Figure 2. Schematic diagram of the lithium intercalation–de-intercalation reaction mechanism in
a rechargeable lithium-ion battery containing solid electrodes and a liquid electrolyte (Reprinted
with permission from Roy et al., Copyright©2015, Royal Society of Chemistry)
Applications of batteries
The LIBs are mainly used in electric cars due to their light weight nature and high energy density
as battery packs, cell phone towers, and electronic gadgets like mobile phone, cameras etc.
Statistics and legislation of LIBs
Data reveals that the production of LIBs has reached 500 million units in 2000 worldwide and in
2010, it is almost 4.6 billion units. The production of the LIBs in China has come to 5.287 billion
units in 2014 (Li et al., 2013, Shin, 2005, Jha et al., 2013). The greater the number of LIBs being
produced; the more spent LIBs will be generated, which need to be recycled. Statistics explained
that the lifetime of LIBs used in digital products will only be one to three years and the same will
be five to eight years for the power vehicles (Contestabile et al., 2001, Zheng et al., 2018).
According to these statistics, by 2020 it is expected that China will produce 2.5 billion of spent
LIBs with a mass of about 500000 t (Zeng et al., 2014).
According to the available report, a directive for collection and recycling of batteries is introduced
by European Union. Collection rate of 25% and 45% was targeted for all the batteries sold in 2012
and 2016, respectively. At least 50% of them needs to be recycled from the batteries collected.
LIB recycling is carried out in North America, Asia and Europe only. However, the drawback of
this collective recycling facilities is capability of treating less than 30% of the world’s LIB
production.
Benefits of recycling of LIBs
Environmental Protection Agency (EPA) states that, “batteries contain heavy metals such as lead,
cadmium, mercury, and Ni, which can harm the environment due to improper disposal of batteries
(Sun and Qiu, 2011). The spent LIBs usually consist of large amounts of valuable metals such as
Co, Mn, Fe, Li, etc. Although, the presence of metal contents is higher than natural ores in the
spent LIBs, however, these are recognized as typical hazardous solid waste as these contain toxic
metals as well as corrosive electrolytes. Dumping of waste LIBs in landfill sites contaminates the
soil. Leakage of the organic electrolyte and the heavy metals causes serious threats to the
environment. Recycling of spent LIBs is a preservation and recovery of valuable resources
according to the environmental point of view. Thus, recycling of spent LIBs is highly desirable.
Hence, the challenges and benefits on recycling spent LIBs highly depend on the finding green
and effective way of recovering the valuable metals. There should be emerging technical resources
to measure discards, find solutions and safe guard the environment. Government should enforce
strict environmental rules over battery recycling to safeguard the environment from dumping of
harmful metals arising from spent LIBs. Figure 3 illustrates the recycling of spent LIBs from
different sources.
Figure 3. Recycling of spent LIBs from different sources
Techniques for recovery of Li from LIBs
Li is extracted from the primary sources like mineral/clay and brines as well as from the secondary
sources (LIBs). LIBs are a huge waste across the world, which will increase the health risk of
humans, animals, etc. Recovering Li and other valuable metals from these waste batteries will
avoid the risk of environment pollution as well as will have advantage at economic level. There
are different processes to recover the heavy metals.
Apart from the highly valuable metals such as Li, Ni, and Co, but also Fe, Al, P, and other elements
with low recovery values are present in the spent LIBs. Recently, many researchers have come out
with the state-of-the-art processes for the metal recovery through recycling from spent LIBs which
are basically divided into three types such as pretreatment processes, metal- extraction processes,
and product preparation processes (Zeng et al., 2014, Ordoñez et al., 2016).
Pretreatment Processes
In the pretreatment process, the spent LIBs undergo manual dismantling or mechanical separation
process. This helps in segregation of cathode, anode and other components (Zheng et al., 2018).
After that the separated constituents are taken for metal- extraction process. Since the cathode
material is basically adhered to aluminum foil, separating the cathode from the foil is very difficult.
In order to effectively separate the cathode material from foil, different methods such as solvent
dissolution method (Yang et al., 2015, Yao et al., 2015, Song et al., 2013), ultrasonic-assisted
separation, sodium hydroxide (NaOH) dissolution method (Chen et al., 2011, Ferreira et al., 2009,
Nan et al., 2006, Nan et al., 2005), mechanical method (Zhang et al., 2013, Zhang et al., 2014) and
thermal treatment method (Yang et al., 2016, Hanisch et al., 2015, Sun and Qiu, 2011) are
implemented.
Metal Extraction Processes
Metal extraction processes are the most important method to recover the valuable metals (Li, Co,
Mn, etc.). Most commonly procedures essentially are (i) Hydrometallurgy, (ii) Pyro-metallurgy,
(iii) Biometallurgy, and (iv) Other process for the valuable metal recovery from the spent Li ion
batteries (Swain, 2017). These processes have different steps to get Li from spent LIBs as shown
in Figure 4. We will now discuss various processes in detail.
Figure 4. Classification of Lithium-ion battery recycling process
Hydrometallurgy
The metals were leached from the spent LIBs usually using the hydrochloric acid (Zhang et al.,
1998, Joulié et al., 2014, Barik et al., 2017, Takacova et al., 2016); sulfuric acid (Joulié et al., 2014,
Chen et al., 2015a); phosphoric acid (Pinna et al., 2017, Chen et al., 2017) and nitric acid (Joulié
et al., 2014, Lee and Rhee, 2002) etc. The metals (Co, Mn, etc.) were reduced from the high valent
state (in solid phase) to easily soluble Co+2, Mn2+, etc. using reducing agents e.g. hydrogen
peroxide, sodium carbonate, etc. The metal removal efficiency was affected by the temperature,
reaction time, type of leachants, concentration of leachants and reducing agents and solid to liquid
ratio.
Zhang et al. separated and recovered the valuable metals (e.g. Co and Li) from the spent LIBs.
They also examined the effect of leachant concentration, different leachants (e.g. hydrochloric
acid, hydroxyamine hydrochlorine, sulphurous acid, etc.), solid to liquid ratio, temperature and
reaction time for the removal of Co and Li (Zhang et al., 1998). Hydrochloric acid was found to
be the best leachant, which recovered 99% of Co and Li using 4 M HCl solution at 80 oC for 1 h
reaction (Zhang et al., 1998). Co was extracted by the solvent extraction and in sequence Li was
precipitate as carbonate (Zhang et al., 1998). The separation and selective removal of Ni and Li
was carried out from LiNiO2 based LIBs. The PC-88A was used as a commercial extractant for
the recovery of Ni and Li was recovered in form of lithium carbonate via precipitation using
Na2CO3 (Nguyen et al., 2015). Similarly, Lee et al. extracted Li from LiCoO2 using oxalic acid
leachant. They suggested that leachants like hydrochloric acid, sulfuric acid etc. leaches both Co
and Li in the solution and add complication towards the recovery of pure Li. Oxalic acid could
selectively recover/leach Li at low pH range. Li was recovered with less than 1% Co leaching as
impurity. The leached Co (1%) could be precipitated in the form of Cobalt oxalate. The process
was able to recover 90% Li from the LIBs at the optimum conditions. The Li ion in the solution
can be transformed into Li2CO3 using Na2CO3, after recovering of Co (Lee et al., 2004).
Pyrometallurgy
A typical pyrometallurgy process is a high temperature, smelting and reduction process for the
recovery of metals from the spent LIBs. The reduced valuable metals were then recovered in the
form of the alloy (Zheng et al., 2018, Zheng et al., 2017). Pyrometallurgy processes are mainly
focused on the recovery of the other metals (Co, Ni, etc.), while Li was lost in the slag owing to
its high reactivity (Zheng et al., 2017). In this process, spent LIBs were directly burned in the
smelted furnace, where plastics, graphite and organic components were combusted. The metals
were found in the alloy form, which were further purified using leachants and solvent extraction
(Zheng et al., 2018). This process results in loss of Li recovery. So, researchers have combined
pyrometallurgy process with hydrometallurgy or other processes.
Li et al. proposed the “waste + waste → Resources” approach (Li et al., 2016). The anodic
materials of graphite were utilized to reduce the cathodic materials of LiCoO2 under the oxygen
free conditions. The reaction was carried out at 1000 oC for 30 min under the nitrogen atmosphere
separately. The residue consisted of mixture of Co, Li2CO3 and graphite. The following reactions
might be happening during oxygen free environment (Li et al., 2016).
[3]
[4]
[5]
The residue mixture was further separated by the wet magnetic separation. The recovery of Co, Li
and graphite were found to be 97.52%, 98.93% and 91.05%, respectively (Li et al., 2016).
Similarly, Hu et al. presented a recovery of valuables from the cathodic materials LiNixCoyMnzO2.
Al was recovered via the alkaline leaching in the form of NaAlO2. The residue was further
undergone reduction roasting followed by the carbonated water and sulfuric acid leaching. The
reduction roasting was found to be optimum at 650 oC for 3 h with 19 wt% carbon dosage and
materials were transformed into Li2CO3, Co, Ni, and MnO. The residue mixture was further treated
with carbonate water leaching (20 mL min-1 CO2, solid to liquid ratio 1:10, reaction time 2 h) to
recover Li and acid leaching (H2SO4) of concentration 3.5 mol L-1 at 85 oC for 3 h to recover the
metals (Ni, Co, Mn). The recovery of Li was found to be 84.7%, while Ni, Co, and Mn were 99%
leached out by this process (Hu et al., 2017). In another work, Xiao et al. showed the mechanical
separation of mixed electrode materials from the spent LIBs containing binder, graphite and
LiMn2O4 followed by the oxygen free roasting of the mixed metal materials. In this process, binder
was decomposed into the gaseous products, while MnO and Li2CO3 were formed in the oxygen
free roasting at 1073 K for 45 min. 91.3% Li was leached in the form of Li2CO3 from the roasted
powder. Filtered residue was burnt in the air to get Mn3O4 and remove graphite (Xiao et al., 2017).
Träger et al. combined the mechanical pre-treatment process with the pyrometallurgical process to
recover the valuable components of batteries, while these pyrometallurgical process was carried
out to recover Li at higher than 1400 oC, makes it a high energy consumption process (Träger et
al., 2015). Georgi-Maschler et al. proposed a process to recover all the spent batteries components
using the combination of mechanical pre-treatment with pyro and hydrometallurgy. Co alloys and
Li2CO3 were the main products after the process (Georgi-Maschler et al., 2012).
Biometallurgy
Biometallurgical processes require less equipment, environment friendly besides being a low-cost
and high efficiency process. These processes can be promising alternatives than the
pyrometallurgy and hydrometallurgy processes. In typical biometallurgy process, the bacteria
produces organic and inorganic acids to leach the valuable metals from the spent batteries (Zeng
et al., 2014). Horah et al. used the fungal activities of Aspergillus niger for the bioleaching of the
spent LIBs. The citric acid was found to be important for the effective leaching compared to other
produced organic acids (gluconic, malic and oxalic acid). The process was conducted in three types
i.e. one step (suspension containing battery powder was inoculated in sucrose medium for 30 days),
two step (fungi was pre-cultured in sucrose medium for 3 days, which enters in the logarithmic
phase after that battery powder was added for 27 days), and spent medium process (A. niger was
first cultivated for 14 days, which enters in stationary phase and after that battery powder was
added for 16 days). The spent medium process showed high recovery (100% Cu, 95% Li, 38% Ni,
65% Al, 70% Mn and 45% Co), while one step process showed leaching of 100% Li, 11% Cu and
8% Mn with negligible Ni and two-step process showed 100% Li, 61% Al, 10% Mn, 6% Cu and
1% Co leaching with negligible Ni (Horeh et al., 2016). In another work, Acidithiobacillus
ferrooxidans and Acidithiobacillus thiooxidans were used for the removal of metals from the spent
LIBs. 99.2% Li, 50.4% Co and 89.4% Ni were recovered under the optimum conditions (iron
sulfate =36.7 g L−1 , sulfur = 5.0 g L−1, initial pH=1.5, best inoculum ratio of Acidithiobacillus
ferrooxidans / Acidithiobacillus thiooxidans = 3/2) (Heydarian et al., 2018). Mishra et al. utilized
Acidithiobacillus ferrooxidans bacteria for the bioleaching of LIBs containing LiCoO2, which
provided the elemental sulfur and ferrous ion to produce sulfuric acid and ferric ion in the leaching
medium. It has been found that Co showed faster leaching compared to Li, but slower dissolution
for Li than Co (Mishra et al., 2008). Xin et al. investigated mixed culture of sulfur-oxidizing and
iron-oxidizing bacteria for the bioleaching of the spent LIBs using different systems i.e. S, FeS2,
and S+FeS2. The bioleaching of Li was independent of energy sources, and mainly driven by acid
dissolution mechanism. The bioleaching Co was favored by the collective action of acid
dissolution and Fe2+ reduction in FeS2 and S+FeS2 systems, while the acid dissolution was the
main mechanism for the S system (Xin et al., 2009). The Acidithiobacillus thiooxidans and
Leptospirillum ferriphilum were used for the bioleaching of metals (Li, Ni, Mn, Co) from the spent
LIBs (LiFePO4, LiMn2O4 and LiNixCoyMn1-x-yO2 based batteries) and showed high recovery of
metals (Xin et al., 2016). Li recovery was maximum in the case of sulfur Acidithiobacillus
thiooxidans system owing to the biogenic H2SO4, while other metals were recovered in the mixed
energy source and mixed culture systems. The recovery of other metals (Co, Ni, Mn) was driven
by the acid dissolution and Fe2+ reduction (Xin et al., 2016). Niu et al. investigated the bioleaching
behavior utilizing licyclobacillus sp. (sulfur-oxidizing) and Sulfobacillus sp. (iron-oxidizing)
bacteria’s. The bioleaching efficiency was affected by the pulp density. 2% pulp density showed
the maximum removal efficiency of 89% and 72% for Li and Co, respectively (Niu et al., 2014).
The bioleaching efficiency was decreased from 52% to 10% and 80% to 37% for Co and Li,
respectively with increasing pulp density from 1% to 4% (Niu et al., 2014).
Other processes
Pyrometallurgy and hydrometallurgy are the main processes to recover the valuable metals from
the spent LIBs. Pyrometallurgy is high energy consumption and high metal loss process, and
environments hazards are produced in the form of gases and dust. The hydrometallurgy process
requires high quantity of chemicals. In the recent years, researcher have started new processes for
the recovery of valuable metals (Zheng et al., 2018).
Wang et al. achieved Co and Li recovery via mechanochemically. LiCoO2 materials were first
ball-milled with some additives, followed by water leaching procedure and subsequently recovery
of Li and Co in the form of Li2CO3 and Co3O4 by chemical precipitation process. The
ethylenediaminetetraacetic acid (EDTA) was found to be the best additive for the extraction of
valuable metals. After ball milling, Li-EDTA and Co-EDTA were formed by solid-solid reaction
owing to lone pair electrons (two nitrogen atoms and four hydroxyl oxygen atoms) of EDTA,
which can enter the empty orbitals of Co and Li. Li-EDTA and Co-EDTA were easily recovered
via water leaching. 98% Co and 99% Li could be recovered under the optimum conditions
(LiCoO2/EDTA mass ratio =1:4, ball milling time = 4 h, rotary speed of ball mill 600 rpm, and
ball/powder mass ratio = 80:1) (Wang et al., 2016). Saeki et al. investigated Li and Co recovery
via grinding with polyvinylchloride (PVC) using planetary ball mill. Li and Co were transformed
into the respective chlorides, which were leached out using water to recover Li and Co. The Co
and Li yields were increased to 90% after 30 h of grinding. The following reaction takes place
during the mechanochemical process (Saeki et al., 2004).
[6]
Wang et al. used PVC and other additives (Fe, Fe2O3, KOH, and many more) for the grinding of
LiCoO2.The ground mixture consisted of Li in the form of LiCl, Co in the form of magnetically
separable CoFexOy. Li was 100% converted into LiCl with the zero-valent Fe additive (Wang et
al., 2017). Liu et al. treated LiCoO2 (spent from LIBs) and PVC by the subcritical water oxidation,
where PVC acts as hydrochloric acid for the metal leaching. 95% Co and 98% Li were extracted
from the spent LIBs under the optimum conditions (reaction temperature = 350 oC, time= 30 min,
PVC/LiCoO2 ratio = 3:1, solid/liquid ratio =16:1 in g L-1) (Liu and Zhang, 2016). Yang et al.
targeted Li and Fe extraction from the spent LiFePO4 batteries through the combination of
mechanochemical process and H3PO4 leaching. 97.67% Fe and 94.29% Li were recovered from
the spent LIBs at the end of the process. The leached metals were further extracted by selective
precipitation and overall 93.05% Fe and 82.55% Li were recovered in the form of FePO4.2H2O
and Li3PO4 (Yang et al., 2017).
Table 2 contains consolidated data on the materials recovered from the spent LIBs.
Table 2. Consolidated data over the materials recovered from spent LIBs
S.No.
Recovery Conditions
Materials
Recycled
Recovery
References
Hydrometallurgy
1
Hydrochloric acid
Co and Li
99% of Co and
Li
Zhang et al., 1998
PC-88A
Ni and Li
-
Nguyen et al.,
2015
Oxalic acid
Co
-
Lee et al., 2004
Pyrometallurgy
2
High temperature, smelting
and reduction process
Li
-
Zheng et al., 2018
Co, Li and
graphite
97.52% of Co,
98.93% of Li
Li et al., 2016
and 91.05% of
graphite
Li, Ni, Co, and
Mn
84.7% of Li and
99% of Ni, Co,
and Mn
Hu et al., 2017
Li
91.3% of Li
Xiao et al., 2017
Li
Träger et al.,
2015
Co alloys and
Li2CO3
Georgi-Maschler
et al., 2012
Biometallurgy
3
Aspergillus niger
Cu, Li, Ni, Al,
Mn and Co
100% of Cu,
95% of Li, 38%
of Ni, 65% of
Al, 70% of Mn
and 45% of Co
Horeh et al., 2016
Acidithiobacillus
ferrooxidans and
Acidithiobacillus thiooxidans
Li, Co and Ni
99.2% of Li,
50.4% of Co
and 89.4% of
Ni
Heydarian et al.,
2018
Acidithiobacillus
ferrooxidans
Li and Co
Mishra et al.,
2008
sulfur-oxidizing and iron-
oxidizing bacteria
Li and Co
Xin et al., 2009
Acidithiobacillus thiooxidans
and Leptospirillum
ferriphilum
Li, Ni, Mn, and
Co
Xin et al., 2016
licyclobacillus sp. (sulfur-
oxidizing) and Sulfobacillus
sp. (iron-oxidizing) bacteria’s
Li and Co
89% of Li and
72% of Co
Niu et al., 2014
Other processes
4
Mechanochemical
Co and Li
98% of Co and
99% of Li
Wang et al., 2016
Co and Li
90% of Co and
Li
Saeki et al., 2004
Co and Li
100% of Li
Wang et al., 2017
Co and Li
95% of Co and
98% of Li
Liu and Zhang,
2016
Fe and Li
93.05% of Fe
and 82.55% of
Li
Yang et al., 2017
Post treatment (product preparation)
The Products can be prepared via many ways. The valuable metal salts have been recovered by the
biometallurgy, hydrometallurgy, pyrometallurgy etc., which usually consist of different metal
salts/ions. The metal salts can be separated by different processes such as solvent extraction,
floatation, chemical precipitation, etc. to get the individual metal salts. In other methods, the
cathode material precursor can also be directly prepared through proper solution composition.
Different metal ions were collected in leachate form at the end of metal extraction process. These
are separated by different processes such as solvent extraction, floatation, crystallization, etc.
Many authors have implemented several techniques to recover CoSO4 (Ferreira et al., 2009); Cu,
Co, Mn, Ni, and Li from spent LIB leachate (Chen et al., 2015b); Li, Fe, and Mn from mixed
cathode materials (combined LiMn2O4 and LiFePO4) (Huang et al., 2016). However, it is reported
that due to the involvement of large amounts of chemical reagents used in the recovery process,
the recovered product is not pure enough. In the case of preparation of precursors for cathode
materials, direct preparation methods are followed to avoid complicated separation processes
through fine tuning the composition of the leaching solution (Zheng et al., 2018). Further, as
obtained cathode material was processed further through co-precipitation (Sa et al., 2015, Krüger
et al., 2014) and sol–gel (Yao et al., 2015, Yao et al., 2016) to regenerate the same.
Conclusion
In this chapter, we have reviewed about the recycling of LIBs. We have discussed in-detail about
the type of components present in the spent LIBs and their recycling processes to recover valuable
metals. Statistics and legislation of LIBs are discussed as well and benefits of recycling of LIBs
are brought out briefly. Green and affordable recycling process is essential to safeguard the
environment from heavy metal contamination present in the spent LIBs. Further, effective
recycling of spent LIBs will bring down the cost of the raw materials and will help in improving
economics at the industrial scale.
Acknowledgements
BB acknowledges Department of Science and Technology (DST) support for providing the women
scientist project award (Grant No: SR/WOS-A/CS-17/2017).
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