Energy Reports 9 (2023) 6362–6395

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Energy Reports
journal homepage: www.elsevier.com/locate/egyr

Review article

A review on recycling of spent lithium-ion batteries

∗
Zsolt Dobó a , , Truong Dinh a , Tibor Kulcsár b
a
Institute of Energy, Ceramics and Polymer Technology, University of Miskolc, 3515, Miskolc, Egyetemváros, Hungary
b
Metal Shredder Hungary Zrt., 9012 Győr, Hegymester u. 62, Hungary

article info a b s t r a c t

Article history: Lithium-ion batteries (LIBs) with high power density are commonly used in electric vehicles and
Received 12 December 2022 portable electronic devices. Their applications have been soaring in recent years resulting in an
Received in revised form 12 May 2023 increasing number of used LIBs. Spent LIBs containing heavy metals and toxic hazardous are becoming
Accepted 30 May 2023
a severe threat to the environment and human health which must be addressed properly. Recycling
Available online 9 June 2023
is an option for end-of-life LIBs, which not only prevents the pollution of toxic components but also
Keywords: saves natural sources. This paper introduces battery structures and gives an overview of the current
Lithium-ion batteries state of waste LIBs and their recycling status. Moreover, recent advancements in hydrometallurgy,
Waste management pyrometallurgy, and direct recycling at both research and industrial levels are deeply analyzed. This
Recycling processes document can serve as a useful reference resource for researchers or engineers, who might profit from
Hydrometallurgy applying the concept to the examples summarized in the comprehensive review paper.
Pyrometallurgy © 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
Direct recycling
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction..................................................................................................................................................................................................................... 6363
2. Possible options for spent LIBs ..................................................................................................................................................................................... 6364
2.1. Management hierarchy of spent LIBs.............................................................................................................................................................. 6364
2.2. Re-use of spent LIBs .......................................................................................................................................................................................... 6365
2.3. The ultimate fate of lithium-ion batteries is recycling ................................................................................................................................. 6365
3. Recycling of spent LIBs .................................................................................................................................................................................................. 6366
3.1. Preliminary treatment processes ..................................................................................................................................................................... 6366
3.1.1. Discharge ............................................................................................................................................................................................. 6368
3.1.2. Dismantling ......................................................................................................................................................................................... 6370
3.1.3. Separation ........................................................................................................................................................................................... 6370
3.2. Pyrometallurgy ................................................................................................................................................................................................... 6372
3.2.1. Smelting .............................................................................................................................................................................................. 6372
3.2.2. Thermal reduction.............................................................................................................................................................................. 6373
3.2.3. Salt roasting ........................................................................................................................................................................................ 6374
3.2.4. Industry demonstrations ................................................................................................................................................................... 6374
3.3. Hydrometallurgy ................................................................................................................................................................................................ 6378
3.3.1. Leaching............................................................................................................................................................................................... 6379
3.3.2. Separate and recover valuable elements from leaching solutions............................................................................................... 6381
3.3.3. Industry demonstrations ................................................................................................................................................................... 6383
3.4. Direct recycling of spent LIBs........................................................................................................................................................................... 6385
3.4.1. Solid-phase sintering ......................................................................................................................................................................... 6385
3.4.2. Hydrothermal re-lithiation................................................................................................................................................................ 6387
3.4.3. Other regeneration processes ........................................................................................................................................................... 6388
3.4.4. Industry demonstrations ................................................................................................................................................................... 6388
4. Conclusion and perspectives ......................................................................................................................................................................................... 6388
Declaration of competing interest................................................................................................................................................................................ 6389
Data availability .............................................................................................................................................................................................................. 6389

∗ Corresponding author.
E-mail address: [email protected] (Z. Dobó).

https://doi.org/10.1016/j.egyr.2023.05.264
2352-4847/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Z. Dobó, T. Dinh and T. Kulcsár Energy Reports 9 (2023) 6362–6395

References ....................................................................................................................................................................................................................... 6389

capable of holding lithium in its layers. The active material of

Nomenclature carbon is attached to a copper conductor plate using polyvinyli-
dene fluoride (PVDF) binder (Arshad et al., 2020). In a similar way,
Abbreviation cathodes are a composite of PVDF binder, carbon powder, and Li
transition metal oxides such as LCO (LiCoO2 ), LMO (LiMn2 O4 ), LFP
D2EHPA Di-(2-ethylhexyl) phosphoric acid
(LiFePO4 ), NCA (LiNix Coy Alz O2 ) and NCM (LiNix Coy Mnz O2 ) which
DES Deep eutectic solvents
are coated by an Al foil. The comparison of the different cathode
DMAC N, N-dimethylacetamide materials of LIBs is shown in Fig. 2. The mostly utilized cath-
DMC Dimethyl carbonate ode material is LCO owing to its durability and elevated energy
DMF N, N-dimethylformamide density (Whittingham, 2004). Electrolytes are composed of a Li-
DMSO Dimethylsulfoxide containing salt solution like LiClO4 , LiBF4 , and LiPF6 dissolved in
EDTA Ethylenediaminetetraacetic an organic solvent of DMC (dimethyl carbonate) or EC (ethylene
EV Electric vehicle carbonate) (Bernardes et al., 2004). The electrolyte behaves as
LCO LiCoO2 a medium that allows ions to transport from one electrode to
LFP LiFePO4 the other one (Xu, 2004, 2014). A separator is placed between
the anode and cathode to obviate short-circuiting from direct
LIB Lithium-ion battery
contact between the two electrodes. The separator is composed of
LMO LiMn2 O4
polymeric materials such as PP (polypropylene) or PE (polyethy-
NCA LiNix Coy Alz O2 lene) acting like a non-conductor or a barrier (Arora and , John).
NCM LiNix Coy Mnz O2 Understanding the structures and compositions of lithium-ion
NCM (NMC) LiNix Coy Mnz O2 batteries could assist in the disassembly and mechanical process
NMP N-methylpyrrolidone of LIB recycling.
PDA Personal digital assistant Although lithium-ion batteries vary in manufacturers, cathode
PE Polyethylene materials, applications, shapes, etc, the mechanism of the bat-
PP Polypropylene teries is similar. The electro-chemical operating mechanism in a
lithium-ion battery is illustrated in Fig. 3. During discharging, Li+
PTFE Polytetrafluoroethylene
generated through reversible reactions at the anode migrates to
PVDF Polyvinylidene fluoride
the positive electrode. In contrast, during the charging process,
an external power supply provides electrons that combine with
Li+ to form metallic lithium (Li), intercalated into anodic graphite
layers. The chemical reactions happening at the two electrodes
are shown as follows (Xu et al., 2008):
1. Introduction
At the cathode:
A battery is an electrochemical device that stores and converts 6C + xLi+ + xe− ⇐⇒ C6 Lix (1)
chemical energy into electrical energy with elevated effective-
ness. Depending on the utility, batteries can be classified into At the anode:
primary and secondary batteries (Kosaraju, 2012). The primary LiCoO2 ⇐⇒ Li(1−x) CoO2 + xLi+ xe− (2)
battery is not able to recharge, meanwhile, the secondary battery
is rechargeable and possible to reuse for many cycles. Recharge- The direction forward means the charging reaction, mean-
able batteries mainly comprise LIBs, nickel-cadmium (Ni-Cd) bat- while, the reverse one is the discharge process. The energy is
teries, nickel-metal hydride (NiMH) batteries, and lead–acid bat- stored in the LIBs via the movement of Li+ , which is represented
teries. Compared to other secondary batteries, lithium-ion batter- in the equation (Xu et al., 2008).
ies have many superior advantages such as higher cell voltage, LiCoO2 + 6C ⇐⇒ Li(1−x) CoO2 + C6 Lix (3)
higher energy density, long lifespan, less memory effect, sim-
ple to charge and maintain, low self-discharge, environmentally A LIB can last up to three years in a small electronic device,
sound, the possibility of miniaturization, and very thin form fac- and from five to ten years in a larger device. Currently, more
tors (Zeng et al., 2014). LIBs were initially investigated in the late than 80% of lithium-ion batteries are utilized for small portable
1970s by Armand, however, Sony was the first to commercialize electronic devices, and the applications of LIBs in EVs and energy
the batteries in 1991 (Blomgren, 2016). Lithium-ion batteries storage systems make up less than 20% (Thompson et al., 2020).
have represented a turning point in the field of power sources, LIB disposal was estimated to be 10 700 tonnes in 2012 (Bae
they have been utilized in a variety of applications encompass- and Kim, 2021). This value has increased progressively each year,
ing communication equipment, remote car locks, and portable with an estimate of up to 250 000 tonnes in 2020 (Thompson
devices including camcorders, digital cameras, watches, PDAs et al., 2020). Despite the massive amounts of spent LIBs from
(personal digital assistants or handheld PC), thermometers, laptop portable electronics, most of the population stores them at home
BIOS, calculators, etc. Lithium-ion batteries are also commonly (59.6%) or throws them away (15.9%), meanwhile only 29.5% of
used in electric vehicles (EVs) with the purpose of ecological the population collects the spent LIBs properly (Mossali et al.,
friendliness (Dunn et al., 2011). 2020). Statistically, in the US, the EU, and Australia, the propor-
The typical composition of LIBs is depicted in Table 1 predomi- tion of used LIBs that are suitably collected and recycled is only
nantly comprises anode, cathode, separator, and electrolyte (Win- from 2% to 5% (Jacoby, 2019). The current state of waste LIBs is
ter and Brodd, 2004). Additionally, LIBs also have an electronic briefly presented in Fig. 4. End-of-life LIBs contain toxic materials
control unit, a protective metal casing, and covering plastic. The that can cause severe environmental pollution and pose a threat
components and shapes of some Li-ion battery configurations to human health. From another point of view, the used lithium-
are shown in Fig. 1. Anodes typically comprise carbon graphite ion batteries consist of significant quantities of metals (lithium,
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Table 1
Typical component and composition of LIBs Mossali et al. (2020).
Cell components Chemical composition %wt. Additional information
Fe–Ni alloy 20–26 Steel case is typical of cylindrical cells.
External casing
Al 10 Aluminum case is found in prismatic cells.
Cathode 25–30 –
Aluminum Al (Current collector foil) 5–8 –
Binder Usually PVDF 1–2 Alternatives: PTFE, butadiene-styrene rubber
(SBR) or modified cellulose (e.g. CMC).
Li 1.5–7 LCO gives better performances but is highly
Co LCO (LiCoO2 ) 5–20 expensive.
Metal oxide
It is replaced by NMC, LMO (where Mn gives
Ni LNO (LiNiO2 ) 5–10 structural stability) or C-coated LFP (LiFePO4 )
NCA (LiNi0.8 Co0.15 Al0.05 O2 ) that is safer.
Mn LMO (LiMnO2 ) 5
NMC (LiNix Coy Mnz O2 )
Polymeric separator Microporous PP or PE 4–10 –
Electrolyte 10–15 EC is the most used organic solvent, combined
Li salts LiPF6 , LiAsF6 , LiClO4 , LiBF4 – with others to lower its high melting T.
LiPF6 has high conductivity in any medium.
Organic solvents DMC-EC, PC-DME, BL-THF –
Anode 15–25 –
Copper Cu (Current collector foil) 8–10 –
Binder Usually PVDF 1–2 Inert, thermo-resistant and current-resistant
binder helping the adhesion.
Graphite 15–17 Low storage capacity of graphite (372 mAh/g).
Alternatives: C-NT, Sn compounds, metallic NP.

Fig. 1. The shape and components of some Li-ion battery configurations. (a) Cylindrical, (b) Coin, (c) Prismatic, (d) Thin and flat (Tarascon and Armand, 2001).

cobalt, nickel, copper, iron, aluminum, and manganese) (Zeng are given in Table 2, in which the cathode material accounts for
and Li, 2014b) which can even be greater than natural ores (Yao roughly 90% of the entire value.
et al., 2018). The composition of LIBs slightly differs between
the manufacturers and generally includes 7% of plastics, 15% of 2. Possible options for spent LIBs
organics, 5%–7% of Ni, 5%–7% of Li, and 5%–20% of Co (Shin et al.,
2005). Hence, recycling used lithium-ion batteries is vital for the 2.1. Management hierarchy of spent LIBs
protection of the environment and for saving natural resources.
The disposal not only prevents pollution of hazardous materials Management hierarchy of spent LIBs in particular or waste,
but also provides alternative metal resources, especially Li, Co, in general, is depicted in Fig. 5. The management possibilities
and rare metals which are deemed as important strategic ele- include prevention, re-use, recycling, recovery, and disposal in
ments (Zhu et al., 2012). The economic values of LIB components descending order of environmental desire.
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Fig. 2. Comparison of different cathode materials of LIBs (Jin et al., 2022).

• ‘‘Recycling’’ means that valuable materials presented in

spent LIBs are recycled and returned back into the value
chain.
• ‘‘Recovery’’ involves utilizing some materials of spent LIBs as
fuel for processes such as pyrometallurgy to recover energy
from waste.
• ‘‘Disposal’’ relates to disposing of spent LIBs without
recovered-value, the end-of-life LIBs go to landfills or to a
municipal waste combustion facility for incineration.

2.2. Re-use of spent LIBs

Batteries are suggested to be retired if their current electric

energy is less than 80% of their original value (Hesselbach and
Herrmann, 2011). A significant amount of power remains in these
end-of-life LIBs which can be capitalized via ‘‘re-use’’ options.
It is economically important as power batteries could make up
approximately 50% of total vehicles’ costs (Li et al., 2018c). Re-
use of spent electric vehicle LIBs includes remanufacturing and
repurposing.
Remanufacturing is an option for retired LIBs, whereby power
LIBs are refurbished and employed in their original applica-
Fig. 3. The electro-chemical operating mechanism of a LIB (Mossali et al., 2020). tions (Chen et al., 2019b). Remanufacturing includes diagnosis,
dismantling packs of LIBs, replacing damaged battery cells and
Table 2 damaged battery modules in the packs, and reassembling them
The economic value of LIB components Mossali et al. (2020). into new packs of LIBs. The quantities of spent vehicle LIBs are
Component Price (USD/tonne) anticipated to reach roughly 50% of the new battery demand
2001 2017 2019 between the years 2020 and 2033, and remanufacturing of spent
LIBs is assessed to save approximately 40% cost of new LIBs
Al 1250 2000 1800
Li 7500 9000 10000 usage (Foster et al., 2014).
Cathode Co 38000 55000 35500 Repurposing refers to reconfiguring retired vehicle batteries
Ni 8600 10000 13200 for ‘‘second life’’ usage in a non-vehicle application like stationary
Mn 1100 2000 2000 storage which is less stressful than EVs. By expanding the service
Cu 1800 5500 5800 lifetime of the used LIBs, the additional value could be extracted.
Anode
Graphite 550 1000 800 This management option requires replacements of damaged bat-
tery cells or modules and then reconfigurations of the modules
or packs to accommodate stationary applications (Chen et al.,
2019b).
• ‘‘Prevention’’ relates to LIBs that should be designed by using
less-critical materials, and electronic devices are lighter with 2.3. The ultimate fate of lithium-ion batteries is recycling
smaller LIBs to prevent and reduce waste generation.
• ‘‘Re-use’’ refers to giving spent LIBs a second usage to extend According to the hierarchy of waste management, remanufac-
their service lifetime. This option is mainly discussed in turing, and repurposing are preferable to recycling. Remanufac-
terms of electric vehicle (EV) batteries. turing is the most ideal option for spent LIBs as it maximizes the
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Fig. 4. Sources, quantity, and collection of discarded LIBs (Bae and Kim, 2021).

no matter whether they are first repurposed or remanufactured

for a second-use application. Remanufacturing or repurposing
just postpones the recycling which is the eventual fate for all
lithium-ion batteries (Fig. 6).

3. Recycling of spent LIBs

Hydrometallurgy, pyrometallurgy, and direct recycling are the

three main pathways used to recycle spent LIBs (Fig. 7). Pyromet-
allurgy refers to treating batteries under elevated temperatures
followed by separation steps. Hydrometallurgy involves using
aqueous solutions to dissolve valuable metals from spent LIBs
and reclaim the metals via the concentration and purification
stage. Direct recycling means that the structure of batteries’ ac-
tive materials is directly restored. Currently, pyrometallurgical
and hydrometallurgical processes are widely applied in industry,
while the direct recycling technique is mainly at the laboratory
level. The pros, cons, and challenges of these recycling methods
Fig. 5. Management hierarchy of the spent LIBs and the preference.
Source: Adapted from (Harper, 2019).
are briefly depicted in Table 3.
In terms of LIB recycling, only nickel, cobalt, aluminum, cop-
per, and steel are presently recycled on the grounds of techni-
cal viability and economical feasibility. Other elements such as
value of the batteries and minimizes emission and energy con-
graphite, lithium, and manganese are barely considered, mean-
sumption. Nonetheless, stringent battery quality requirements
while, plastics are used as fuel for energy recovery purposes
are a significant hurdle for this scenario. Recycling directly LIBs (Mossali et al., 2020). The recycling processes or treatments for
from first-life usage (in vehicles) is less preferable for the reasons the LIB components are summarized in Table 4. It is concluded
of insufficient benefit and the inevitable energy and material that the major studies are focused on cathode materials (Xu et al.,
losses during the process. On the other hand, recycling is advanta- 2008).
geous as instead of being refused, end-of-life lithium-ion batteries
are becoming a part of the circular economy, which partially 3.1. Preliminary treatment processes
reduces the demand for the extraction of new resources. In terms
of desirability, repurposing retired batteries for non-automotive The composition of end-of-life LIBs is intricate, thus prelim-
applications lies between these two approaches. However, recy- inary treatment processes are necessary to segregate disparate
cling is considered the most uncomplicated and applicable option battery elements and gain the active valuable substances which
for spent LIBs (Chen et al., 2019b). later are subjected to further processing. Preliminary treatment
Retired LIBs are reused or recycled mainly depending on the of spent LIBs generally compromises three major stages namely
expense of refurbishing the used batteries for a second-use ap- discharge, dismantling, and separation. The separation step con-
plication and the benefit that could reap from recycling retired sists of physical (floatation), mechanical (shredding and crush-
batteries instead. Recycling is the favored approach if the price ing), thermal (organic components evaporation), chemical (dis-
of second-use applications is less than the total of refurbish- solution of binder or foils), or mechano-chemical processes (Yao
ment cost and the recycling profit. For the time being, re-use et al., 2018). Some materials or valuable metals such as anode,
is firmly set for used LIBs from the economical point of view. Cu, and Al can be easily recycled via pre-treatment owing to
Nevertheless, the increasing number of retired LIBs is expected their physical property differences. While preliminary treatment
to greatly surpass the capacity of the second-use market (Sun processes are used with the purpose of segregating cathodic sub-
et al., 2018a). In the end, the retired LIBs finally must be recycled, stances from organic binders and Al foils, the components make
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Fig. 6. Lifecycle of a power LIB .

Source: Adapted from (Li et al.,
2018c).

Fig. 7. Typical processes for recycling spent LIBs .

Source: Adapted from (Chen et al., 2019b).

Table 3
Pros, cons, and challenges of different recycling processes Zhou et al. (2020).
Process Advantages Disadvantages Challenge
Hydrometallurgical • High recovery rate • More wastewater • Wastewater treatment
process • High purity product • Long process • Optimize the process
• Low energy consumption
• Less waste gas
• High selectivity
Pyrometallurgical • Simple operation and • Li and Mn are not • Reduce energy
process short flow recovered consumption and pollution
• No requirement for • High energy consumption emissions
categories and the size of • Low recovery efficiency • Reduce environmental
inputs • More waste gas and the hazards
• High efficiency cost of waste gas treatment • Combine hydrometallurgy
well
Direct recycling • Short recovery route • High operational and • Reduce recovery costs
process • Low energy consumption equipment requirements • Lower the requirements
• Environmental friendly • Incomplete recovery for categories
• High recovery rate • Further optimize product
performance

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Table 4
Summary of recycling processes or treatments for the LIB components Xu et al. (2008).
Components Elements Recycling processes References
Fe Mechanical processes; thermal treatment Shin et al. (2005),
Shells
Castillo (2002),
Dorella and Mansur
(2007) and Nan
et al. (2005)
Plastics Mechanical processes Shin et al. (2005)
and Dorella and
Mansur (2007)
Aluminum foil Al Mechanical processes; acid leaching; chemical Shin et al. (2005)
precipitation and Dorella and
Mansur (2007)
Cu Mechanical processes Shin et al. (2005)
Anode
C (graphite) Mechanical processes; thermal treatment Shin et al. (2005)
and Castillo (2002)
Adhesive agent PVDF binder Thermal treatment Castillo (2002) and
Lee and Rhee (2002)
Electrolyte (organic Thermal treatment; Thermal treatment; solvent extraction Castillo (2002),
liquid-LiPF6 , LiBF6 , solvent extraction Bahgat et al. (2007)
LIClO4 ) and Lain (2001)
Co Mechanochemical process; dissolution process; thermal Castillo (2002),
Cathode (LiCoO2 , treatment; acid leaching; bioleaching; solvent Dorella and Mansur
LiNiO2 , LiMnO4 ) extraction; chemical precipitation; electrochemical (2007), Brandl and
process Faramarzi (2006),
Zhang et al.
(1998b), Lin et al.
(2003), Tanii et al.
(2003), Myoung
et al. (2002), Nan
et al. (2005), Lee
and Rhee (2002),
Lain (2001),
Mantuano et al.
(2006), Mishra et al.
(2008), Zhang et al.
(1998a),
Contestabile et al.
(2001) and Saeki
et al. (2004)
Li Mechanochemical process; thermal treatment; Castillo (2002),
dissolution process; acid leaching; bioleaching; Solvent Dorella and Mansur
extraction (2007), Brandl and
Faramarzi (2006),
Zhang et al.
(1998b), Lin et al.
(2003), Tanii et al.
(2003), Myoung
et al. (2002), Nan
et al. (2005), Lee
and Rhee (2002),
Lain (2001),
Mantuano et al.
(2006), Mishra et al.
(2008), Zhang et al.
(1998a),
Contestabile et al.
(2001) and Saeki
et al. (2004)
Ni Mechanochemical process; chemical precipitation; Castillo (2002) and
electrochemical process Lupi and Pasquali
(2003)
Mn Chemical precipitation Castillo (2002)

the waste hard to leach or increase the complexity of leachate (Lv 3.1.1. Discharge
et al., 2018). Pre-treatment reduces impurities, facilitates the sub- In order to minimize short-circuit and self-ignition, the resid-
sequent recovery process, and enhances the overall efficiency of ual power in retired lithium-ion batteries needs to be eliminated
recycling spent LIBs. Several studies regarding preliminary treat- via a discharging process. The end-of-life LIBs could be discharged
ment processes with optimal operating conditions are presented by utilizing a salt solution, for instance, sodium sulfate (Na2 SO4 )
in Table 5. or sodium chloride (NaCl) (Wang et al., 2017a; Nie et al., 2015).
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Table 5
Preliminary treatment processes for LIBs with optimal operating conditions Mossali et al. (2020).
Process Operating parameters Ref. Pros Cons
Discharge
Salts saturated • 10%wt NaCl 36 h; 5%wt NaCl 24 h Chen et al. • Ionic contamination
solution (2018a) and
Wang et al.
(2018)
Thermal pre-treatment
Calcination • In a muffle furnace Xu et al. • Cell opening and • Cu corrosion
• 300 ◦ C; 450 ◦ C 15 min; (2008), Wang deactivation • Toxic gaseous
◦ ◦
500 C 2 h; 500 C 30 min et al. (2018), • Binder and organic emission
with a heating rate of Diekmann et al. compounds removal • High energy
5 ◦ C/min; 500–580 ◦ C; 700 ◦ C (2017), Paulino • Easiness consumption
1 h et al. (2008), • Economically
Yang et al. sustainable
(2017b) and
Rahman and
Afroz (2017)
Oxygen-free • N2 atmosphere in a tube Li et al. (2016a)
roasting furnace and Yang et al.
• 1000 ◦ C 30 min; 600 ◦ C 15 (2016)
min
Enclosed- • 800 ◦ C Xiao et al.
Vacuum (2017a)
Environment
Vacuum • Pressure 1 kPa Zhang et al.
Pyrolysis • 600 ◦ C 30 min with a (2013b) and
◦
heating rate of 10 C/min Sun and Qiu
(2011)
Mechanical and physical pre-treatment
Grinding • 4 mm crushing; hammer Shin et al. • Valuable metals • Not complete
(Mechanical mill 6 mm 2000 RPM (2005), Jha segregation separation
pre-treatment) • Initially 20 mm, then fine et al. (2013) • Scrap volume • Impurities
crushing 10 mm and Gratz et al. reduction • Gaseous emissions
(2014) • Reduces costs and • Cathodic powder
Physical pre-treatment high throughput input
• Flexibility • LiCoO2 -graphite
Sieving • Sieves at 300 µm; 300 µm 3 Gratz et al. • Increased contamination.
min; 250 µm (2014), hydrometallurgical
• Sieves at 850 m, 200 m, and Al-Thyabat selectivity
106 m et al. (2013), • Low energy
• Vibrating sieve 10 min Zhou et al. consumption
2 mm, 1 mm, and 500 µm (2010), • No external
• Air jet separation 1 min with Pagnanelli impurities
sieve 50 µm et al. (2016)
and Hanisch
et al. (2015)
Ultrasonic • 12 mm aperture 15 min Huang et al.
washing • With NMP 70 ◦ C 90 min (2018) and
240 W Zheng et al.
(2018b)
Floatation • Combined with grinding 5 min Wang et al.
(2018) and Yu
et al. (2018)
Chemical pre-treatment
Electrolyte • Supercritical CO2 ; anhydrous Al-Thyabat • Wastewater
dissolution solvent with boiling T < 80 ◦ C et al. (2013) production
and Huang
et al. (2018)
Binder • NMP 40 ◦ C 14 min; NMP Lv et al. (2018),
dissolution 100 ◦ C 1 h Al-Thyabat
• DMF 60 ◦ C 2 h et al. (2013),
• Citrus Fruit Juice 90 ◦ C; Zhou et al.
Citrus Pseudolimon Tanaka (2010), Huang
90 ◦ C 20 min et al. (2018),
• DMAC 30 ◦ C 30 min with Bankole et al.
solid(g)/liquid(mL) 1:20 (2013) and
Pant and
Dolker (2017)

(continued on next page)

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Table 5 (continued).
Process Operating parameters Ref. Pros Cons
Mechano- • EDTA chelate agent in a Yang et al. • Room temperature • Long reaction times
chemical grinding mill at 600 RPM 4 h (2017b), Wang • Low energy • Noise generation
pre-treatment with ball/powder 80:1 et al. (2016b) consumption
• EDTA-2Na 2 h with a and Wang • Simple procedure
cathode/agent ratio 3:1 et al. (2017a) • Economically
• PVC + Fe 12 h with sustainable
cathode/agent/Fe ratio 1:1:2 • Environmentally
friendly

This discharging approach’s efficiency strongly depends on the investigations study the cooperation of humans and robot to
batteries’ state of charge, the operating time, the operating tem- remarkably lower costs and times, proposing possible options to
perature, and the specific conductivity of the solution. He et al. deal with various product sizes, disassembly tasks, etc (Wegener
completely discharged scrap lithium batteries by submerging the et al., 2015).
batteries in a 5 wt% sodium chloride solution (He et al., 2017a).
Li and his colleagues researched the influence of discharging time 3.1.3. Separation
and NaCl solution concentration on the spent LIB discharging The pre-treatment step of separation comprises mechanical
process (Li et al., 2016b). It was shown that the submersion of and physical, thermal, chemical, and mechano-chemical pro-
used LIBs in a 10 wt% NaCl solution for 358 min results in an ideal cesses. Its major purposes are enriching metallic fraction,
discharge efficiency of 71.96% and reasonable cost. The critical lowering scrap volumes and energy consumption, enhancing re-
drawback of using salt solutions is the release of toxic gases covering rate, and managing safety issues (Lv et al., 2018). The
(HF) due to the leakage of electrolytes into the water, which is pre-treatment step of separation is essential prior to the hy-
represented in the following equation (Lv et al., 2018). drometallurgy because the leaching process is hindered by the
impurities from aluminum foil and copper foil.
LiPF6 + 2H2 O ⇐⇒ LiF + POF3 + 2HF ↑ (4)
Mechanical and physical preliminary treatment processes
Connecting retired LIBs to resistors is another way to discharge The combination of physical pre-treatments and mechanical
spent LIBs, in which the remaining energy in the batteries could pre-treatments is commonly employed in industry to segregate
be collected and reused (Mossali et al., 2020). By connecting to valuable materials, remove the outer case and reduce scrap vol-
a resistor, the batteries can be discharged between 3 and 0 V, umes of spent LIBs. This technique includes several processes
and 7 MJ of the residual energy could be recovered from 1 ton such as crushing, magnetic separation, sieving, ultrasonic wash-
of batteries (Sonoc et al., 2015). Nonetheless, the moderate gain ing, flotation, and so on. The typical procedure of this approach
is inadequate to cover the investment costs, this approach is involves a first shredding stage, the external case is eliminated via
inappropriate for treating a massive amount of scrap LIBs. magnetic segregation. This is followed by fine crushing and siev-
The discharging step largely is eliminated in the industry cur- ing to separate organic materials and current collector foils from
rently. End-of-life LIBs can be directly disassembled and shredded the active leachable powder (Gratz et al., 2014). After crushing
under the protection of industrial technology to lower the cost and sieving, copper foil, aluminum foil, plastics, etc., mostly exist
and processing of LIB recycling as well as to avoid problems in coarse particles (Zhou et al., 2010) as they tend to be curled
that arose from the discharging stage. For instance, Batrec In- than shredded. Meanwhile, electrode substances like LiCoO2 and
dustrie AG crushes spent batteries under a carbon dioxide at- graphite are mainly fine particles (Zhang et al., 2013a). Cop-
mosphere (Anon, 2022h), and Recupyl Valibat shreds cells in per and aluminum in the coarse fractions can be separated via
an inert gas mixture (Ar or CO2 or a mix of these gases) to Eddy Current separation techniques, while the plastics can be
prevent violent Li reactions (Velázquez-Martínez et al., 2019). eliminated by a densimetric table as reported in Fig. 8.
Retriev (Toxco) crushes scrap batteries under a lithium brine to The crushing process generates impact stresses transferring ki-
reduce the reactivity of the batteries, obviate gas emissions, and netic energy into breakage energy to break the agglomerates and
neutralize the electrolyte (Anon, 2022a). create different particle size factions (Hanisch et al., 2015). Crush-
ing is characterized by simple operation, low cost, high efficiency,
3.1.2. Dismantling and strong processing capacity. Additionally, the increased sur-
Following the discharging process, the discharged batteries face area of crushed products promotes metal dissolution during
are manually disassembled and segregated into disparate com- acid leaching of the subsequent hydrometallurgical process (Al-
ponents namely steel or plastic cases, organic separators, anodes, Thyabat et al., 2013). The crushing technique is typically classified
and cathodes aiming to lessen the treated material volume. The into the wet crushing process and the dry crushing process. The
cases of the batteries are disassembled and eliminated at first spent LIBs are shredded in dry after discharging referred to dry
to obtain the cell core, followed by uncurling and separating the crushing while gridding directly waste LIBs in salt solutions is
anode and the cathode. Some tools like knives, saws, and pincers wet crushing. The wet crushing approach could efficiently de-
are used in the manual dismantling process which is conducted crease the release of hazardous gases and Li reactivity (Diekmann
under safety precautions (Yao et al., 2018). The manual operations et al., 2017), but this method can make fine particles intricate
are inappropriate for the treatment of mass scrap LIBs. Thus, me- and lost because of the flow erosion influence (Zhang et al.,
chanical treatments are used instead including shredding, sieving, 2013a). Dry crushing spent LIBs in an inert gas atmosphere is suit-
magnetic classification, and segregation. The mechanical separa- able from safety and practical perspectives. This manner obviates
tion process has an advantage from the economical and industrial short-circuiting and the dangers triggered by impacts or frictions.
points of view (da Costa et al., 2015). However, this method also Furthermore, crushing end-of-life LIBs in an inert gas atmosphere
shows the disadvantage of penetrating inorganic materials, or- can also advance processing effectiveness (Lain, 2001).
ganic substances, and metals of complicated LIBs into each other, Sieving is a separation process based on the particle size differ-
which makes the separation process more difficult (Xu et al., ence of the battery components; this treatment is used after the
2008). The mechanical separation processes will be discussed in crushing step. Used LIBs are found to possess high selective shred-
the following section. In terms of electric vehicle LIBs, several ding properties, the shredded particle fractions can be separated
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Fig. 8. Combination of mechanical pre-treatment and physical pre-treatment to separate cathode active materials (Mossali et al., 2020).

into three portions (Zhang et al., 2014b). The fraction above 2 mm 550 ◦ C (e.g. Li4 Mn5 O12 to → LiMnO4 and LiCoO2 → Co3 O4 ) which
largely consists of aluminum, the particles ranging from 0.25 mm improves the subsequent leaching efficiency (Mossali et al., 2020).
and 2 mm are rich in copper and aluminum, while the pro- Meanwhile, temperatures higher than 600 ◦ C make Al layers
portion below 0.25 mm mainly contains Co and graphite. Wang fragile hindering the segregation of active metals powder (Sun
et al. indicate that the material concentrations of the particle and Qiu, 2011).
size fractions differ from lithium-ion battery types (Wang et al., In addition to temperature, pressure is another important fac-
2016a). Hence, pre-sorting LIB types is recommended to minimize tor in thermal preliminary treatment processes. Vacuum pyrolysis
the uncertainty of the inputs and to enhance the segregation is an emerging method, which can protect valuable metals from
effectiveness of waste streams. oxidation and offers direct foil recycling (Jin et al., 2022). Oxygen-
The combination of crushing and sieving might be not suf- free roasting in the N2 atmosphere is another thermal pathway
ficient for segregating fine particle fractions. Flotation operated remarkably enhancing wet magnetic separation in which Co is
on the hydrophilic dissimilarity of the substance surface can be magnetized and attached to the magnetic stirrer, graphite is pre-
employed instead to segregate LiCoO2 powder from graphite. It cipitated in the bottom of the beaker and collected by filtration,
is an effective segregation technique and has a high potential and roasted LiCO3 is dissolved in water (Li et al., 2016a).
for industrial applicability. However, the organic material such as
Chemical preliminary treatment processes
PVDF used as binders in both electrodes reduces the selectivity of
Chemical preliminary treatment pathways utilize alkaline so-
flotation and makes segregation extremely difficult (Zhang et al.,
lutions and organic solvents to liberate the electrode substance
2014c). Therefore, the organic binder needs to be eliminated to
from aluminum foils or employ supercritical fluids to extract
enhance the wettability disparity and advance the efficiency of
electrolytes. Based on the principle of similarity-intermiscibility,
the flotation process. The organic compounds could be removed
the use of the organic solvent is to dissolve binders and detach
by thermal treatment, which releases toxic and hazardous gases.
the active substances from Al layers, hence the structure of the
The binder can also be dissolved through chemical solutions, but
electrode materials is relatively preserved. N-methylpyrrolidone
it can generate impurities.
(NMP) is a commonly used organic solvent because this solvent
Ultrasonic washing is another physical preliminary treatment,
and PVDF binder are polar allowing their easy dissolution into
where the rinsing effect is coupled with cavitation phenomena,
each other (Yao et al., 2018). It was observed that the cathodic
it efficiently advances the segregation of active materials to the
active substances could be separated easily from the supports af-
aluminum current collector foil. The effectiveness of this method
ter immersing the cathodes in N-methylpyrrolidone at 100 ◦ C for
might achieve 99% if it is combined with the usage of solvents
1 h (Li et al., 2014). In another study, positive electrodes are firstly
that act on the organic binders (Mossali et al., 2020). Ultrasonic
immersed in N-methylpyrrolidone at 80 ◦ C for 1 h, followed
washing consumes less energy compared to thermal preliminary
by an ultrasonic treatment (Yao et al., 2015). The ultrasonic-
treatments and multiple shredding processes (Huang et al., 2018).
assisted process was found to enhance the effectiveness and the
Thermal preliminary treatment processes yield of segregating the positive electrode substances from the
Thermal preliminary treatments are commonly utilized to re- Al sheet (Yao et al., 2015). The influence of ultrasonic treatment
move binders and carbon (C) in cathodes and segregate the ca- on the separation of cathodic active materials was also reported
thodic active substances. This manner decomposes binders at ele- in (Yang et al., 2015). In addition to N-methylpyrrolidone, other
vated temperatures and separates the active metals powder from organic solvents including dimethylsulfoxide (DMSO) (Bankole
Al foil. The high-temperature technique is usually associated with et al., 2013), N, N-dimethylformamide (DMF) (Xu et al., 2014),
crushing, sieving, flotation, and ultrasonic cleaning to obtain the N, N-dimethylacetamide (DMAC) (Zheng et al., 2016a), and ionic
required materials. Thermal preliminary treatment is appropriate liquid (Zeng and Li, 2014a) are also utilized to separate the active
for large-scale levels owing to its simplicity. Nonetheless, energy cathodic substances.
consumption and the cost of equipment for this treatment should Aluminum current collectors are recovered in metallic form
be taken into account in the economic sense. Additionally, the during the process of dissolution, and the used organic reagents
decomposition of organic binders (PVDF) generates highly toxic could be reutilized. Nevertheless, this pre-treatment method is
gases of HF and the release of heavy metals. Thus, it is necessary strongly dependent on the chemical composition, using only
to use a cleaning system to dispose of hazardous emissions. one organic solvent is not able to dissolve all types of binders.
The decomposition of binders in an oxygen atmosphere was If binders are composed of PTFE instead of PVDF,
found to start at 350 ◦ C (Hanisch et al., 2015). The optimal tem- N-methylpyrrolidone does not work well as they are not polar.
perature for burning off organic components ranges from 500 ◦ C The organic solvents could not eliminate the impurities com-
to 600 ◦ C (Mossali et al., 2020), resulting in the spitting of C chains pletely, thus further calcination processes are necessary to burn
into shorter units and the detachment of substances from current off all the residuals of PVDF or C. Furthermore, the dissolution
collector foils (Chen et al., 2018a; Yang et al., 2016). On the other reagent is known as a toxicant, it is costly and inappropriate
hand, metal phase transformations occur at a temperature of for large-scale applications (Lv et al., 2018). A green reagent of
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citrus fruit juice was used as a dissolution solvent to avoid the (Windisch-Kern et al., 2022). In short, pyrometallurgy is an ele-
environmental drawback of employing hazardous reagents (Pant vated temperature technique, which usually involves two stages
and Dolker, 2017). However, the dissolution process utilizing of burning and subsequent separation. The pyrometallurgical
citrus fruit juice needs to be conducted under high-temperature process for recycling used LIBs could be typically divided into
conditions of over 90 ◦ C. thermal reduction, high-temperature smelting, and salt roasting.
Because alkali does not react with oxide cathodic materials, Pyrometallurgy is a prevalent and mature recycling technique,
hence, alkali solutions are employed to efficiently separate active it is commonly used due to its rapidity, simple operation, and
materials. In this method, alkaline solutions (NaOH) dissolve Al flexibility (Chen et al., 2019b). Additionally, in the pyrometallur-
layers, while binders are eliminated via further calcining pro- gical process, pre-sorting of batteries is unnecessary, a medley
cesses to obtain a somewhat pure electrode active substance (Nan of NiMH batteries and LIBs could be recycled. The products of
et al., 2005; Ferreira et al., 2009). This technique achieves high pyrometallurgy including elemental ‘‘building blocks’’ could be
aluminum extraction efficiency and preserves other metals; how- utilized to synthesize new cathodic substances. On the other side,
ever, losses are inevitable and aluminum plates are not in metal the generation of toxic gases (such as CO2 ) during pyrometallurgy
form. On the other hand, the alkaline solution dissolution intro- is a severe environmental concern of this technique. The smelting
duces impurities hindering further recovery processes (Jin et al., process is characterized by high energy consumption, and subse-
2022). quent treatments are required for the obtained alloy, extending
the cost of the overall procedure. The number of substances
Mechano-chemical preliminary treatment processes reclaimed via pyrometallurgy is limited, only copper of the foil
Mechano-chemical technology is a combination of mechanical and nickel and cobalt from positive electrodes are recovered
pre-treatment and chemical pre-treatment means to separate ac- making up 30 wt % of batteries in electronic devices, while other
tive substances. This technique takes benefits of integrated effects materials like plastics, graphite, and Al are not. This technology
of mechanical shredding and chelate reagents like polyvinyl chlo- possibly does not work well for the LIBs used in electrical vehicles
ride (PVC) and Ethylenediaminetetraacetic (EDTA). The surface because of the poor cobalt content. Additionally, the industry
area enhancing and particle size lessening lead to polymorphic of vehicle LIBs is moving towards cobalt reduction, eventually
transformations of cathode substances and the bond breakage, achieving free-cobalt electrodes. Table 6 shows a summary of
which advances reaction activities for further acid-leaching pro- studies regarding the pyrometallurgical recycling processes of
cesses (Wang et al., 2016b). The energy converted to battery LIBs.
elements is assisted by chelate reagents enabling to change or
disrupt the crystal structure of used LIBs. Mechano-chemical pre- 3.2.1. Smelting
treatment is utilized to destroy the original structure of waste One of the efficient pyrometallurgical options for reclaiming
LIBs to improve the leaching effectiveness (Yang et al., 2017b). valuable elements from end-of-life LIBs is smelting. Owing to
This technique is quite simple and economically sustainable, but its superior productivity and simplicity, smelting is prevalently
it is far from industrial applications due to the long reaction applied in industrial implementations. During this processing, the
times (Wang et al., 2017a). substances of LIBs are heated over their melting points, facili-
Although many studies regarding preliminary treatment pro- tating the segregation of metallic elements in the liquid phase
cesses have been carried out, technical challenges and obsta- through reductions and ensuing formations of immiscible molten
cles still exist. The mechanical separation technology focuses on layers (Makuza et al., 2021). Smelting is conducted in two stages;
the productivity and the effectiveness of the process; however, battery materials are heated at low temperatures at first aiming at
the precision of the segregation is quite poor. Chemical pre- evaporating electrolytes and preventing the explosion of the bat-
treatments and thermal pre-treatments can attain relatively pure tery caused by overpressure. This is followed by heating the feeds
materials and obviate drawbacks in further recovery process- at elevated temperatures and the battery materials are melted.
ing; however, they are still far from the ideal effect. Moreover, The main outputs of smelting processing include slags and metal
disordered classifications of end-of-life LIBs, the complexity of alloys. The metal alloy contains valuable elements like Ni, Co,
dismantling processing, and poor extraction effectiveness of high- and Cu which can be further reclaimed through hydrometallurgy.
value elements such as Li still impede implementations of sep- The slag fraction usually containing lithium and manganese can
aration processes. Hence, to effectively, completely, and purely be recovered by hydrometallurgy or alternatively be utilized in
separate active substances from current collectors, integrating the cement industry (Harper, 2019). In the smelting process,
various methods is necessary. At present, pre-treatments remain aluminum performs as a reductant reducing energy requirements.
a huge challenge to achieving the aim of recycling all high-value The battery components namely plastics, electrolytes, and anodes
metals or materials in retired lithium-ion batteries. are oxidized providing energy for the smelting processing.
Xiao et al. (Xiao et al., 2017b) recycled scrap lithium-ion
3.2. Pyrometallurgy batteries by using a MnO–SiO2 –Al2 O3 slag system. The process
consists of two critical steps which are the smelting reduction and
Pyrometallurgy uses high temperatures to recover (Yun et al., refining steps. In the first step, the mixture of shredded used LIBs,
2018; An, 2019) and purify valuable metals via physical and roasted polymer waste LIBs, and aluminum cans were heated at
chemical transformations (Lv et al., 2018; Liu et al., 2019a). Struc- 1550 ◦ C to obtain Mn-rich slag comprising lithium and Co–Ni–
tural changes and phase transitions occur at lower temperatures, Cu–Fe–Mn alloy. To refine the metallic alloy fraction, SiO2 was
meanwhile, chemical reactions take place at higher tempera- added formatting MnO–SiO2 thereby manganese was eliminated,
tures (Yu et al., 2022). The necessary energy for pyrometallurgy and MnO–SiO2 slag can be reutilized in the smelting processing.
comes from electric energy, combustion, and exothermic reac- The high-value elements in Mn-rich slag and the metallic alloy
tions. Pyrometallurgy predominantly depends on temperature, eventually were leached and recovered by subsequent hydromet-
processing time, flux addition, and types of purge gas (Makuza allurgical processes. A novel FeO–SiO2 –Al2 O3 slag system with
et al., 2021). Pyrometallurgy alone generally is not able to at- the use of inexpensive Cu slag as an additive for the process
tain the complete recovery of LIBs. It aims at transforming the was developed to recycle retired LIBs (Ren et al., 2017). It was
battery elements into favorable phases for the further process of observed that 93.57% of copper, 98.39% of nickel, and 98.83% of
hydrometallurgy. Therefore, hydrometallurgical procedures like cobalt were recovered under the optimal conditions of smelting
leaching are needed in pyrometallurgical-based processes at 1723 K for 30 min and slag former/battery mass ratio of 4:1.
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Table 6
Studies on pyrometallurgical recycling of spent LIBs.
Pyrometallurgy Cathode Additive Pretreatment Thermal Separated material Secondary process Recovery rate Ref
Technique material treatment
condition
◦
Smelting Mixed spent LIBs SiO2 Roasting at 800 C 1550 ◦ C for Co–Ni–Cu–Fe–Mn Acid leaching 98.67% Cu, 99.84% Xiao et al. (2017b)
for 2 h 15 min alloy and (H2 SO4 ) Co, and 99.77% Ni
manganese-rich
slag containing
lithium

Smelting LiCoO2 Cu slag (slag – 1450 ◦ C for Co, Ni, Cu, and Fe Manual separation 98.83% Co, 98.39% Ren et al. (2017)
former) 30 min Alloy and slag FeO, of slag & alloy Ni, and 93.57% Cu
SiO2 , Al2 O3 , CaO, Comminution
MgO
◦ ◦
Smelting LiNiMnCoO2 (NCM) Pyrolusite slag Roasting at 800 C 1475 C, 30 Co–Ni–Cu–Fe alloy Manual separation, 79.86% Li, Guoxing et al. (2016)
former, SiO2 , CaO for 120 min to min and comminution, acid 94.85%Mn
remove carbon lithium-containing leaching (sulfuric
manganese-rich acid)
slag

Reduction Roasting LiNiMnCoO2 (NCM) Carbon – 650 ◦ C, Li2 CO3 , Co, Ni, Water and acid 93.67% Li, 93.33% Liu et al. (2019b)
(Thermal reduction) 30 min NiO, MnO, CO2(g) leaching (H2 SO4 ) Ni, 98.08% Co, and
98.68% Mn
◦
Reduction Roasting NCM Carbon Alkali leaching, 650 C for Li2 CO3 , NiSO4 , Water and acid 84.7% Li, more Hu et al. (2017)
(Thermal reduction) 1.5 mol L−1 NaOH 3 h CoSO4 and MnSO4 leaching (H2 SO4 ) than 99% Ni, Co,
and Mn
◦
Vacuum pyrolysis LiCoO2 Carbon NaCl discharging, 600 C Co, CoO, Li2 CO3 , Water leaching 93% Li, 99% Co Tang et al. (2019)
(Thermal reduction) Manual CO2(g)
dismantling,
Vacuum pyrolysis
◦
Plasma Spray LiNiMnCoO2 (NCM) – NaOH dissolution 600 C Regenerated Zheng et al. (2019)
Pyrolysis (Thermal LiNiMnCoO2
reduction)

Microwave LiNiMnCoO2 (NCM) Carbon NaCl discharge, (900 ◦ C) – Acid leaching 99.68% Li, 97.65% Fu et al. (2020)
Carbothermic Manual 500 W, 30 (HCl(aq) ) Ni, 97.85% Co, and
Reduction (Thermal dismantling, min 96.73% Mn
reduction) Comminution

Oxygen-free roasting LiCoO2 Carbon – 1000 ◦ C, Li2 CO3 , Co Wet magnetic 95.72% Co, 98.93% Li et al. (2016a)
(Thermal reduction) 30 min separation Li

Thermal reduction NCM – – Stage 1: Ni metal Magnetic – Huang et al. (2019)

691 ◦ C Co metal separation
Stage 2:
873 ◦ C

Thermal reduction NCM – Dismantling and 520 ◦ C, 60 LiAlO2 , NiO, CoO, Alkaline leaching 99.78% Li, 98.62% Wang et al. (2020)
crushing min and MnO (NaOH) and Acid Ni, 99.29% Co, and
leaching (H2 SO4 ) 99.91% Mn

Thermal reduction LiCoO2 – Crushing 600 ◦ C, 60 Li2 O, LiAlO2 , and Alkaline leaching 93.67% Li and Wang et al. (2019)
min CoO (NaOH) 95.59% Al

Chlorination LiCoO2 NH4 Cl Discharging, 350 ◦ C, 20 LiCl, CoCl2 , H2 O(g) , Water leaching 99.18% Li, 99.3% Co Fan et al. (2019)
calcination (Salt Manual min Cl(g) , N2(g) , NH3(g)
roasting) dismantling, NaOH
dissolution

Chlorination NCM NH4 Cl Dismantling and 350 ◦ C, 30 NH4 MCl3 (M==Ni, Water leaching Over 98% of Li, Ni, Jian et al. (2021)
calcination (Salt crushing min Co, Mn) and Co, and 97%
roasting) of Mn

Sulfation Roasting LiCoO2 SO2(g) – 700 ◦ C, Li2 SO4 , Li2 Co(SO4 )2 , Water leaching 99.5% Li, 17.4% Co Shi et al. (2019b)
(Salt roasting) 120 min CoO, O2(g)

Sulfation Roasting LiNiMnCoO2 (NCM) Na2 SO4 NaCl submersion, 750 ◦ C, Li2 SO4 , MnO, NiO, Water leaching 85.43% Li, Di et al. (2020)
(Salt roasting) Manual 90 min CoO, CuO2 , efficiencies of Ni,
dismantling, Co, and Mn were
Calcination 84.93%

Nitration Roasting LiCoO2 HNO3 Mechanical 250 ◦ C, LiNO3 , Co(NO3 )2 , Water leaching 93% Li, efficiencies Peng et al. (2019)
(Salt roasting) pretreatment 60 min NO(g) , O2(g) , H2 O(g) of Co, Ni, and Cu
were 92.9%

3.2.2. Thermal reduction waste lithium-ion batteries (Huang et al., 2019). In the first stage
Another extractive pyrometallurgical processing used to re- of the reduction process, nickel compounds in NCM materials
cycle waste lithium-ion batteries is thermal reduction (roast- were lessened to nickel metallic form at the optimized lower
ing/calcination). Pre-treatments of LIBs are usually done before- temperature of 691 ◦ C, meanwhile, the cobalt compounds were
hand to obtain the cathode material for extractive processing (An, not reduced. By applying magnetic segregation, nickel metal was
2019). During the thermal reduction, active cathodic substances subsequently segregated from the mixed particles. In the second
are heated with a reductant of coke, charcoal, or C, leaving C stage of thermal reduction at 873 ◦ C, cobalt in the residual was
residual and a medley of intermediate compounds for subse- lessened to metallic form which was also segregated from the re-
quent refinements. Carbon material, specifically the waste anodic duction products by magnetic separation. Wang et al. introduced
graphite material is an alluring reductant for the process as an in situ thermal reduction pathway for the recovery of high-
it is inexpensive and has high effects (Zhang et al., 2020b,c). value elements from waste LIBs of NCM (Wang et al., 2020). The
Compared to the high-temperature smelting process, thermal cathode was first shredded into powders without separation of
reduction shows the superiorities of high metal recovering rates Al foil, followed by thermal reduction under 520 ◦ C for 60 min.
and low energy requirements. The current collector of aluminum performs as a reductant for
Huang and his colleagues developed a thermal reduction pro- the reduction of adhered cathodic materials. It was observed
cessing with the use of spent graphite as a reductant to step- that 99.78%, 98.62%, 99.29%, and 99.91% of lithium, nickel, cobalt,
by-step recover nickel and cobalt from the electrode powder of and manganese respectively were recovered from the spent NCM
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3.2.3. Salt roasting

A transition from thermal reduction to salt-assisted roasting
has occurred recently since the formation of Li2 CO3 in thermal
reduction leads to a low lithium leaching rate due to the poor
solubility of Li2 CO3 (Makuza et al., 2021). Salt-assisted roasting
aims to convert metallic compounds into water-soluble salts by
roasting with salts, this technique has proved efficient to seg-
regate metals in Li transition metal oxides (Shi et al., 2019b).
By generating readily water-soluble salts, salt-assisted roasting
could potentially enhance the recycling effectiveness, and lower
hazardous gas emissions and acid consumption. Several salts also
are characterized by great volatility, great solubility, and low
melting points (Fan et al., 2019). Salt-assisted roasting includes
nitration, chlorination roasting, and sulfation roasting, classified
based on the reagent employed.
An approach of chlorination roasting coupled with water
leaching was proposed to recover manganese, cobalt, nickel, and
lithium from NCM cathodic substances (Jian et al., 2021). Under
the optimal conditions (350 ◦ C roasting temperature, 30 min, the
mass ratio of NH4 Cl to cathodic powder is 2:1), over 98% of Co,
Li, and Ni, and 97% of Mn are leached into the liquid with a high
concentration. During the chlorination roasting process, NH4 Cl
added is first sublimated and transformed into H3 N···HCl(g) , de-
composing the cathode’s structure and forming the intermediate
of (NH4 )2 MCl4 · 2H2 O in which M==Mn, Co, and Ni. The interme-
diate then is disintegrated into NH4 MCl3 (M==Mn, Co, and Ni)
and subsequently recovered via a process of water leaching. In
addition to chlorination roasting, nitration, and sulfation roasting
are widely applied to recycle used lithium-ion batteries (Shi et al.,
2019b; Di et al., 2020; Peng et al., 2019).

3.2.4. Industry demonstrations

Pyrometallurgy is a prevalent method for recycling spent LIBs
at industrial scales owing to its maturity, great productivity, and
relative simplicity (Chen et al., 2019b). Pyrometallurgical proce-
dures can be designed to recycle either specific LIBs or batteries
with other materials. LIB recycling facilities are usually expanded
from the Ni-MH or Ni-Cd ones for most enterprises; thus, they
could handle various battery types. A summary of the pyrometal-
lurgical recycling processes applied on an industrial scale is given
in Table 7.
Umicore uses a smelting technique at elevated temperatures
for recycling batteries with a capacity of 7000 tons/year (Anon,
2022j). The energy requirement for treating one ton of battery
materials is 5000 MJ. The pyrometallurgical technology with a
vertical shaft furnace is able to handle all sizes and kinds of
lithium-ion batteries. In this process, pre-treatment is unneces-
sary since LIBs are directly fed into the vertical shaft furnace.
The battery needs to be dismantled to module-level if it exceeds
the handling size prerequisite. The commercial feasibility of the
Fig. 9. A schematic representation of reclaiming high-value elements from used Umicore process largely depends on the level of cobalt in LIBs
lithium-ion batteries (Hu et al., 2017). and the price of this element. Therefore, from an economic point
of view, the concentration of cobalt in the batteries should range
from 30 to 50%. The first step of the Umicore process is the prepa-
cathodic materials in the subsequent alkaline leaching and acid ration of a batch for the furnace in which end-of-life batteries
leaching process. Hu et al. [104] proposed a potential combined are mixed with small amounts of slag formers, coke (C) sand
recycling approach for end-of-life LIBs using alkaline leaching (SiO2 ), and limestone (CaCO3 ). Following that, the batch is then
followed by thermal reduction and subsequent leaching of car- fed into a three-zone furnace. In the first zone of the furnace, the
batch is preheated to evaporate the electrolyte: the temperature
bonated water and sulfuric acid (Fig. 9). It was shown that, after
is gradually increased and maintained below 300 ◦ C to avoid
the thermal reduction process (19.9% carbon dosage, 3 h, 650 ◦ C),
explosions caused by rapid heating. The second zone is plastic
84.7% of lithium was recycled by carbonated water leaching. Over
pyrolysis: the temperature in this partition is 700 ◦ C, which
99% of manganese, nickel, and cobalt, were recovered in forms of causes the melting of plastics and the complete decomposing of
MnSO4 , NiSO4 C, and CoSO4 through sulfuric acid leaching. This the organic components. The hot gasses emitted in the pyrolysis
approach is promising for recycling spent LIBs at the industrial stage are utilized in the preheating phase, thereby compensating
scale. for the fuel requirements. In the last zone, smelting and reduction
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Table 7
Industrial pyrometallurgical battery recycling technologies.
Source: Adapted from Makuza et al. (2021).
Company Country Capacity Battery type Pre-treatment Pyrometallurgy Post-treatment Products Secondary Losses Ref
(t/year) processed Products

Valdi (Eramet) France 20 000 LIB and other – (not reported) – FeNi/FeMn alloy – – Pinegar
batteries and Smith
(2019)

Umicore Belgium 7000 LIB, Ni-Cd, Ni-MH No pre-treatment Smelting Leaching, solvent CoCl2 , Co, Ni, Slag (Al, Si, Ca, Electrolyte, Lv et al.
Only dismantling for Shaft furnace extraction Cu, Fe Fe, Li, Mn, REE) plastics, (2018),
large batteries graphite Velázquez-
Martínez
et al.
(2019) and
Anon
(2022l)

Xstrata (Glencore) Switzerland 7000 All LIB chemistry No pre-treatment Conditioning Hydrometallurgy alloy Li slagged and No recovery of Lv et al.
(rotary kiln) and (Co–Ni–Cu) ignoble metals Li, Al, (2018) and
introducing into a electrolyte, Georgi-
Co-Ni winning graphite, Maschler
process (EAF) plastics et al.
(2012)

Inmetco USA 6000 LIB, Ni-Cd, Ni-MH Sorting Calcination (rotary Iron casting alloy (Co–Ni–Fe) Li slag The organic Lv et al.
hearth furnace), material used (2018) and
smelting as a chemical Van
(submerged reagent Der Werf
electric arc (2011)
furnace)

Accurec Germany 6000 All LIB chemistry Sorting, Dismantling, Smelting Acid leaching Li2 CO3 Metallic alloy Electrolyte, Velázquez-
Pyrolysis Co-Alloy polymers, Martínez
Milling, separation, graphite et al.
agglomeration, (2019) and
filtration Anon
(2022c)

JX Nippon Mining Japan 5000 – Incineration, Smelting Leaching, selective Li2 CO3 , Ni, – Electrolyte Haga et al.
and Metals comminution precipitation, MnCO3 , Co (2018),
electrowinning Pinegar
and Smith
(2019) and
Knights
and
Saloojee
(2015)

Dowa Japan 1000 All LIB – Co, Ni, Mn Knights

and
Saloojee
(2015),
Larouche
et al.
(2020) and
Anon
(2014)

SNAM France 300 – Crushing (not reported) – Black mass (Cu, – – Lv et al.
Pyrolysis Ni, Co) (2018)
Magnetic separation

Sumitomo Japan 150 LIB (LiCoO2 ) Sorting, dismantling Calcination Acid leaching, CoO Co–Ni–Fe alloy Electrolyte, Shi et al.
hydrometallurgy Cu, Al, Fe plastics, Li, Ni, (2019b),
graphite Assefi
et al.
(2020) and
Jie et al.
(2020)

G & P Batteries UK 145 LIB – (not reported) (not reported) – – – Knights

and
Saloojee
(2015)
Kushnir
(2015)

LithoRec Germany 2000 – Manual disassembly, Drying, Calcination Undisclosed Li2 CO3 , Al–Cu, plastic Electrolyte Velázquez-
Two-stage crushing, leaching agent Metal oxides fractions Martínez
two-stage air et al.
classification (2019)

GRS Batteries Germany – LiMnO2 – Vacuum – Co, Ni, Cu, FeNi – – Kushnir
distillation and FeMn (2015)

Battery resources Germany – – Discharging, shredding, Sintering Leaching by LI2 CO3 , metal Al–Cu, plastic Electrolyte Kushnir
magnetic separation, NaOH, H2 O2 , oxides fractions (2015)
sieving, DMS H2 SO4 , Na2 CO3

Nickelhütte Aue Germany – LIB, Ni-MH – Smelting (not reported) Co, Ni, Cu – – Larouche
GmbH matte et al.
(2020) and
Pistoia and
Liaw
(2018)

of the batch take place, the temperature in this zone ranges sisting of aluminum, calcium, silicon, lithium, and iron; and a gas
between 1200–1450 ◦ C. The pyrometallurgical process produces fraction. The metallic alloy is used for refining metals through
three output streams: a metallic alloy comprising copper, nickel, subsequent hydrometallurgy processes. The alloy first is dissolved
cobalt, lithium, and small quantities of iron; a slag fraction con- in a solution of HCl, followed by a solvent extraction process
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Fig. 10. The battery recycling process of Umicore (Vezzini, 2014).

to extract metals in the leachate. The obtained products include fraction and the added binder material are pelletized to improve
Ni(OH)2 , Fe, Cu, and CoCl2 which can be employed for LiCoO2 the material handling. The agglomerated pellets charged into
synthesis. While the slag is utilized for the production of con- the furnace are smelted to produce Co-Ni-Mn-Fe alloy. While
struction materials. The temperature of waste gasses leaving the lithium is slagged and furtherly recovered in Li2 CO3 form through
furnace is around 450 ◦ C and must be treated to prevent their a subsequent hydrometallurgy process including acid leaching,
condensation. The temperature of these waste gasses between precipitation, and filtration. The Accurec recycling process can
the shaft and post-combustion chamber is increased to 1150 ◦ C recover Li2 CO3 with high efficiency of 90%, and the reclaimed
by a plasma torch; toxic halogens or volatile organic compounds Li2 CO3 can be utilized in glass manufacturing or as cathodic
evolved from electrolyte and binder evaporation are captured by precursors.
injection of sodium or calcium or zinc oxide. In a post-combustion Sony and Sumitomo in Japan developed an integrated process
chamber, the waste gases are cooled to 300 ◦ C by injection of of pyrometallurgy and hydrometallurgy for recycling end-of-life
water, followed by filtration in conventional filters. The flow lithium-ion batteries LIBs (Chen et al., 2019b; Makuza et al.,
chart of this overall pyrometallurgical pathway is presented in 2021). Sony-Sumitomo offers an annual capacity of 150 tonnes,
Fig. 10. The approach shows the superiorities of great recovery and the energy requirement for incinerating one tonne of organic
rates and no need for mechanical pre-treatments at the begin- material is 992 MJ. The recycling process starts at the Sony plant,
ning. However, the loss of lithium in the dust and complicated where the spent batteries are fed and calcined in a furnace at the
hydrometallurgical treatments to recover this element in the slag temperature of 1000 ◦ C. During the calcination, the inflammable
are drawbacks of Umicore technology. constituents such as electrolytes, plastics, and other organic sub-
Accurec is a German company, which can recycle all types stances are incinerated compensating for the energy requirement,
of batteries (Anon, 2022b). Accurec battery recycling technique leaving metallic parts and active materials. Lithium and organic
integrates mechanical process, pyrometallurgy, and hydromet- substances are lost in the flue dust, and the vaporized gases are
allurgy as seen in Fig. 11 to obtain a Co-Ni-Mn-Fe alloy and removed from the dust by a scrubber. Following the calcination
a Li2 CO3 cathode precursor. In the beginning, used lithium-ion step is shredding and screening the obtained calcine. The metallic
batteries from electric devices and electric vehicles are sorted residue containing Al, Fe, and Cu is separated by magnetic separa-
and manually dismantled. The dismantled batteries are heated tion. The powder derived from mechanical treatment consists of C
in a furnace under vacuum conditions aiming at eliminating and active cathodic substances. The powder is transported to the
volatile hydrocarbons, electrolytes, and solvents. The pyrolysis Sumitomo facility, where the cobalt in the powder is recovered
temperature in the thermal pre-treatment is controlled under as cobalt oxide by a hydrometallurgy process. The purity of the
250 ◦ C to not affect the metals’ state. Thereafter, the batteries reclaimed cobalt oxide is relatively high, which can be utilized
undergo the operations of grinding and milling for exposing en- for synthesizing LiCoO2 cathodic substance. Sony and Sumitomo
closed components. The shredded materials are divided into four pathway initially aimed at recovering only Co, so other elements
size proportions by mechanical classification including magnetic are lost which is a disadvantage of this process. Recently, an
separation, vibrating screen, zig-zag classier, and air separation. emerging approach to reclaim Cu (via pyrometallurgical pro-
Fe-Ni, aluminum, and current collectors are the three obtained cessing) and Ni (via hydrometallurgical processing) is released
fractions, and base metals could be recovered from these pro- by Sony-Sumitomo (Anon, 2022g). The new recycling procedure
portions. The remaining fraction of fine particles contains target enables the extraction of more value from end-of-life batteries
elements like lithium, cobalt, and manganese. This fine particle which enhances resource sustainability.
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Fig. 11. The flow chart of the Accurec battery recycling process (Velázquez-Martínez et al., 2019).

Glencore (formerly Xstrata Nickel) operates a pyro- are either incinerated or used as reducing agents in the process
hydrometallurgical facility at an industrial scale for recycling of reduction of active cathodic substances. The emitted gases
waste lithium-ion batteries (Anon, 2022k). Glencore can handle are disposed of by scrubbers, and the scrubbed solution then is
7000 tonnes of used batteries per year, and the company intends treated before being recycled back into the process. The obtained
to increase its capacity. End-of-life batteries are deactivated and molten fraction is refined by smelting in another furnace. The
dismantled into individual packs (with 6–12 battery cells) or cells elements of iron, nickel, and cobalt are reclaimed in a metallic al-
by the collectors that Glencore works with. Waste lithium-ion loy, and the alloy then undergoes casting processing. Meanwhile,
batteries are fed and treated at 1300 ◦ C in a smelting furnace. lithium is lost in the slag phase and organic materials are burnt as
The organic material is incinerated, and afterburners are utilized the Inmetco recycling process was not initially designed to treat
to treat the emitted gases to obviate the release of dioxins. The LIBs.
obtained alloy of this process undergoes a subsequent hydromet- JX Nippon Mining and Metals Corporation uses an integrated
allurgical treatment for metal recovery. The Glencore process procedure of pyrometallurgy and hydrometallurgy to recycle end-
reclaims only nickel, copper, and cobalt, the other fractions are
of-life LIBs (Haga et al., 2018). The facility was originally designed
either consumed to produce heat or slagged or used as reducing
for treating cathodic scraps, then it was adjusted to process spent
agents. This procedure was not developed for LIB recycling at the
LIBs due to the difficulty in waste cathode material collection.
beginning, therefore, some materials were lost including lithium
The facility annually deals with 5000 tons of used LIBs. In the JX
slag.
Nippon process, spent LIBs are fed and incinerated in a furnace for
Inmetco (International Metals Reclamation Company) utilizes
a high-temperature melting recovery process for recycling spent recovering cathodic substances and segregating them from other
LIBs (Li et al., 2018c; Lv et al., 2018; Makuza et al., 2021). The things such as the casing, wires, connectors, and so on. During
industrial-scale pyrometallurgical facility offers a LIB recycling the incineration stage, the organic electrolyte is evaporated and
capacity of 6000 tons/year. Inmetco procedure comprises me- burnt out leaving a clinker, and fluorine in organic electrolytes is
chanical pre-treatment, reduction, melting, and casting. The pre- reclaimed via precipitating. The clinker obtained from the furnace
treatment step includes opening batteries, disassembling, and is crushed and separated into two portions namely fine material
draining electrolytes, ensued by crushing batteries. The other and coarse material. The fine particle fraction mainly containing
solid materials are mixed with the addition of a C-based reducing cathodic substances is treated by a leaching process, solvent ex-
agent. The blend is agglomerated into pellets by adding the liquid traction process, and electrowinning process. The major products
waste containing Ni and Cd. In the reduction stage, the shredded obtained from the hydrometallurgy procedure include electrolytic
batteries along with the reducing pellets are heated at 1260 ◦ C cobalt and electrolytic nickel, while the minor ones are Mn and Li
in a hearth furnace for 20 min. Carbon and organic materials carbonate. The course proportion of the shredded clinker together
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Fig. 12. The flow chart of the LithoRec battery recycling process (Velázquez-Martínez et al., 2019).

with the residual of the hydrometallurgy treatment are furtherly The precipitate containing Li is blended with the metal oxides.
smelted for reclaiming Cu. The mixture is fed into the ‘‘Calcination’’ processing to produce
Duesenfeld company evolves an integrated procedure of me- precursors for the regeneration of LIBs (Kwade and Diekmann,
chanical process, thermodynamic process, and hydrometallurgy 2018; Diekmann et al., 2016).
to recycle spent LIBs. This battery recycling approach is adopted
from the LithoRec pathway (Velázquez-Martínez et al., 2019; 3.3. Hydrometallurgy
Anon, 2022i), which is depicted in Fig. 12. The recycling pro-
cedure aims at recovering high-purity cathodic substances from After pre-treatments, hydrometallurgy is employed to reclaim
spent EV batteries, the facility offers an annual operating capac- high-value elements from spent LIBs such as manganese, lithium,
ity of 2000 tons/year. The lithoRec process starts with a deep nickel, and cobalt into individual metals, new cathodic sub-
battery discharge process to obviate explosions. Following that, stances, or precursors. The hydrometallurgical recycling technol-
the discharged batteries are disassembled manually to eliminate ogy consists of two phases, which are leaching LIBs and
peripherals like protective cases, plastics, wiring, and contami- recovering high-value elements from the leachate (Chagnes and
nants. The disassembled batteries are subsequently shredded by Pospiech, 2013). The leachant commonly utilized in the leaching
a crusher (20 mm) under an N2 atmosphere between 100–140 ◦ C. stage comprises bacteria solution, alkaline, and acid (including
The shredded material is transported into a zig-zag air classifier, organic acid and inorganic acid). High-value elements in the
where plastic, copper, iron, and aluminum are segregated. The leachate are separated and recovered via various technologies
fine fraction (black mass) containing mainly cathode and anode such as solvent extraction, electrolysis, precipitation, ion ex-
substances undergoes a secondary crushing step and a sieving change, and so on. A comparison of disparate leaching techniques
process (500 µm of sieving size). After sieving, the particle size and metal recovery processes is shown in Table 8. Hydromet-
fraction above 500 µm is sent to a second air classifier, where allurgy shows the superiorities of low emissions, low energy
it is divided into proportions consisting of plastics, copper, and requirements, and great recovering rates of metals with great
aluminum. The other fraction below 500 µm is transferred to purities, compared to the pyrometallurgy technique (Chen et al.,
hydrometallurgical processing where the material is dissolved in 2019b). Hence, hydrometallurgy is considered more appropriate
an unrevealed leachant. Graphite is eliminated firstly from the to recycle retired lithium-ion batteries. However, this method
solution in the dissolution step, this is ensued by manganese, also has some drawbacks. One of them is the requirement of
cobalt, and nickel, these elements are precipitated in the form battery sorting which escalates the expense and the complexity
of metal oxides. Lithium leached out in the leachate is recovered of the overall recycling process. Additionally, the separation of
in a medley of Li2 CO3 and LiOH through a precipitating process. aluminum, copper, iron, manganese, nickel, and cobalt in the
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Table 8
Hydrometallurgical treatments of LIBs.
Source: Adapted from Jung et al. (2021).
Hydrometallurgy Chemical used Advantage Disadvantage
treatment
HCl • Chemical inexpensive • Equipment corrosion
• Cl contamination
Inorganic acid
Leaching HNO3 • High extraction rate on Co and Li • Dissolve Al
• Oxidize Mn and Co
• NOx in discharge
H2 SO4 • Chemical inexpensive • Sulfate ion has solubility limitation.
H3 PO4 • Low acid consumption • Phosphate has very limited solubility.
Organic acid • Environmental friendlier • Lower extraction rate
Bioleaching • Environmental friendlier • Low kinetic
• Low extraction rate
Precipitation NaOH, LiOH, Na2 CO3 , Li2 CO3 • Low energy consumption • pH adjustment difficult to
• Low cost control
• Metals often co-precipitated
Solvent D2EHPA, Cyanex 272, • Able to extract individual • Process very complicated
extraction Acorga M5640, PC-88A, metal ions • Multiple extraction stages
TODGA, P66614-Cl, DES • High separation efficiency • High cost of solvents
Low energy consumption • Generated wastewater and
emission
• Toxic solvents needed to be
waste treated

leaching solution remains a challenge because of their similarly et al., 2017b). Alternatively, low-concentration H2 SO4 was used
chemical properties. The cost of disposal of generated wastewater to treat LFP cathodic substances (Li et al., 2017a). During this
is another shortcoming of the hydrometallurgical process. To low-concentration acid leaching process, only Li was leached out,
keep hydrometallurgy profitable under the trend of decreasing while phosphorus and iron mostly remained in the form of FePO4
valuable metals like Co in LIBs, it is necessary to ensure the in the residual. It differs from the excess acid leaching where all
simplicity of the process, high metal recovery effectiveness, and the elements are leached into the solution. Under optimal leach-
low reagent consumption rate. ing circumstances given in Table 9, 1.95% of phosphorus, 0.027%
of iron, and 96.85% of lithium were dissolved in the leaching
3.3.1. Leaching solution. Lithium in the leachate was subsequently precipitated
Leaching is paramount in the overall process of hydromet- and reclaimed as Li3 PO4 by adding Na3 PO4 as a precipitant. The
allurgy to recover high-value elements from used lithium-ion leaching residual was burnt for 4 h at the temperature of 600 ◦ C
batteries. The leaching step aims at dissolving and converting to eliminate the C slag and produce FePO4 . The reduction in using
valuable elements in batteries to metal ions in leaching solutions. inorganic acid can lessen the overall cost of hydrometallurgical
The metallic ions in the leachate are furtherly separated and processing and the amount of secondarily hazardous waste arisen
recovered by subsequent separation and recovery processes. Acid, from leaching such as toxic emissions and excess acid solution.
alkaline, and bioleaching are commonly utilized to leach waste Organic acid leaching is an emerging method to treat used
LIBs. Table 9 shows a summary of the research results regarding lithium-ion batteries. Organic acids utilized include tricarboxylic
different types of leaching reagents. acid (ex. citric acid (Refly et al., 2021; Li et al., 2018b; Chen
Acid leaching et al., 2016a)), dicarboxylic acid (ex. succinic acid (Li et al., 2015),
Acid leaching comprises inorganic acid leaching and organic ascorbic acid (Refly et al., 2020), and oxalic acid (Zeng et al.,
acid leaching, which is prevalently utilized for dissolving met- 2015a)), and monocarboxylic acid (ex. lactic acid (Li et al., 2017),
als in spent LIBs. Inorganic acid used for LIB leaching includes acetic acid (Li et al., 2018a), and formic acid (Gao et al., 2017)).
HCl (Xuan et al., 2019; Barik et al., 2017), H2 SO4 (Fan et al., 2021; The organic acids used for battery leaching possess many benefits
Li et al., 2019; Zhang et al., 2018), HNO3 (Cognet et al., 2020), compared to inorganic acids, such as recyclability, easy degra-
and H3 PO4 (Chen et al., 2019a). Moreover, reducing agents like dation, ample acidity for leaching, and less secondary emissions.
Na2 SO3 or H2 O2 can be employed to improve the efficiency of the Therefore, organic acid leaching has lured more and more atten-
leaching process. Leaching of the inorganic acid is characterized tion from researchers recently (Yao et al., 2018). Although organic
by simple operation and high leaching effectiveness. Nonetheless, acid leaching exhibits many advantages, it might be unsuitable
this leaching method still has some drawbacks such as equipment for industrial applications due to the following reasons. The cost
corrosion, waste acid pollution, and hazardous gas emissions of organic acids is typically higher than that of inorganic ones
(NOx , Cl2 , etc.). leading to an escalation in the total expense. On the other hand,
Joulié et al. (2014) investigated the leaching of LiNi0.8 Co0.15 organic acids generally have slower leaching speeds versus inor-
Al0.05 O2 (NCA) cathodes in different inorganic acid solutions of ganic acids. Furthermore, the treatment capacity of organic acids
H2 SO4 , HNO3 , and HCl. Hydrochloric acid was observed as the is lower than the capacity of inorganic acids (Gao et al., 2018a).
most efficient leaching agent because of the dissolution promo- In short, poor capacities, high costs, and slow speeds of leaching
tion of chloride ions. Under the optimized circumstances (a ratio still limit the applications of organic acids in industry.
of 5% solid to liquid, 4 M HCl, 18 h, 90 ◦ C), approximately 100% Citric acid has been commonly employed for leaching spent
of high-value elements in the cathodic material namely cobalt, LiFePO4 (Yang et al., 2018) and NCM (Chen and Zhou, 2014; Yao
nickel, lithium, and aluminum were leached out. In other studies, et al., 2015) cathodic substances because of the great chelating
around 99% of manganese, cobalt, and lithium were dissolved capability for metallic ions. Chen et al. (2016a) used citric acid
in dense HCl (Barik et al., 2017) and in H2 SO4 − H2 O2 (He coupled with d-glucose to dissolve waste cathode materials after
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Table 9
Studies on leaching of end-of-life lithium-ion batteries.
LIBs type Leaching agent Leaching condition (T, t, and S/L) Efficiency (%) Ref

Inorganic acid

Mixture 1 M H2 SO4 95 ◦
C, 4 h, 50 g L−1 Li = 93.4, Co = 66.2, Ni = 96.3, Mn = Meshram et al. (2015b)
50.2
◦ −1
LiCoO2 2 M H2 SO4 + 5 vol% H2 O2 80 C, 1 h, 50 g L Li = 99, Co = 99 Sun and Qiu (2011)
LiCoO2 2 M H2 SO4 + 50 g/L glucose 80 ◦
C, 2 h, 35 g L−1 Li = 92, Co = 88 Pagnanelli et al. (2014)
LiCoO2 3 M H2 SO4 + 0.25 M Na2 S2 O3 90 ◦
C, 3 h, 66.7 g L−1 Li = 100, Co = 100 Wang et al. (2012)
◦
Mixture 1.34 M H2 SO4 + 0.45 g/g Na2 S2 O5 20 C, 45 min, 10.9% Mn = 94, Cd = 81, Zn = 99, Co = 96, Tanong et al. (2017)
Ni = 68
Mixture 1 M H2 SO4 + 0.075 M NaHSO3 95 ◦
C, 4 h, 20 g L−1 Li = 97, Co = 92, Ni = 96, Mn = 88 Meshram et al. (2015a)
LiCoO2 2 M H2 SO4 + 2 vol% H2 O2 60 ◦
C, 2 h, 33 g L−1 Li + 87.5, Co + 96.3 Zhu et al. (2012)
LiCoO2 2 M H2 SO4 + 5 vol% H2 O2 75 ◦
C, 1 h, 100 g L−1 Co + 70, Li + 99.1 Jha et al. (2013)
LiCoO2 2 M H2 SO4 + 8 vol% H2 O2 75 ◦
C, 1 h, 50 g L−1 Co + 98 Bertuol et al. (2016)
LiCoO2 2 M H2 SO4 + 6 vol% H2 O2 60 ◦
C, 1 h, 100 g L−1 Li + 97, Co + 98 Kang et al. (2010a)
3 M H2 SO4 + 0.4 g/g cellulose 95 ◦
C, 2 h, 25 g L−1 Li + 100, Co + 54
LiCoO2 3 M H2 SO4 + 0.4 g/g sucrose 95 ◦
C, 2 h, 25 g L−1 Li + 100, Co + 96 Chen et al. (2018b)
3 M H2 SO4 + 0.4 g/g glucose 95 ◦
C, 2 h, 25 g L−1 Li + 98, Co + 96
LiFePO4 2.5 M H2 SO4 60 ◦
C, 4 h, 100 g L−1 Li + 97, Fe + 98 Zheng et al. (2016b)
Li4 Ti5 O12 4 M H2 SO4 + 20 vol% H2 O2 80 ◦
C, 4 h, 25 g L−1 Li + 97, Ti + 98 Tang et al. (2014)
1 M H2 SO4 95 ◦
C, 4 h, 50 g L−1 Li = 93.4, Co = 66.2, Ni = 96.3, Mn =
Mixture 50.2 Meshram et al. (2016)
1 M H2 SO4 + 5 wt% H2 O2 95 ◦
C, 4 h, 50 g L−1 Li = 94.5, Co = 79.2, Ni = 96.4, Mn =
84.6
1 M H2 SO4 + 0.075M NaHSO3 95 ◦
C, 4 h, 20 g L−1 Li = 96.7, Co = 91.6, Ni = 96.4, Mn =
87.9
Mixture 2 M H2 SO4 + 6 vol% H2 O2 60 ◦
C, 1 h, 100 g L−1 Co + 99 Kang et al. (2010b)
Mixture 4 M H2 SO4 + 10 vol% H2 O2 85 ◦
C, 2 h, 100 g L−1 Li = 96, Co = 95 Chen et al. (2011)
◦
LFP 0.3 M H2 SO4 + H2 O2 /Li molar ratio 2.07, 60 C, 2 h Li + 96.85, Fe + 0.027, P + 1.95 Li et al. (2017a)
H2 SO4 /Li molar ratio 0.57
NCM 1 M H2 SO4 + 1 vol% H2 O2 40 ◦
C, 1 h, 40 g L−1 Li/Co/Ni/Mn = 99.7 He et al. (2017b)
LiCoO2 4 M HCl 80 ◦
C, 1 h, 10 g L−1 Li = 99, Co = 99 Zhang et al. (1998a)
◦
LiCoO2 4 M HCl 80 C, 2 h Li = 97, Co = 99 Li et al. (2009)
Mixture 4 M HCl 80 ◦
C, 1 h, 20 g L−1 Li = 99.9, Co = 99.5, Ni = 99.8, Mn = Wang et al. (2009)
99.8
NCA 4 M HCl, 90 ◦ C, 18 h with a 5% (w/v) solid to 90 ◦
C, 18 h, 5% (w/v) Li/Co/Ni/Al + 100 Joulié et al. (2014)
liquid ratio
◦
Mixture 1.75 M HCl 50 C, 2 h, 20% (w/v) Li + 99.2, Co + 98, Mn + 99 Barik et al. (2017)
LiCoO2 2% H3 PO4 + 2 vol% H2 O2 90 ◦
C, 0.5 h, 8 g L−1 Li/Co > 95 Pinna et al. (2017)
LiCoO2 1.5 M H3 PO4 + 0.02 M glucose 80 ◦
C, 2 h, 20 g L−1 Li = 100, Co = 98 Meng et al. (2017)
LiCoO2 0.7 M H3 PO4 + 4 vol% H2 O2 40 ◦
C, 1 h, 50 g L−1 Li + 99.9, Co + 99.7 Chen et al. (2017)
LiCoO2 1 M HNO3 + 1.7 vol% H2 O2 75 ◦
C, 1 h, 20 g L−1 Li = 95, Co = 95 Lee and Rhee (2003)

Organic acid

LiCoO2 1.25 M citric acid + 1 vol% H2 O2 90 ◦

C, 0.5 h, 20 g L−1 Li = 99, Co = 91 Li et al. (2010b)
LiCoO2 0.1 M citric acid + 0.02 M ascorbic acid 80 ◦
C, 6 h, 10 g L−1 Li = 100, Co = 80 Nayaka et al. (2015)
LiCoO2 n(citric acid)/n(LiCoO2 ) + 4:1 + 1 vol% H2 O2 90 ◦
C, 5 h, 15 g L−1 Co + 99.07 Zheng et al. (2016a)
NCM 1 M citric acid + 12 vol% H2 O2 60 ◦
C, 40 min, 80 g L−1 Total metals > 98 Yao et al. (2015)
NCM 0.5 M citric acid + 1.5 vol% H2 O2 90 ◦
C, 1 h, 20 g L−1 Li = 99.1, Co = 99.8, Ni = 98.7, Mn = Li et al. (2018b)
95.2
Mixture 1.5 M citric acid + 0.5 g/g glucose 80 ◦
C, 2 h, 20 g L−1 Li = 99, Co = 92, Ni = 91, Mn = 94 Chen et al. (2016a)
Mixture 2 M citric acid + 2 vol% H2 O2 80 ◦
C, 1.5 h, 33 g L−1 Li = 99, Co = 95, Ni = 97, Mn = 94 Chen and Zhou (2014)
2 M citric acid + 0.6 g/g H2 O2 70 ◦
C, 80 min, 50 g L−1 Li = 99, Co = 98
LiCoO2 1.5 M citric acid + 0.4 g/g tea waste 90 ◦
C, 2 h, 30 g L−1 Li = 98, Co = 96 Chen et al. (2015b)
1.5 M citric acid + 0.4 g/g Phytolacca 80 ◦
C, 2 h, 40 g L−1 Li = 96, Co = 83
Americana
1.25 M citric acid + 1 vol% H2 O2 90 ◦
C, 30 min, 20 g L−1 Li ∼ 100, Co > 90
LiCoO2 1.5 M malic acid + 2 vol% H2 O2 90 ◦
C, 40 min, 20 g L−1 Li ∼100, Co > 90 Li et al. (2013)
1.5 M aspartic acid + 4 vol% H2 O2 90 ◦
C, 2 h, 10 g L−1 Li ∼ 60, Co ∼ 60
LiCoO2 1.5 M malic acid + 2 vol% H2 O2 90 ◦
C, 40 min, 20 g L−1 Li = 100, Co > 90 Li et al. (2010a)
LiCoO2 1.2 M DL-malic acid + 1.5 vol% H2 O2 90 ◦
C, 30 min, 40 g L−1 Li = 98.9, Co = 94.3, Ni = 95.1, Mn = Sun et al. (2018b)
96.4
NCM 3.5 M acetic acid + 4 vol% H2 O2 60 ◦
C, 1 h, 40 g L−1 Li = 99.97, Co = 93.6, Ni = 92.7, Mn Gao et al. (2018b)
= 96.3
◦
1 M acetic acid + 2 mL H2 O2 70 C, 1 h Li = 98.83, Co = 97.85, Ni = 97.93,
NCM Li et al. (2018a)
Mn = 97.74
◦
2 M maleic acid + 3 mL H2 O2 70 C, 1 h Li = 99.45, Co = 98.45, Ni = 98.58,
Mn = 98.16
NCM 2 M formic acid + 6 vol% H2 O2 60 ◦
C, 45 min, 50 g L−1 Li = 99.93, Co = 37.77, Ni = 49.80, Gao et al. (2017)
Mn = 62.42, Al + 4.54
◦ −1
LiCoO2 n (formic acid)/n (LiCoO2 ) + 10:1 60 C, 20 min, 20 g L Li = 99.9, Co = 99.96 Zheng et al. (2018a)
LiCoO2 1 M oxalic acid 95 ◦
C, 2.5 h, 15 g L−1 Li = 98, Co = 97 Zeng et al. (2015a)
LiCoO2 1 M oxalic acid 80 ◦
C, 2 h, 50 g L−1 Li = 98 Sun and Qiu (2012)
LiCoO2 1.5 M succinic acid + 4 vol% H2 O2 70 ◦
C, 40 min, 15 g L−1 Li > 96, Co ∼ 100 Li et al. (2015)
NCM 3 M trichloroacetic acid + 4 vol% H2 O2 60 ◦
C, 0.5 h, 50 g L−1 Li = 100, Co = 92, Ni = 93, Mn = 90 Zhang et al. (2015b)
LiCoO2 1.25 M ascorbic acid 70 ◦
C, 20 min, 25 g L−1 Li = 98.5, Co = 94.8 Li et al. (2012b)
Mixture 2 M tartaric acid + 4 vol% H2 O2 70 ◦
C, 0.5 h, 17 g L−1 Li = 99, Co/Ni/Mn = 99 He et al. (2017a)
NCM 1.5 M lactic acid + 0.5 vol % H2 O2 70 ◦
C, 20 min, 20 g L−1 Li = 97.7, Ni = 98.2, Co = 98.9, Mn = Li et al. (2017)
98.4

Alkali leaching

Mixture 15 wt% NaOH 50 ◦ C, 1 h, 0.1 g mL−1 Al = 58 Ferreira et al. (2009)

Mixture 5 wt% NaOH Room temperature, 4 h, 0.1 g mL−1 Al = 99.9 Chen et al. (2011)
Mixture 4 M NH3 + 1.5 M (NH4 )2 SO4 + 0.5 M Na2 SO3 80 ◦ C, 5 h, 10 g L−1 Li = 96.7, Co = 88.4, Ni = 94.8, Mn = Zheng et al. (2017)
6.34
Mixture 3 M (NH4 )2 SO4 + 0.75 M (NH4 )2 SO3 180 ◦ C, 2 h, 83 g L−1 Li = 98, Co = 81, Ni = 98, Mn = 92 Chen et al. (2018a)
Mixture NH3 + (NH4 )2 SO3 + (NH4 )2 CO3 40 min Cu/Co = 100 Ku et al. (2016)
NCM 367.5 g/L NH3 · H2 O + 140 g/L NH4 HCO3 + Li = 81.2, Co = 96.3, Ni = 96.4, Mn: Wang et al. (2017b)
63.24 g/L H2 O2 hardly leached out
Mixture 1.5 M NH3 + 1 M (NH4 )2 SO3 + 1 M NH4 HCO3 60 ◦
C, 3 h, 20 g L−1 Li = 60.53, Co = 80.99, Ni = 96.32 Wu et al. (2019)

(continued on next page)

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Table 9 (continued).
LIBs type Leaching agent Leaching condition (T, t, and S/L) Efficiency (%) Ref

Bioleaching

Mixture Bacteria: Acidithiobacillus ferrooxidans + 30 ◦

C, 20 d, 5 g L−1 Li = 10, Co = 65 Mishra et al. (2008)
elemental sulfur 1% + 3 g L−1 Fe(II)
◦
LiCoO2 Bacteria: Acidithiobacillus ferrooxidans + 0.75 g 35 C, 6 d Co = 99.9 Zeng et al. (2012)
L−1 copper ions
◦
LiCoO2 Bacteria: Acidithiobacillus ferrooxidans + 0.02 g 35 C, 7 d Co = 98.4 Zeng et al. (2013)
L−1 Ag+
Mixture Bacteria: H2 SO4 produced by sulfur-A.t pH of 1 Li/Ni/Co/Mn > 95 Xin et al. (2016)
(Acidithiobacillus thiooxidans) system
◦
Mixture Fungi: Organic acid produced by Aspergillus niger 30 C, 16 d, pulp density 1% (w/t) Li = 95, Co = 45, Ni = 38, Mn = 70, Horeh et al. (2016)
Cu = 100, Al = 65
Mixture Fungi: Aspergillus niger Cu = 100%, Li = 100%, Mn = 77%, Al Bahaloo-Horeh and Mousavi (2017)
= 75%, Co = 64%, Ni = 54%

pre-treatment. Consequently, 99% of lithium, 92% of cobalt, 94% et al., 2014). Poor metal concentrations of leaching solutions lead
of manganese, and 91% of nickel were dissolved in the optimized to arduousness for subsequent processing.
circumstances given in Table 9. High-value elements of lithium, Bacteria and fungi are typically used in bioleaching. Fungi
nickel, and cobalt were then segregated and recovered by selec- produce organic acids, meanwhile, inorganic acids are secreted
tive precipitation technique. In another study, formic acid was by bacteria. Acidithiobacillus ferrooxidans (bacteria) was utilized
utilized to recover lithium from cathodic scraps of LIBs (Gao et al., with the addition of copper ions (0.75 g L−1 concentration) to effi-
2017). In this process, Li was dissolved in the leachate, mean- ciently leach spent lithium-ion batteries in a reported study (Zeng
while, Al did remain in metal form, and other metallic elements et al., 2012). After 6 d, 99.9% of the cobalt presented in the
were precipitated out for precursor production. The leaching rate batteries was dissolved in the leaching solution. Similarly, using
of lithium reached 99.93% under optimized conditions shown in Acidithiobacillus ferrooxidans with 0.02 g L−1 silver ions in a period
Table 9. After removing metal residues, Li2 CO3 with a purity of of 7 d could leach 98.4% cobalt from spent LIBs (Zeng et al.,
99.9% could be achieved. 2013). Fungi possess a faster leaching rate, shorter lag phase, and
stronger toxic tolerance compared to bacteria. Fungal bioleaching
Alkali Leaching
has been commonly employed to recover heavy metals from var-
Alkali leaching utilizes interactions between metallic elements ious solid refuse (Zeng et al., 2015b; Madrigal-Arias et al., 2015).
and hydroxide ions in an alkali medium. This method has lured Horeh and colleagues (Horeh et al., 2016) proposed a process for
attention as it selectively dissolves metals and potentially avoids leaching retired lithium-ion batteries by utilizing the fungi named
further expensive phases of purification or separation. NaOH is Aspergillus niger. The used fungi could secrete citric acid, oxalic
usually used for leaching battery materials to selectively remove acid, gluconic acid, and malic acid during the bioleaching process.
Al as this metal is able to dissolve in alkali or in acid environ- Of the produced acids, the effectiveness of the leaching process
ments, whereas other metals like Mn, Co, and Ni are insoluble primarily depends on citric acid. Under optimal conditions (30 ◦ C,
in alkali solutions (Yao et al., 2018). It was found that leaching 16 d, pulp density 1% (w/t)), 38% of nickel, 45% of cobalt, 65% of
cathodes with NaOH under the conditions of 15 wt% NaOH so- aluminum, 70% of manganese, 95% of lithium, and 100% of copper
lution, 50 ◦ C, 1 h, and a solid-to-liquid ratio of 0.1 g mL−1 could were leached out.
selectively remove 58% Al and leave most of the lithium and all of
the cobalt in the residue (Ferreira et al., 2009). Likewise, 99.9% of 3.3.2. Separate and recover valuable elements from leaching solu-
aluminum in the electrode battery powder was leached out after tions
4 h of leaching at room temperature in 5 wt% NaOH solution with After dissolving, certain elements in spent LIBs such as iron,
0.1 g mL−1 solid/liquid ratio (Chen et al., 2011). aluminum, copper, manganese, nickel, cobalt, and lithium go into
In addition to NaOH, ammonia is also utilized in alkali leaching leaching solutions. Following that, the high-value elements in the
as this reagent could form firm complexes with elements like leachate need to be separated and recovered. On the other hand,
copper, cobalt, and nickel. Ammonia and/or ammonium sulfate the removal of impurities (iron, copper, and aluminum) is also
coupled with sulphites were used for battery leaching in the essential to producing high-grade products. To do that, several
published studies (Chen et al., 2018a; Zheng et al., 2017). High approaches have been introduced, including electro-chemical de-
leaching rates of lithium, cobalt, and nickel were observed in position, precipitation, sol–gel method, and solvent extraction.
the two investigations, whereas manganese exhibited disparate Nonetheless, using only one individual manner can hardly seg-
trends as seen in Table 9. regate all the high-value elements due to the intricacy of the
Bioleaching leaching solution composition. Hence, two or more techniques
Bioleaching is another leaching method utilizing acids gener- are usually applied to separate and recover high-value metallic
ated from metabolizations of microorganisms for leaching end- elements from the leachate. The integration between chemical
of-life LIBs. Bioleaching is an attractive alternative to traditional precipitation and solvent extraction is considered a pragmatic
acid leaching due to its lower cost, environmental friendliness, pathway for separating and recovering metals from leaching solu-
and less demand in industrial implementations. Nonetheless, this tions (Yao et al., 2018). The studies regarding the segregation and
method is time-consuming and susceptible to pollution, these reclaiming of elements from leaching solutions are summarized
shortcomings limit its applications. To be more specific, bioleach- in Table 10.
ing requires a long treatment period even if catalysts were uti- Solvent extraction
lized because of the slow leaching velocity, and the difficulty in Solvent extraction is commonly utilized for the separation of
incubating microbes. Moreover, high concentrations of metal ions metals from leachate. During the liquid-liquid extraction process,
in the leaching solution are deemed to be hazardous for cells, target metals and other elements are concentrated and separated
therefore only the low metal concentration solution is produced into two different immiscible liquids. In which, the desired metals
by bioleaching. It was found that the leaching rates of lithium and are presented in associated liquids called solvents or extractants.
cobalt significantly declined from 72% to 37% and from 89% to This method has been demonstrated to be an effective approach
10% respectively, with the rise of pulp densities (2% to 4%) (Niu for metal separations as the great selectivity of the solvent for
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Table 10
Studies on separating and reclaiming high-value elements from leaching solutions.
Method Condition Result Ref.

50% saponified 0.4 M Cyanex 272 at equilibrium Co = 95%–98%, Ni ∼ 1% Kang et al. (2010a)
pH 6

20 vol.% D2EHPA, extraction time of 300 s, pH = Mn = 97% Chen et al. (2015d)

5, A:O = 0.5
Solvent extraction ®
20 vol.% Mextral 272P, extraction time of 300 s, Co = 97.8% Chen et al. (2015c)
equilibrium pH = 4.5, A:O = 1:1

15 vol.% Co-D2EHPA, extraction time of 5 min, Mn = 91.1% Chen et al. (2015a)

equilibrium pH = 3.5, A:O = 1:1

30 vol.% N1923, extraction time of 10 min, A:O = Ti = 98.8% Tang et al. (2014)
0.5, 40 ◦ C

Initial aqueous feed pH of 3.5, P507 concentration 95% Co was extracted with < 5% Ni and Li Chen et al. (2011)
of 25 wt%, and phase ratio O/A of 1.5 co-extraction

Mixture of 0.23 M LIX 84-I and 1.41 M Versatic 98.3% Ni extraction and, 0.23% Co, 0.15% Mn, Joo et al. (2016a)
10 acid, and an O/A ratio of 1, pH of 5 at 25 ◦ C 0.19% Li co-extraction

0.43 mol L−1 D2EHPA + 0.7 mol L−1 Versatic 10 98.30% Mn extraction and 4.11% Co, 1.06% Joo et al. (2016b)
acid, an O/A ratio of 1, pH of 4.5, and at room Ni, 0.25% Li co-extraction
temperature

40% D2EHPA with an A:O = 1:3 at pH = 3.5 100% Mn, 99% Co and 85% Ni are co-extracted Yang et al. (2017a)
into organic phase and about 70.0% Li remain in
aqueous phase

Precipitants: Oxalic acid and H3 PO4 Co = 99%, Li = 88% Pinna et al. (2017)
Na3 PO4 for precipitate Li at 65 ◦ C Li = 95.56% Li et al. (2017a)
Na2 CO3 for precipitate Li at 95 ◦ C Li = 95% Peng et al. (2019)
Adjust pH to 5 to precipitate Mn Mn = 93.6% Zhang et al. (2020c)
Precipitation
Adjust pH to 13 to precipitate Li Li = 96.9%
Precipitants: Na2 CO3 and Na3 PO4 Li as Li2 CO3 and Li3 PO4 : 74.72% and 92.21% Guo et al. (2017)
Precipitant: H3 PO4 Li = 82.55%, Fe = 93.05% Yang et al. (2017b)
Precipitant: NaClO Mn = 97.7%, Co = 26.9% Barik et al. (2017)
Precipitant: Na3 PO4 Li = 95.56% Li et al. (2017a)

disparate metallic ions. Solvent extraction possesses some ad- Chemical precipitation
vantages such as the high purity yield of products and the short Chemical precipitation is another pathway commonly em-
reaction time (roughly 30 min). However, its application is lim- ployed for separating and recovering high-value elements from
ited by the complexity of the operation and the high cost of the leaching solutions. This method has the ability to precipitate out
valuable metals and remove trace amounts of impurities, includ-
solvent. In the liquid-liquid extraction process, solvents have the
ing Fe, Cu, and Al. The separation mechanism of chemical precip-
most vital role. Several efficient solvents employed comprise 5-
itation depends on the disparate insolubility of the metal com-
nonylsalicylaldoxime (Acorga M5640) (Pranolo et al., 2010), di-(2- pound under specific conditions of temperature and pH value,
ethylhexyl) phosphoric acid (D2EHPA) (Chen et al., 2015a; Yang which must be attentively adjusted in the precipitating process.
®
et al., 2017a), Cyanex 272 (Pagnanelli et al., 2016; Kang et al., The commonly used precipitants are CO3 2− -containing salts like
2010a), and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl es- (NH4 )2 CO3 and Na2 CO3 as they can form insoluble compounds
ter (PC-88 A) (Virolainen et al., 2017). Different solvents are with almost all high-value metals, comprising Mn2+ (Meshram
utilized for extractions of different metal ions (Acorga M5640 et al., 2015a; Chen et al., 2020), Ni2+ (Nayl et al., 2015, 2017),
for copper (Nan et al., 2005; Suzuki et al., 2012), D2EHPA for Co2+ (Pagnanelli et al., 2016), and Li+ (Zhu et al., 2012; Peng
et al., 2019; Zhao et al., 2019). Additionally, many other pre-
manganese, cobalt, and nickel (Chen et al., 2015a; Yang et al.,
® cipitants have also been reported, such as sodium phosphate
2017a), and PC-88 A and Cyanex 272 for cobalt (Virolainen
® (Na3 PO4 ) (Song and Zhao, 2018), phosphoric acid (H3 PO4 ) (Chen
et al., 2017; da S. Leite et al., 2017; Sattar et al., 2019)). Cyanex et al., 2017), ammonium oxalate [(NH4 )2 C2 O4 ] (Nan et al., 2005),
272 performs superior stability and elevated effectiveness in ex- and oxalic acid (H2 C2 O4 ) (Sohn et al., 2006). Determining the
tracting cobalt (Olushola et al., 2013), therefore it has lured the optimized condition and selecting the suitable precipitant is most
most attraction worldwide among the mentioned solvents. For important in chemical precipitation operation to avoid precipitate
instance, cobalt was selectively extracted from the leachate by dissolution. The advantages of chemical precipitation are low
®
using 50% saponified 0.4 M Cyanex 272, at 5.5–6.0 equilibrium costs, low equipment requirements, and simple operations. This
pH (Kang et al., 2010a). It was observed that 95 to 98 percentage method is commonly associated with the liquid-liquid extraction
of cobalt is extracted, while the extraction rate of nickel is only technique to recover high-value metallic elements from intricate
leachates.
1%. In another work, Olushola et al. (2013) compared various
® Pinna and colleagues (Pinna et al., 2017) dissolved lithium
Cyanex solvents in extracting and separating nickel and cobalt. and cobalt in a leaching solution of H3 PO4 (leaching agent) and
® ®
The examined extractants include Cyanex 923, Cyanex 921, H2 O2 (reducing agent). Following the leaching process, sodium
® ® ®
Cyanex 421X, Cyanex 301, and Cyanex 272. The outcomes hydroxide and oxalic acid were added to the solution. Conse-
®
indicated that Cyanex 272 is the most appropriate solvent for quently, 99% of cobalt was precipitated in the form of CoC2 O4
the separation of Co and Ni. (97.8% purity), and 88% lithium was recovered as Li3 PO4 , at a
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Table 11
Industrial hydrometallurgical battery recycling technologies.
Company Country Capacity Pre-treatment Hydrometallurgy Products Secondary Losses Ref.
(t/year) Products
Retriev Canada 4500 Dismantling; Precipitation Li2 CO3 Steel, Cu, Co, Plastic Anon
Wet comminution, Al (2022a),
screening, shaking Vezzini
table, filtration (2014)
Recupyl Valibat France 110 Crushing, vibrating Hydrolysis leaching Li2 CO3 , LiCO2 , Steel, Cu, Al, Cu, graphite Mossali
screen, secondary Li3 PO4 metal oxides, et al.
screen, magnetic C, Co (2020),
separator, densimetric Velázquez-
table, Martínez
et al.
(2019)
Batrec Industrie AG Switzerland 200 Crushing in inert CO2 Leaching and washing – – – Chen
atmosphere in acidifies aqueous et al.
solutions (2019b),
Vezzini
(2014)
American Canada – Sorting, active H2 SO4 , SO2 reductive LiOH, Ni(OH)2 , – – Jung
Manganese material/ Current leach Co(OH)2 , et al.
collector separation Mn(OH)2 , (2021)
Al
Brunp China – – Sulfuric acid and – – – Chen
hydrogen peroxide et al.
(2019b),
Jung
et al.
(2021)
Green China 20000 – Leaching, purifying, and Co powder – – Lv et al.
Ecomanufacture leaching- resynthesis (2018)
HiTech Co
Bangpu Ni/Co China 3600 – Leaching, purifying, and Cathode – – Lv et al.
High-Tech leaching- resynthesis material, (2018)
Co3 O4

purity of 98.3%. Because certain elements such as Co, Ni, and recovery. However, it is relatively costly because of the large con-
Mn have identical properties, hence, complicated procedures are sumption of organic acid and the long reaction time. Furthermore,
required for separating these metals. To decrease the precip- additional chemicals are required aiming at adjusting the leachate
itation steps and to reclaim valuable elements from intricate composition to meet the prerequisite of the re-generated cathodic
solutions, an efficient way is the coprecipitation of all the target substances.
metals and direct sintering of precursors into cathodic materials. Another method to separate and reclaim target metals from
The potential recovery approach of coextraction-coprecipitation- used LIB leaching solutions is electrochemical deposition. The
resynthesis was proposed by Yang and colleagues (Yang et al., principle of this technique is on the ground of the redox potential
2017a). In this procedure, firstly 85% Ni, 99% Co and 100% Mn dissimilarity of the metallic ion. The studies regarding electro-
in the leachate of spent LIBs were co-extracted and separated chemical deposition mainly focus on recovering Co from the used
from lithium by utilizing D2EHPA in kerosene. Then, lithium battery leachate (Garcia et al., 2011; Freitas and Garcia, 2007).
from the raffinate was treated with sodium carbonate to obtain Besides, the application of ion exchange (Strauss et al., 2021)
lithium carbonate with 99.2% purity. Following that, transitional and electrodialysis (Iizuka et al., 2013) also have been reported.
elements were stripped by 0.5 M sulfuric acid, and the metals The commercial implementation of these techniques is restricted
namely manganese, cobalt, and nickel were co-precipitated as because of their complicated operation and exorbitant costs.
metal hydroxide (Ni1/3 Mn1/3 Co1/3 (OH)2 ) via co-precipitation pro-
cessing. Eventually, NMC111 cathode material was regenerated 3.3.3. Industry demonstrations
via the calcination of the mixture of metal hydroxide and lithium A summary of hydrometallurgical technologies of recycling
carbonate. The combination of co-precipitation and co-extraction used lithium-ion batteries in the industry is given in Table 11.
is a potential recovery approach. This integrated pathway can Retriev initially called Toxco developed a hydrometallurgical pro-
eliminate the expensive stage of separation and produce cathodic cedure (Fig. 13) to recycle retired LIBs with an annual capacity
substances with good quality. of 4500 tons (Anon, 2022a). Retriev processing commences with
sorting and dismantling the cases of large battery packs. Waste
Other methods lithium-ion batteries are subsequently shredded by a hammer
In addition to precipitation and liquid-liquid extraction, some mill in the liquid solution of lithium brine or liquid nitrogen
emerging techniques also could be used to separate and re- aiming at reducing the violent reactivities of LIBs, obviating the
claim high-value elements from leachate. One of those is the release of toxic gases, and neutralizing electrolytes. A fluff frac-
sol–gel method which directly recovers cathodic substances from tion containing plastic and steel is obtained during the shredding
waste battery-leaching solutions. The leachate initially under- process, and the steel of the fluff could be recovered in further
goes a number of treatments to convert into its gel form. Solid treatment. The residual of the shredding process is sent to a
products are then produced from the formed gel by applying shaker table, and from there a mixture of Cu, Co, and Al is
subsequent thermal treatments. The reported recovered prod- formed, this mixture could be used to recover the metals in the
ucts including LiCoO2 (Santana et al., 2017; Li et al., 2012a), subsequent processing. The remnants after the shaker table are
LiMn2 O4 (LMO) (Yao et al., 2021), and NCM (Li et al., 2018b; transferred into a mix and a storage tank, where they are heated
Zhang et al., 2020a). Sol–gel is usually used in association with and reacted with other materials. The residual from the tank is
organic acids due to the chelating effect of these acids. The sol– filtered to obtain cobalt filter cake and lithium brine. The cobalt
gel method is an environmentally friendly technique, which can filter cake allows the recovery of cobalt, and the lithium brine can
tremendously simplify the complex processing of separation and be used to recover Li in subsequent processes.
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Fig. 13. Retriev (Toxco) technology of battery recycling (Vezzini, 2014).

Recupyl proposed a hydrometallurgical approach to recycle ei- Batrec Industrie AG uses a hydrometallurgy pathway (Fig. 16)
ther primary or secondary LIBs (Velázquez-Martínez et al., 2019). for recycling spent lithium-ion batteries. The annual nominal
The annual capacity of this facility is 110 tons. The Recupyl recy- capacity of this facility is 200 tons (Chen et al., 2019b). The Batrec
cling procedure is presented in Fig. 14 or in Fig. 15 in more detail. process commences with generating a protective atmosphere of
In this process, spent LIBs initially undergo two-step comminu- CO2 ; and spent LIBs are crushed in that protective atmosphere
tion. The first grinding aims to expose the internal compounds, it to minimize possible reactions. The shredded battery material
is carried out by a shear at 11 rpm in an inert gas of Ar or CO2 as then undergoes a neutralization treatment in humid air, followed
a protective atmosphere. The secondary shredding is conducted
by using a scrubber to purify the CO2 prior to being released.
by a high-speed rotary (90 rpm) impact mill to lower the particle
Afterward, an acidified aqueous liquid is employed to treat the
size of the battery materials. The crushed materials are put onto a
processed battery material. During this process, all metal frac-
vibrating screen and divided into two fractions above and below
3 mm. Ferrous elements of the proportion above 3 mm are elim- tions are recovered and could be sent to pyrolysis or mechanical
inated via the magnetic separation step. The obtained substances separation for further purification. A liquor fraction obtained from
are sent to a densimetric table, where two different fractions the leaching step can be processed to recover more substances.
of the low-density material (containing plastics and paper) and However, the details of the Batrec recycling process are not
the high-density material (including aluminum and copper) are available in the literature.
separated. Meanwhile, the portion below 3 mm is sieved in a Hydrometallurgy is also a prevalent method for recycling
screen with smaller holes (500 µm) to eliminate the remaining spent LIBs in China. Brunp is a subsidiary of CATL which is a
Cu particles. Removing the impurity of copper is important as this giant Chinese LIB manufacturer. Brunp processes retired LIBs by
element can badly hurdle further hydrometallurgy processing. acid leaching (H2 O2 as a reductant and H2 SO4 as a leachant), and
After fine sieving, the derived powder is stirred in water with cathodic materials can be fabricated from the obtained metallic
the addition of lithium hydroxide. The water-leaching process can hydroxides (Anon, 2022d). Other Chinese enterprises adopting
release hydrogen because of hydrolysis, so it must be conducted the same way for recycling retired batteries are Highpower In-
in an atmosphere with limited oxygen content. During water ternational, TES-AMM, GHTECH, and GEM. In South Korea, a
leaching, the lithium salt is soluble in the solution, meanwhile,
company named SungEel HiTech employs a hydrometallurgy
the graphite and metallic oxides are not, and they are segregated
process to recover high-value elements (copper, lithium, cobalt,
through further processing of filtration. LiCoO2 or Li2 CO3 in the
manganese, and nickel) from waste lithium-ion batteries. The
aqueous phase can be reclaimed either via solid/liquid separation
or by adding CO2 . The residue obtained after water leaching and reclaimed substances can be utilized for the fabrication of new
filtration is dissolved at 80 ◦ C by using sulfuric acid. After acid LIBs (Anon, 2022e). American Manganese a facility located in
leaching, copper is cemented with steel, and carbon is filtered. Canada proposes a hydrometallurgy procedure (leaching com-
Lithium in the leachate could be recovered as lithium phosphate bined with electrochemical processing) for recycling waste cath-
via precipitating with phosphoric acid. Meanwhile, cobalt can odes. American Manganese approach can recover approximately
either be reclaimed in the metallic form via electrolysis or in the 100% of Al, Mn, Ni, Co, and Li from various cathode chemistries
form of cobaltous hydroxide by adding sodium hypochlorite. comprising LMO, LCO, NMC, and NCA (Anon, 2022f).
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Fig. 14. LIB recycling processes of several companies: Retriev, Duesenfeld, Akkuser, Recupyl, and Umicore (Harper, 2019).

3.4. Direct recycling of spent LIBs Direct recycling typically involves pre-treatments and regen-
eration of electrode materials. Pre-treatments include discharg-
ing, dismantling, and separation of battery constituents. The
Another way to recycle retired LIBs is direct recycling. In this
separation of LIB components can be done by utilizing physical,
processing, LIB structures are retained, meanwhile, active sub-
magnetic, and moderate thermal treatments aiming at preventing
stances of the batteries are directly recovered and harvested (Shi
the chemical breakdowns of target substances. Regeneration of
et al., 2018a,b; Ji et al., 2021). Direct recycling shows many
active materials can be achieved via hydrothermal re-lithiation,
superiors over pyrometallurgy and hydrometallurgy in terms of
solid-phase re-lithiation, electrochemical re-lithiation, and chem-
simple operation, lower secondary wastes, and less hazardous ical re-lithiation. The studies regarding LIB direct recycling pro-
emissions (Ciez and Whitacre, 2019). Besides, after regenerating, cesses are summarized in Table 12.
the electrodes can be reutilized directly is another benefit of
direct recycling. However, direct recycling exists many challenges 3.4.1. Solid-phase sintering
which keep the recovery approach mainly at the lab scale (Chen Solid-phase sintering employs Li agents in the solid phase as
et al., 2019b; Bai et al., 2020). One of the major barriers is the a Li resource to regenerate cathode materials. In this process,
varieties of cathodic chemistry since multiple material inputs can the Li-ion is integrated into the available locations at elevated
result in poor recovering efficiency and low purity outputs. Thus, temperatures, and it is utilized for supplementing the loss of
laborious sorting and separation processes are required to reach Li. Solid-phase sintering is considered the most direct pathway
single-material chemistry. Another hinder to the direct recycling for restoring lithium from deficiencies and producing new cath-
approach is ensuring the consistency as well as the quality of the ode powder (Bai et al., 2020). LiOH (lithium hydroxide), LiNO3
produced materials to meet the industry prerequisites of LIBs. (lithium nitrate), or Li2 CO3 (lithium carbonate) can be used as a Li
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Fig. 15. Recupyl battery recycling technology (Velázquez-Martínez et al., 2019).

Fig. 16. Batrec technology of battery recycling (Vezzini, 2014).

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Table 12
Studies on direct recycling of spent LIBs.
Method Conditions Cathode Performance (mAh g−1 ) Ref.
First-discharge Capacity retention
capacity
Solid-state • 850 ◦ C, with Li2 CO3 LCO 150.3 (at 0.1 C) 140.1 (after 100 cycles) Chen et al. (2016b)
re-lithiation
Solid-state • 900 ◦ C, 12 h, with Li2 CO3 LCO 152.4 – Nie et al. (2015)
re-lithiation
Solid-state • 850 ◦ C, 12 h, with Li2 CO3 LCO 152.1 (3–4.3 V, at 135.4 (at 1 C, after 100 Shi et al. (2018a)
re-lithiation 0.1 C) cycles)
Solid-state • 800 ◦ C, 10 h, with Li2 CO3 NMC 165 (at 0.2 C) 133.3 (after 100 cycles) Meng et al. (2019)
re-lithiation
Solid-state • 300 ◦ C, 4 h, with LiNO3 and NMC523 143.9 (at 0.1 C) 134.6 (at 1 C, after 100 Shi et al. (2019a)
re-lithiation LiOH • 850 ◦ C, 4 h, with cycles)
Li2 CO3
Solid-state • 850 ◦ C, 4 h, with Li2 CO3 , in NMC111 157.4 (at 1 C) 123.8 (at 1 C, after 100
Shi et al. (2018b)
re-lithiation O2 cycles)
NMC523 – 127.4 (at 1 C, after 100
cycles)
Solid-state • 700 ◦ C, 8 h, spent LFP to LFP 144 (0.1 C) 135 (after 100 cycles) Song et al. (2017)
re-lithiation new LFP ratio of 3:7
Solid-state • 650 ◦ C, 1 h, with Li2 CO3 LFP 147.3 (2.5–4.2 V) 140.4 (at 0.2 C, after 100 Li et al. (2017b)
re-lithiation cycles)
Solid-state • 350 ◦ C, 2 h, spent LMO to LMO Roughly 35 Roughly 35 (after 10 Wang and Whitacre (2018)
re-lithiation LiOH of 1:1 molar ratio cycles)
• 850 ◦ C, 4 h
Hydrothermal • 1M LiOH and 1.5 M Li2 SO4 , LCO 153.1 (at 0.1 C) 135.1 (at 1 C, after 100 Shi et al. (2018a)
re-lithiation 220 ◦ C, 4 h cycles)
• 800 ◦ C, 4 h
Hydrothermal • 2 M LiOH, 6 h, 80 ◦ C, 600 W LCO 133.5 132.9 (after 40 cycles) Zhang et al. (2014a)
re-lithiation ultrasonic power
Hydrothermal • 2 M LiOH, 10 h, 120 ◦ C, LCO 131.5 129 (after 20 cycles) Zhang et al. (2015a)
re-lithiation 999 W ultrasonic power
Hydrothermal • 0.1 M LiOH with aqueous LCO 132.9 (at C/5) 126.7 (2.8–4.2 V, at C/5, Zhu (2016)
re-lithiation pulsed discharge plasma after 50 cycles)
Hydrothermal • LiOH, 4 h, 220 ◦ C NMC111 158.4 (at 1 C) 122.6 (at 1 C, after 100
Shi et al. (2018b)
re-lithiation • 850 ◦ C, 4 h cycles)
NMC523 – 123.8 (at 1 C, after 100
cycles)
Hydrothermal • 0.1 M LiOH, 12 h, 180 ◦ C LMO 111 (at 0.5 C) 98 (3.0–4.3 V, at 0.5 C, Gao et al. (2020)
re-lithiation after 100 cycles)
Hydrothermal • Spent LMO with LiOH (1:1 LMO Roughly 98 Roughly 95 (after 10 Wang and Whitacre (2018)
re-lithiation molar ratio), 165 ◦ C, 24 h cycles)
Electrochemical • Cycle spent cathode coating
LFP 150–155 – Ganter et al. (2014)
with pure lithium metal
Chemical • Immerse spent cathode
power in lithium-containing
solution

resource in the solid-state sintering process. The amount of added work, used LCO cathodes were regenerated via thermal process-
Li resources is calculated based on the level of Li loss which stems ing at 850 ◦ C in the presence of lithium carbonate (Chen et al.,
from the change of undesired phase and the solid-electrolyte 2016b). The discharging capacity of the renovated cathodes could
interface thickening. reach 150.3 mAh g−1 , being close to commercial LCO (roughly
Song et al. successfully recycled cathode materials of spent 150 mAh g−1 ). After 100 charge–discharge cycles, regenerated
LiFePO4 (LFP) batteries by solid-state sintering (Song et al., 2017). cathode materials delivered a good retention rate of 93.2%. The
After the pre-treatment steps of disassembly and separation, the study also disclosed that a small amount of Al and Cu residue
spent LFP was directly regenerated at 700 ◦ C with doping of the would improve the electro-chemical property of recycled cath-
new LFP (3:7 doping ratio). It is shown that the discharge capacity odes. Threshold impurity limits for Al and Cu are 0.4 wt.% and
of the recycled cathode can attain 144 mAh g−1 , while that of
0.6 wt.%, respectively.
commercial LFP is around 150 mAh g−1 . In addition to LiFePO4 ,
Li2 CO3 can also work for LFP-based cathode re-lithiation. In one,
Li and colleagues calcinated used LFP cathodes with lithium car- 3.4.2. Hydrothermal re-lithiation
bonate at 650 ◦ C for 1 h for the regeneration purpose (Li et al., Hydrothermal re-lithiation is another potential method of
2017b). The capacity for the initial discharge of the recycled spent LIB direct recycling. Initially, a solution with an excess Li
LFP is 147.3 mAh g−1 . After 100 cycles of charge and discharge, source is used to treat spent battery materials, and the added
the retention rate of the renovated cathode was 95.32%, which lithium is incorporated into the structures of the spent cathodes.
meets the commercial LFP requirement of over 92.43%. In another It is usually ensued by a short annealing processing, aiming to
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reconstruct material crystallinities and improve restorations of 3.4.4. Industry demonstrations

structures. Some technologies could be involved to accelerate Li The application of LIB direct recycling is mainly at the lab
ions transfer including aqueous pulsed discharge plasma (Zhu, scale. In industry, only two companies apply direct recycling for
2016) and ultrasonication (Zhang et al., 2014a). Stoichiometric recovering end-of-life LIBs as seen in Fig. 17. The hydromet-
supplements of lithium are not required as the hydrothermal allurgy technique is the most prevalent recycling approach for
approach can self-limit lithium restorations, unlike solid-phase spent lithium-ion batteries at the industrial scale, followed by
re-lithiation (Bai et al., 2020). The degraded cathodes with any the pyrometallurgical one. However, in terms of LFP recycling,
levels of deficiencies could be accommodated by the hydrother- hydrometallurgy or pyrometallurgy is not economically viable
mal technique. Hydrothermal re-lithiation can efficiently work because of its poor essential value (Chen et al., 2019b). On the
with many cathodic chemistries such as NMC 111 (Shi et al., contrary, the recovery of spent LIBs could be profitable via direct
recycling (Gaines, 2018). OnTo Technology headquartered in the
2018b), NMC 523 (Sloop et al., 2019), NMC 622 (Sloop et al.,
USA develops an integrated procedure of hydrothermal and ther-
2019), and LCO (Shi et al., 2018a; Sloop et al., 2020).
mal treatment to directly recycle spent LIB cathodes (Sloop et al.,
A two-stage process of hydrothermal treatment and annealing
2018). The recycling pathway is feasible in the economic sense,
for regenerating spent LiCoO2 cathode was proposed in a pub-
which is stated by the enterprise. Another direct recycling process
lished study (Shi et al., 2018a). The spent LCO cathode first is
for retired lithium-ion batteries is proposed by Farasis, and the
treated in a mixed solution of 1M LiOH and 1.5 M Li2 SO4 (or 4 manufacturer claims achievements regarding its approach (Chen
M LiOH) for 4 h, at the temperature of 220 ◦ C. Electro-chemical et al., 2019b).
performances of the recycled LCO furtherly were improved via
a short-duration annealing process (800 ◦ C for 4 h). The rejuve- 4. Conclusion and perspectives
nated cathode performed a good discharging capacity of 153.1
mAh g−1 at 0.1C (commercial LCO: ∼150 mAh/g). After 100 The lithium-ion battery is an outstanding technique for storing
discharge–charge cycles, it still can be maintained at 135.1 mAh energy in electric vehicles, energy systems, and electronics. Its
g−1 at 1C, corresponding to 91.2% of retention rate. It was also applications have been booming in recent decades leading to
concluded that the LiCoO2 particles renovated through the hy- mounting quantities of spent LIBs. The retired lithium-ion battery
drothermal approach exhibit a superior rate capability compared is a serious problem that must be addressed for protecting hu-
to the LiCoO2 sample repaired by the solid-phase re-lithiation man health and the ecosystem, as well as for preserving natural
method. The combination of hydrothermal treatment and anneal- resources. In this paper, we introduce the structure of LIBs and
ing processing also can be utilized for rejuvenating the cathode review possible options for end-of-life LIBs including re-use and
of NCM. Shi et al. recycle the spent NMC111 and NMC523 by recycling which minimize the number of spent batteries ending
treating them in LiOH solution for 4 h, at the temperature of up in landfill or incineration facilities. The re-use approach com-
220 ◦ C, ensued by a brief annealing processing (4 h, 850 ◦ C) (Shi prises remanufacturing and repurposing considered preferable in
et al., 2018b). Recycled NCM materials displayed a good electro- the waste management hierarchy. However, these options only
chemical performance. Specifically, the capacities of NMC111 in lengthen the battery lifespan and delay the recycling horizon
the first cycle and after 100 cycles are 158.4 and 122.6 (mAh g−1 ) which inevitably is the final fate for all lithium-ion batteries.
respectively. Meanwhile, after 100 cycles of charge and discharge, Direct recycling, hydrometallurgical recycling, and pyrometallur-
the capacity of NMC532 was kept at 128.3 mAh g−1 . gical recycling are the three main approaches used to recycle
Zhang et al. use hydrothermal re-lithiation assisted by ul- retired lithium-ion batteries. The pyrometallurgy method refers
to treating spent LIBs under high temperatures followed by sep-
trasound to recycle degraded LiCoO2 (Zhang et al., 2014a). The
aration steps. The hydrometallurgical process involves dissolving
re-lithiation is accelerated via the effect of cavitation produced
target metallic elements from LIBs in a leaching solution and re-
by ultrasonic waves. Under the reported conditions (600 W ul-
claiming the metals via the further stage of separation and purifi-
trasonic power, 2 M LiOH, 6 h, 80 ◦ C), the discharging capacity
cation. Direct recycling relates to recovering LIB active substances
of the renovated LCO is 133.5 mAh g−1 in the first cycle. After
directly, meanwhile, maintaining the battery structures.
40 cycles, the discharging capacity is still kept at 132.9 mAh g−1 , Pyrometallurgy is featured by simplicity and reliability, and
corresponding to 98.4% of retention rate. In another work, Zhu hydrometallurgy offers less emissions and superior effectiveness.
et al. rejuvenate the degraded LCO by using 0.1 M LiOH assisted Both pyrometallurgy and hydrometallurgy have been commer-
by an aqueous pulsed discharge plasma (Zhu, 2016). The first cialized, meanwhile, direct recycling is mainly at laboratory and
discharge capacity of repaired LCO is 132.9 mAh g−1 . After 50 pilot scales, requiring beyond advancements for having meaning-
discharge and charge cycles, its capacity retention is reported at ful impacts. To date, none of the existing recovery approaches
97.2%. offers a perfect solution for recycling all LIB components with no
harmful emissions, low energy consumption, and low cost. Py-
rometallurgy is not able to reclaim some battery substances such
3.4.3. Other regeneration processes
as Al, graphite, and plastics; it requires high energy consumption
Other approaches such as chemical and electrochemical pro-
and generates lots of hazardous gases. Hydrometallurgy is costly
cesses can also be used for re-lithiation. Chemical manner refers and intricate, this technology and pyrometallurgy heavily depend
to immersing spent cathodic materials in Li-containing solutions, on the cathode chemistry resulting in the unsustainability. Direct
whereas the electrochemical re-lithiation employs the electro- recycling technique is still far from the practical reality facing
chemical technique for repairing degraded cathodes (Chen et al., many obstacles such as multiple material inputs, the consistency,
2019b). Ganter et al. regenerated the end-of-life LiFePO4 by and the quality of the produced LIBs. Recycling of spent LIBs is
applying electro-chemical and chemical re-lithiation technolo- in the infancy stage, so further endeavors and investment are
gies (Ganter et al., 2014). Re-lithiated cathodes regained the required to accomplish more effective and greener solutions. In
initial discharge capacity ranging from 150 to 155 mAh g−1 . which, not only valuable metals are reclaimed but also other
Both chemical and electrochemical re-lithiation approaches show substances adverse to the ecosystem must be properly disposed
potential results for future applications. of.
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Fig. 17. Spent LIBs recycling facilities around the world (Chen et al., 2019b).

The swift evolving of LIB technology is raising a challenge for Declaration of competing interest
the recycling industry. LIB material is moving towards cobalt re-
duction, ultimately attaining cobalt-free electrodes that will influ- The authors declare that they have no known competing finan-
ence the direction of battery recovery investigations. At present, cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
the recycling approach predominantly focuses on cobalt content.
However, it is crucial to shift the focus towards reclaiming other
Data availability
substances and elements such as Li, Ni, and Mn to accommodate
the advancements in LIB manufacturing. In addition to scientific No data was used for the research described in the article.
considerations, non-technical factors comprising logistics, collec-
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