Comprehensive Review On Concept and Recycling Evol

pubs.acs.
org/EF Review
Comprehensive Review on Concept and Recycling Evolution of

Lithium-Ion Batteries (LIBs)
Kishore K. Jena, Akram AlFantazi, and Ahmad T. Mayyas*
Cite This: https://doi.org/10.1021/acs.energyfuels.1c02489 Read Online
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ABSTRACT: Recycling of spent lithium-ion batteries (LIBs) is an

emergent research area, which may contribute to a sustainable
future with reduced waste. Current recycling strategies only
generate recycled compounds rather than functional materials, and
Downloaded via 181.214.87.118 on October 29, 2021 at 02:54:23 (UTC).
most of those strategies deal with cathodes rather than anodes.

Developing an effective method to recover Co and Li from the
spent LIBs has become a research area of great interest in the past
decade and also a challenging job for the industry and researcher.
Researchers have studied several methods to recycle valuable
metals (Co, Li, Ni, and Mn) from spent lithium-ion batteries.
Valuable metals such as cobalt (Co) and lithium (Li) are mainly
used to prepare lithium cobalt oxide (LiCoO2) for applications in
LIBs. The increasing demand of the LIBs for electronic devices and
electric vehicles has created an additional problem to the initial
and exclusive thought of finding good-performing and long-lasting
batteries. In this present review, recovery of Co and Li from
LiCoO2 powders of spent LIBs by a hydrometallurgical process is
discussed and summarized to aid researchers and policymakers who are working on this area on the best recycling practices.
1. INTRODUCTION predicted future market growth of lithium-ion batteries for

Lithium-ion batteries (LIBs) are widely used in mobile phone, EVs applications. It was found that Co, Ni, and Li could
laptops, camera, an more1 and are expanding their market in become critical materials in the near future for several major
the area of rechargeable batteries. Due to excellent features battery producers in the United States and members of the
such as small size, high power density, long cycle life, high European Union which have no mining activities for Co and
voltage, and moderate self-discharge, LIBs have captured Ni. Recycling of valuable metals (Co, Li, Ni, Mn) from the
attention in the last two decades and left behind the nickel spent LIBs is proposed as a potential solution to meet the
metal−hydride and nickel−cadmium rechargeable batteries, future demand of the key elements in cathode materials. The
which lack such important characteristics needed in recharge-
world’s LIBs production reached 2.05 billion in 2005 and 5.86
able batteries.2−5 Limited resources, environmental issus, and
strong demand for high energy densities in electric vehicles billion in 2012.9 In China, the production of LIBs was 4.18
(EVs) have motivated many entrepreneurs to invest in billion in 2012 and increased to 7.84 billion in 2016.10 The
recovering valuable metals (Co, Li, Ni, Mn) from spent LIBs current status and future demand of Co and Li in the market
and recycle them back to produce next-generation rechargeable are discussed in this review.1,11−13 Nowadays, the economics of
LIBs and other rechargeable battery technologies (e.g., LIBs recycling may be questionable as they contain only a
sodium-ion and lithium−sulfur batteries). The global demand small fraction of lithium carbonate which is inexpensive
for LIB raw materials and tactics in the resynthesis process compared with Co and Ni, whereas Co and Ni recycling may
along with the wide range of growing applications of spent LIB
materials give more attention toward the recycling process.6
Cobalt (Co), nickel (Ni), and lithium (Li) are currently the Received: July 22, 2021
state-of-the-art valuable metals in the cathode layer for most of Revised: October 10, 2021
the commercial LIBs. Different types of cathode-active
materials such as LiCoO2 (LCO), LiNiO2 (LNO), LiMn2O4
(LMO), and LiNi0.33Mn0.33Co0.33O2 (NMC)7,8 have been
recently recognized as significant materials due to the
© XXXX The Authors. Published by
American Chemical Society https://doi.org/10.1021/acs.energyfuels.1c02489
A Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels pubs.acs.org/EF Review
Figure 1. Summary of crystal structure and properties of different LIB cathodes.
be economically attractive. It is predicted that by 2030 the by the formation of a sulfate radical (SO4•−) and a hydroxyl
global LIB recycling market will reach $23.72 billion.11,14,167 radical (HO•) from persulfate, and a Co2+ and Mn2+ leaching
The materials recovered from the recycling process of spent process was prevented. Lin et al.21 used a green chemistry to
LIBs give benefits to make new batteries and can lower the achieve a high concentration of Li and Co from spent LIBs.
manufacturing cost. Recycling LIBs is not straightforward and They reported that 99.3% Li and 98.7% Co were recovered
associated with several challenges before and during the
from LIBs by using a conventional sulfation roasting process.
recycling process which can act as economic determinants to
the adoption of some recycling processes. Fluctuations in the Li et al.,22 Fan et al.,23 Chen et al.,24 and Zheng et al.25 used an
virgin material prices always put question whether recycling organic acid leaching process for recycling LIBs. Li et al.26
LIBs is a good business choice compared with manufacturing reported the leaching mechanism and morphology of a
new batteries with virgin materials. Further, the recycling leaching process. Xu27 reported interphasial chemistry and
process of LIBs is complicated due to the wide variety of the processes in LIBs. They reviewed about electrolyte compo-
battery structures and chemistries. In many cases, recyclers nents, degradation and stabilization of electrolytes, chemistry
have to deal with compact, complex devices and unequal sizes of interphase, and advanced characterization and imaging. Fan
and shapes, and some LIBs are not designed to be et al.11,28 reported sustainable recycling technology for LIBs.
disassembled. As an example, in the early 1990s when Sony
Life-cycle assessment, perspectives of strategic resources, and
commercialized LIBs for the first time, researchers have
repeatedly modified the cathode-active materials to reduce cost economic demand are discussed to justify the sustainability of
and enhance charging capacity, longevity, recharge time, and the recycling technology. Efficiency, economic return, environ-
other performance parameters.15,16 The cathode materials such mental benefit, safety and new challenges, and future prospects
as lithium nickel manganese cobalt oxide (NMC), lithium for battery sustainability are also discussed.
nickel cobalt aluminum oxide (NCA), and lithium iron In this review, the recycling of LIBs to recover Co, Ni, and
phosphate (LFP) are used to improve the storage capacity Li by using a hydrometallurgy process is discussed. The current
and reduce the overall manufacturing cost of LIBs.17−19 In this status such as leaching efficiency, application, cost, and
case, when the cobalt content in g/kWh in the LIBs is very low, environmental effect of LiCoO2 cathodes in the present
recycling in the long term would be done mainly for ecological recycling technologies of LIBs are discussed in this review.
benefits and for adherence to environmental regulations in
This review mainly deals with the lithium cobalt oxide (LCO)
some countries.
Different recycling processes and changes in parameters cathode. The limitation of current technologies and a new
were used to recover the metals from the LIBs. Lv et al.20 perspective toward the future concept of LIBs recycling are
reported a new methodology of advanced oxidation processes also pointed out. Possible research opportunities and
(AOPs) to get high concentrations of Li metal from spent LIBs challenges in recycling process are explained at the end of
during hydrometallurgical leaching. Li leaching was promoted this review.
B https://doi.org/10.1021/acs.energyfuels.1c02489
Energy Fuels XXXX, XXX, XXX−XXX
2. LI-ION BATTERY: TYPES, STRUCTURE, AND
High cost, nickel and cobalt (expensive

limited load capabilities, safety issues
DEGRADATION MECHANISM
Short life span, low thermal stability,
Low specific energy and expensive

Low energy density, elevated self-
Short lifetime, low energy density

LIBs are rechargeable batteries that store energy through
and less abundant materials)

reversible intercalation of lithium ions. It does not involve full
Disadvantages
redox reactions and thus manages to avoid many of the lifetime
Safety issues, high cost

and power limiting problems of fully chemical battery
mechanisms. The ratio of ionization potential to atomic
weight for lithium is higher than that for any other element,
discharge
resulting in energy densities that will be difficult to match with
any other electric storage technologies.29 The lithium-ion
battery is considered a powerful and high efficiency type of
Cheap abundant materials and high power, safer than Li
Long life, fast charge, wide temperature range, safest Li-

battery in comparison with Ni−Cd and Ni−MH batteries due
High capacity and voltage, high power densities, good

Better safety and better performance than LCO, high
Excellent power, good lifetime and safety, abundant

to its high energy and power densities. As a result of these
cobalt, high thermal stability, enhanced safety

facts, most of the devices such as smart watches, laptops, digital
cameras, calculators, and communication equipment have
adopted LIBs as a main source for energy storage, with more
installation capacity year after year in the last two
High performance well understood

Advantages
decades.30−34 This section explains six of the most common
cathode materials of LIBs. Most of the LIBs are constructed
capacity and high power

with graphite in the anode and different metal oxides in the
cathode, which have different chemistries and structures. In the
process of charging and discharging, lithium ion can intercalate
ion batteries
Table 1. Different Electrode Materials of LIBs and Their Specific Capacities, Advantages, and Disadvantages
into and out of layers or tunnel structures. The performance of
materials
life span
the LIBs depends on the structure and chemistry of the
cathode materials. Figure 1 presents a summary of crystal
structures and properties of the most common LIBs cathode.
Electric powertrain (Mitsubishi i-MiEV, Honda

Portable and stationary, need high load current
Medical devices, industrial, electric powertrain

The different types of LIBs and their advantages and
disadvantages are reported in Table 1.
Mobile phones, tablets, laptops, cameras
E-bikes, medical devices, EVs, industrial
Fit EV), solar-powered street lighting

2.1. Types of Lithium-Ion Batteries.35168 2.1.1. Lithium
Power tools, medical devices, electric

Cobalt Oxide (LiCoO2), LCO.36,37 LCO is used in high specific
energy batteries which consist of a cobalt oxide cathode and
Applications
graphite anode and is used in most of the portable electronics

services as hybrid cells
such as mobile phones, laptops, and digital cameras. The

cathode has a layered metal oxide structure, and lithium ions
and endurance
move from anode to cathode during the discharge mode and

powertrains
reverse flow from cathode to anode during the charging mode.

(Tesla)
Some common characteristics of the LCO include high

charging rate (also called C-rate) which is in the range of
0.7−1C and discharge rate (C-rate) that could reach 1C.
Specific capacity
50−80 Wh/kg
2.1.2. Lithium Nickel Manganese Cobalt Oxide (LiNiMn-

(mAh/g)
CoO2), NMC.38 NMC is the common cathode chemistry in

160−170
100−120
180−200
electric vehicles, e-bikes, and electric scooters. Nickel provides

140
170
high specific energy but poor stability, and manganese has the
benefit of forming a spinel structure to achieve low internal
vs Li/Li+
Voltage
resistance but offers a low specific energy. The strength of the

3.9
3.8
3.4
4.1
3.8
2.8
lithium nickel manganese cobalt oxide is enhanced by the

combination of the individual strength of nickel and
Abbreviation
manganese metals. One-third mole of nickel, one-third mole

NMC
LMO
NCA
LCO
LTO
LFP
of manganese, and one-third mole of cobalt is used to make the

NMC cathode, which is also known as 1−1−1 (some
researchers also use 333 to refer to this NMC chemistry).
LiCoO2: cathode (∼60% Co); LiCoO2
cathode (∼9% Co); anode, graphite

LiMn2O4: cathode, LiMn2O4; anode,
Battery manufacturers recently started to change the

LiFePO4: cathode, LiFePO4; anode,
Li2TiO3: LMO or NMC cathode;

LiNi0.8Co0.15Al0.05O2:LiNiCoAlO2
combination of nickel, manganese, and cobalt to 5−3−2 due

LiNi0.33Mn0.33Co0.33O2: cathode,
LiNiMnCoO2; anode, graphite
to the cost of the cobalt raw material, and the evolution of

Cathode Materials
anode, Li2TiO3 (titanate)
NMC is expected to go with lesser amounts of cobalt per kWh

of storage capacity such as 6−2−2 and 8−1−1 cathode
anode, graphite
chemistries. The charge rate (C-rate) is 0.7−1C and charges to

4.20 V,with some going to 4.30 with a 3 h charge typical.
graphite
graphite
Charge current above 1C may shorten the battery life. The

discharge rate (C-rate) is 1C, with 2C possible on some cells,
with a 2.50 V cutoff.
C https://doi.org/10.1021/acs.energyfuels.1c02489
Figure 2. (a) General battery structure. (b) Major components and operating mechanism of lithium-ion batteries (LIBs) (Or et al., reproduced
with permission).42 (c) Degradation mechanisms for rechargeable batteries (Fan et al., reproduced with permission).11
2.1.3. Lithium Manganese Oxide (LiMn2O4), LMO.168 stability, and enhanced safety with low resistance. Li phosphate
LMO is a three-dimensional spinel structure (cubic close- has a higher self-discharge than other LIBs. Li phosphate has
packed oxides with eight tetrahedral and four octahedral sites excellent safety and a long life span but moderate specific
per unit) of lithium manganese oxide as the cathode material energy and elevated self-discharge. A typical C-rate is 1C, and
that improves ion flow on the electrode, which results in lower LFP charges to 3.65 V, with a 3 h charge time typical. The
internal resistance and improved current handling. To improve discharge rate (C-rate) is 1C, with some LFP cells reported to
the specific energy and prolong the life span, most Li− have 25C, with a 40A pulse (2s) and 2.50 V cutoff (lower than
manganese batteries are blended with lithium nickel 2 V causes damage).
manganese cobalt oxide (NMC). Most of the electric vehicle 2.1.5. Lithium Nickel Cobalt Aluminum Oxide (LiNiCoA-
companies adopted this LMO and NMC combination for their lO2), NCA. A lithium nickel cobalt aluminum oxide battery
new generation car development such as the Nissan Leaf, (NCA) offers high specific energy, good specific power, and a
Chevy Volt, and BMW i3. In terms of charging and discharging long-life span. The charge rate (C-rate) is 0.7C and charges to
rates, LMO has a typical C-rate in the range of 0.7−1C, with a 4.20 V (most cells), with a 3 h charge typical, and fast charge
maximum C-rate of 3C, and it charges to 4.20 V (most cells). possible with some cells. The discharge rate (C-rate) is 1C
The discharge rate (C-rate) is 1C, with 10C possible with typically, with a 3.00 V cutoff; a high discharge rate may
some cells, with a 30C pulse (5s) and 2.50 V cutoff. shorten the battery life.
2.1.4. Lithium Iron Phosphate (LiFePO4), LFP. Phosphate as 2.1.6. Lithium Titanate (Li2TiO3), LTO. Li titanate replaces
a cathode material for rechargeable lithium batteries was first graphite in the anode in the typical lithium-ion battery. The
discovered in 1996 by researchers from the University of LTO layer forms into a spinel structure. LMO or NMC is used
Texas. Li phosphate offers good electrochemical performance in the cathode, and Li titanate is used in the anode. LTO
such as a high current rating, long cycle life, good thermal (commonly Li4Ti5O12) has advantages over the conventional
D https://doi.org/10.1021/acs.energyfuels.1c02489
Figure 3. Complete flowsheet of the recycling and regeneration process of the cathode-active material of LIBs (Li et al., reproduced with
permission).46
cobalt-blended Li ion with the graphite anode by attaining development of next-generation electric vehicles since the
zero-strain property, no solid oxide interface film formation, demand on lithium may surpass the supply if not enough
and no lithium plating when fast charging and charging at low investment in lithium extraction is made in the near future.
temperature. Li titanate has excellent safety, long life span, and Today, recycling of LIBs is an important and major task for
good performance at low temperatures. The charge rate (C- recyclers in industry and research institutes, not only because
rate) is 1C typically, with a 5C maximum, and it charges to of the battery’s short service life but also because of other
2.85 V. The discharge rate (C-rate)is 10C possible, and it can factors such as environmentsl concerns and having a potential
reach a discharge rate of 30C in the form of 5 s pulses, with a source to recover expensive valuable materials. The big
1.80 V cutoff on LCO/LTO. question is when the battery is considered at its end of the
Basically, the Li-ion battery compartment is covered with life. First, we need to know that degradation mechanism of the
metal and plastic. At the cell level, LIBs consist of several batteries happens because of structural failure and particle
stacked cells with active parts such as the cathode, anode, cracking, corrosion of the current collector, binder decom-
electrolyte, and separator (Figure 2(a)). The operating position, dissolution, dendritic formation in both electrode
mechanism of LIBs is shown in Figure 2(b). The metals materials (cathode and anode), decomposition and deterio-
such as Co, Mn, Ni, and Li are present in the cathode part of ration of the electrolyte and aging, puncture, and clogging of
LIBs in the form of metal oxide, such as LiCoO2, LiNiO2, the separator.11,42 The schematic diagram of the degradation
LiMn2O4, and LiNi0.33Mn0.33Co0.33O2,8,39 and the anode is mechanism of the cathode, anode, electrolyte, and separator of
graphite or activated carbon. As per reported literature, cobalt, a rechargeable battery is shown in Figure 2(c). Many LIBs are
lithium, manganese, and nickel are dominantly available in considered at the end of their life when their storage capacities
cathode layers. faded by 20%−30% of the original storage capacity.43,44
Recycling of Li and Co from LIBs is economically attractive
and valuable metals for next-generation cathodes. Co is less 3. RECYCLING PROCESS OF LI-ION BATTERIES
abundant and more expensive than other transition metals The recovery of valuable cathode-active materials from spent
such as Mn and Ni that are used in the cathode layer in the lithium-ion batteries has been done using four different
form of a metal oxide. Recycling of cobalt from LIBs is methods, namely, mechanical process, pyrometallurgy, hydro-
important due to the carcinogenic, mutagenic, and toxic effects metallurgy, and direct physical recycling. These methods are
to reproduction. Furthermore, recycling of nickel from LIBs is used alone or in combination such as in the the pyrometallurgy
also equally important from health and environmental points process which needs a hydrometallurgical means to recover
of view.8,40,41 The manganese quantity is negligible, and spot high-value elements such as cobalt and nickel.12 Out of these
price does not make it one of the high-value materials. The four general recycling classes, hydrometallurgy is considered
importance of lithium metal has been increased due to the high unique and the most effective recycling process due to several
demand on LIBs in portable electronic devices. The recycling advantages it possesses such as being ecofriendly, having low
of lithium from spent LIBs is a big advantage in the energy consumptions, effective rate of reaction, ability to reuse
E https://doi.org/10.1021/acs.energyfuels.1c02489
Table 2. Recovered Materials and Advantages and Disadvantages of Different Recycling Processes43,44,47
Recycling methods Recovered materials Advantages Disadvantages Examples (Companies)
Mechanical process32,48,49 Li2CO3 1. Applicable to any battery chemistry and 1. Mechanical process alone not sufficient to recover 1. SNAM (France)
configuration. materials
2. Lower energy consumption 2. Should be combined with hydrometallurgical process 2. Taxco process
Energy & Fuels
3. Enhanced leaching efficiency
Pyrometallurgy (smelting)47,50 Cathode: cobalt nickel copper iron; recoverable 1. Highly effective at recovering nickel, 1. Inherent chemistry of smelter traps, other elements in the 1. Accurec (Germany)
from molten alloys, more than 90% cobalt, copper slag
Anode: not possible to recover 2. High recycling efficiency 2. Recovering lithium from the slag expensive and 2. Batrec (Switzerland)
inefficient
3. Ability to remove toxicity 3. Other chemicals in the battery lost 3. Umicore (Belgium)
4. Potential to scale it for larger scales and 4. Suboptimal from lifecycle perspective 4. Nippon Mining and
simplified logistics Metals (Japan)
5. Already exists at industrial scale and 5. Energy intensive, toxic gas emissions
mature metallurgical technique
Hydrometallurgy50,51 Cathode: cobalt, lithium, nickel, aluminum, copper, 1. Easy recycling and simplified procedures to 1. Environmental and revenue issues in large scale due to 1. Eurodieuze (France)
Li2CO3; recoverable as salt, more than 95% reuse as battery material use of hot water, acid, solvents
Anode: destroyed 2. Almost any material recovered at high 2. Source material needs known (e.g., battery chemistry) to 2. G&P Batteries (UK)
efficiency tailor efficient process
3. Chemistry and procedures fairly mature 3. Potential revenue and costs that make hydrometallurgy 3. Recupyl (France)
approaches promising are highly dependent on scale
4. Low emission of gases 4. Retriev Technologies
F
(Canada)
5. Energy consumption less
Direct Recycling52,53 Almost all components except separators 1. Potential recovery of all battery materials 1. Recently demonstrated at a workable scale and quality 1. On To Tech (USA)
pubs.acs.org/EF
in a reusable form
Cathode: cobalt lithium nickel, manganese, 2. Higher revenues and lower environmental 2. Process depends on knowing battery composition and
aluminum, copper; recoverable as battery impacts battery chemistry
materials
Anode: graphite activated carbon 3. Process not dependent on scale as 3. Old cathode chemistries may not be desired to be reused
pyrometallurgy or hydrometallurgy in new generation LIBs
approaches
4. Manual approach to breaking the cell and extracting its
contents may be difficult to scale
Review

https://doi.org/10.1021/acs.energyfuels.1c02489
some leaching chemicals after filtration and purification, low polyvinylidene fluoride (PVDF), and activated carbon; then,
emission of gases, and high concentration metal recovery. To the slurry is coated on the aluminum surface. Nowadays,
recover the high concentration of leaching solution (leachate), research focuses on separation of cathode-active materials from
the nature of the metal and the acid efficiency are the main an Al foil surface by using a simple and efficient dissolution
factors in the recycling process.45 Li et al.46 presented a process. N-Methylpyrrolidone (NMP) is usually employed to
complete flowsheet of the recycling and regeneration process separate the cathode-active materials from Al foils, which
of the cathode material in Figure 3. The advantages and follows the mechanism of “like dissolves like”. The polarity of
disadvantages of the different recycling process are reported in PVDF and NMP plays major role in the dissolution process,
Table 2. where NMP easily dissolves the PVDF polymer and separates
3.1. Pretreatments. The importance of a pretreatment the cathode-active materials from the Al foil surface.63−67 Li et
process is to get electrode materials from spent LIBs and then al.68 reported that the cathode-active materials were easily
proceed in the subsequent hydrometallurgy process. The separated from an aluminum support in a NMP solution in 1 h
lithium-ion battery contains different metals, plastics, and at 100 °C. An ultrasonic-assisted dissolution process was
polymers; these should be removed before further processing. reported by Yao et al.69 Initially, they immersed the cathode in
The recovery of expensive cobalt metal, which is present in a NMP solution for 1 h at 80 °C and then treated it in an
high concentrations in battery cathodes (e.g., LCO and NMC) ultrasonic bath for 20 min. It was reported that the separating
is really challenging work. Therefore, direct processing without efficiency and yield were significantly improved.
pretreatment may lead to losing high concentration valuable Yang et al.70 used ultrasonic treatment to separate cathode-
metals. In this section, different pretreatment process such as active materials from an Al surface at room temperature. Many
discharging, mechanical separation, dissolution, ultrasonic researchers have used other organic solvents such as N,N-
washing, and heat-treatment methods are explained. dimethylacetamide (DMAC), 25 N,N-dimethylformamide
3.1.1. Discharging. The main objective of this process is to (DMF),71 dimethyl sulfoxide (DMSO),72 and ionic liquid73
reduce the chance of short circuiting and self-ignition of spent for the separation of the cathode-active materials. The
LIBs. LIBs should initially be discharged to release any complete removal of cathode-active materials by a dissolution
remaining stored energy in the battery. Ku et al.54 discussed process is not possible, which needs further processing such as
the process of discharging the spent LIBs to less than 0.1 V by a thermal treatment process (calcination process) to burn off
using a discharger. He et al.55 used 5% NaCl solution to the carbon and PVDF residues. Additionally, for scaled up
discharge the LIBs completely. The duration of discharging recycling processes, organic solvent is not suitable due to its
batteries is an important factor to speed up the recycling
high cost and lack of availability as per the polar and nonpolar
process and proceed to the next step. Shaw-Stewart et al.56
nature.
used different saline and basic solutions and studied the
3.1.4. Ultrasonic Washing. The explosion of small bubbles
discharge characteristics of fully charged LIBs. Li et al.57
during ultrasonic washing produces an impact force, which
studied the discharge efficiency by using different concen-
helps remove the cathode-active materials from aluminum foil.
trations of NaCl solutions and at different discharging times.
In this technique, LIBs are crushed and sieved to smaller sizes
They observed a 72% discharge efficiency with a 10 wt % NaCl
solution in 358 min. Lu et al.58 studied the effect of different then go through ultrasonic washing. This complete process is
NaCl solution concentration (1%, 5%, and 10%) for discharge continued at room temperature in a short duration of time and
of new batteries. At a high concentration of NaCl solution, the thus requires low energy consumptions, without noticeable
cell voltage was dropped significantly. Recently, Li et al.59 and environmental pollutions and with higher levels of operational
Ojanen et al.60 studied the cell discharge phenomenon by safety.
using sodium sulfate (Na2SO4) other than NaCl salt. The first 3.1.5. Heat-Treatment Method. The thermal treatment
work was reported on cell discharge by using sodium sulfate method is an important process to remove PVDF polymers
(Na2SO4) salt by Li et al. Ojanen et al. used different salts and carbon black from the cathode-active materials. In this
(NaCl, NaSO4, FeSO4, and ZnSO4) as aqueous electrolytes in process, the cathode is chopped into small pieces and then
“electrochemical discharge”. treated at high temperature in the furnace to complete the
3.1.2. Mechanical Separation (Dismantling and Separat- burn off of the carbon and organic polymers.40,74,75 In this
ing). After completely discharging, LIBs are manually process, high toxic gases and smoke are released due to the
dismantled to separate the cathode, anode, organic separator, combustion of carbon and organic polymers. To avoid the
steel, and plastic from the battery compartment. However, it is release of toxic gases during thermal treatment, many
very difficult to separate the different parts of LIBs manually, researchers76−78 have introduced vacuum pyrolysis for the
when considering large-scale recycling processes. Therefore, a separation of cathode-active materials. In the pyrolysis process,
mechanical process such as crushing, sieving, magnetic high molecular weight polymers degrade to low molecular
separation, and classification may be more economic from weight products, and then, the adhesion between the cathode
cost and effectiveness perspectives.4,61 Zhang et al.62 reported a materials and Al foil becomes weak, which subsequently helps
crushing method for pretreatment of spent LIBs. They separate cathode-active materials from Al foil. Yao et al.77 used
reported that aluminum foil, copper foil, and plastics were a vacuum furnace at 600 °C for 2 h to peel out the cathode-
removed as coarse particles from the ground parts and a active materials from aluminum foil. Sun et al.78 extracted
mixture of fine particles of graphite and LiCoO2 electrode cathode materials by a vacuum pyrolysis process in which
materials. Then, this mixture undergoes several steps to pressure was maintained at less than 1.0 kPa and the
recover the high-value elements such as cobalt and lithium. temperature at 600 °C. In this process, volatile gases and
3.1.3. Dissolution. Electrode materials are strongly adhered noncondensable gases were collected by a condenser and gas
to copper and aluminum current collector surfaces. The collector, respectively. After complete pyrolysis process, metal
cathode part is prepared with cathode-active materials, oxide (lithium cobalt oxide) was easily peeled from Al foil.
G https://doi.org/10.1021/acs.energyfuels.1c02489
Figure 4. Pyrometallurgical process flowchart of spent LIBs.
3.2. Pyrometallurgical Process. In this pyrometallurgical energy. Battery recycling using thermal treatment is mainly the
process, metal species like Co, Ni, and Cu are recovered from addition of reducing agents to spent battery materials in order
LIBs in the form of alloys, and Li, Al, Si, Ca, and Fe are formed to directly produce alloy and metal oxides.83 Further, the
as a slag.79,80 After the initial mechanical process like the decreasing content of Co in the lithium-ion batteries of EVs
dismantling of the battery pack, the batteries are directly makes pyrometallurgy less favored from the economic
processed in a high temperature smelting furnace without the perspective.84
need to separate cathode or anode layers, especially for the 3.3. Hydrometallurgical Process. Hydrometallurgical
small-sized batteries. This treatment goes through two different process have gained more interest in research and development
heat treatment processes. At low temperature treatment (150− in research institutes and industry due to high recovery rates of
500 °C), electrolytes and organic solvent are slowly removed Co, Ni, and Li (>98%), low energy consumption, greater
from the batteries, and in the second step, the batteries are selectivity, low impurities, and because it is relatively
subject to high temperature treatment (1400−1700 °C), which considered a low cost process at low production volumes.10
produces (Co, Ni, and Cu alloys) and slag (Li2O or Li2CO3). The acid leaching and solvent extraction process opened the
Figure 4 shows the pyrometallurgical process flowchart of eyes of many researchers to extract high purity cobalt from
spent lithium-ion batteries. LIBs at low cost and by using simple techniques. The
Today, a few companies such as Sony, Umicore, Accurec, hydrometallurgical technique deals with four different steps:
and Inmetco81,82 have adopted the thermal process to obtain (1) acid leaching, (2) chemical precipitation, (3) solvent
alloys and slag which go into further processing by hydro- extraction, and (4) electrochemical separation. Initially, the
metallurgical means. Pyrometallurgical or thermal processing cathode-active materials such as LiCoO2, LiNiO2, LiMn2O4,
approaches bring several advantages to the recycling system and LiNi0.33Mn0.33Co0.33O2 are dissolved by acid solutions, and
such as easier scalability and using fewer chemicals, and at the then, the process proceeds to extract Co, Li, Ni, and Mn metals
same time, there is lot of disadvantages associated with this from the solution by a suitable method. A hydrometallurgical
process such as failure to recycle materials in the electrolyte, process flowchart of spent LIBs and flow sheet for the recovery
the loss of valuable Li metal and graphite in the anode, of Co and Li from spent LIBs using D,L-malic acid as a leachant
emission of harmful gases, and also high consumption of are shown in Figure 5(a) and (b).
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Figure 5. (a) Hydrometallurgical process flowchart of spent LIBs. (b) Flow sheet for the recovery of Co and Li from spent Li-ion batteries using
85
D,L-malic acid as a leachant (Li et al., reproduced with permission).
3.3.1. Acid Leaching. Acid leaching is considered as one of complex on the surface of LiCoO2, and then, the leaching
the most effective and widely used methods to extract valuable product of the cobalt acid complex leaves the solid−liquid
metals from the spent LIBs. In the recent years, many interface by diffusion. Li et al.26 explained the leaching
researchers have worked on the acid leaching process to extract mechanism and morphology of the leaching process very
metal from spent LIBs using different inorganic acids like nicely. The leaching process goes through three steps which
HCl,86,87 HNO3,40 and H2SO4.81,88 Organic acids such as citric include particle loosening, breaking, and core shrinking. These
acid (C6H8O7),23,25 oxalic acid (H2C2O4),74,76 D,L-malic acid steps are diagrammatically presented in Figure 6(a). The
(C4H5O6),85,89 L-tartaric acid (C4H6O6),55,90 and mixed mechanisms of the leaching processes with the aid of SEM
acid91,92 have been also used to extract high-value metals (scanning electron microscope) analyses of both acetic acid
from spent LIBs. The details of the acid leaching process by and maleic acid are explained in Figure 6(b). The cathode-
using inorganic acid, organic acid, and mixed acid are discussed active materials appear as aggregated spherical particles before
extensively in the literature. A lot of work has been done in this the leaching process, but after few minutes, the large crystal
domain since the past decade which has been a landmark for particles start to loosen and break. The next sections
the recycling of LIBs.10 In acid leaching process, the leaching summarize the leaching process using inorganic, organic, and
efficiency of cobalt, lithium, nickel, and manganese depends on mixed acids.
the different parameters such as acid concentration, reducing 3.3.1.1. Inorganic Acid Leaching Process. Inorganic acids
agent concentration, reaction temperature, reaction time, and like sulfuric acid,78,88,93 hydrochloric acid,86,87 nitric acid,94
solid to liquid (S/L) ratio. In the leaching process, the phosphoric acid,95,96 and hydrofluoric acid97 as leaching
molecular structure of LiCoO2 is broken down in the presence reagents have been used and studied extensively in the
of an acid solution to form cobalt ion. This is a heterogeneous literature. These acids are strong acids which facilitate a fast
reaction where the reactant of acid initially is diffused to the leaching reaction and give high recovery rates of metals from
surface of LiCoO2 from the bulk phase to form a cobalt acid the spent LIBs. Inorganic acids are less costly, but they are also
I https://doi.org/10.1021/acs.energyfuels.1c02489
Figure 6. (a) Diagrammatic sketch of particle loosening, breaking, and core shrinking (reaction mechanism) in the leaching process. (b) SEM
images of residual powders in acetic acid and maleic acid leaching process after 1, 3, and 5 min reaction (Li et al., reproduced with permission).26
associated with some concerns about their environmental The following reactions summarize the reactions that involve
impacts. As an example, when HCl reacts with LiCoO2 during HCl and reducing agent (H2O2) with LiCoO2:
the leaching process, it produces Cl2 gas due to the oxidation
2LiCoO2 + 8HCl = 2CoCl 2 + Cl 2(g) + 2LiCl + 4H 2O
of HCl. Leaching agents such as H2SO4, HCl, HNO3, and
H3PO4 with reducing agents such as ethanol, hydrogen (oxidation of HCl, Cl 2 gas)
peroxide, sodium hydrogen sulfite, and glucose were used by
many researchers to enhance the leaching effi- 2LiCoO2 + 6H+ + H 2O2 = 2Co2 + + O2 + 2Li+
ciency.98,10,78,94,99−102 The main concern of the reducing + 4H 2O (divalent state of Co)
agent is to reduce the oxidation state of the metal and make it
Chen et al.103 reported recovery of valuable metals using
suitable to soluble in the acid solution. The metals like cobalt
leaching agent H2SO4 and reducing agent H2O2. They
and manganese immediately turn to the Co(III) and Mn(IV) reported high reaction yields of 98.5% for Co, 99.8% for Li,
oxidation states, which are difficult to dissolve in acid solution; 99.8% for Ni, and 98.6% for Mn. The leaching reaction
however, divalent states of Co(II) and Mn(II) are easily and solution was prepared using 2 M H2SO4, 10v% H2O2, and a
quickly soluble in acid solutions. liquid to solid mass ratio of 30 mL/g and maintained the
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Table 3. Summary of Some Research Results for Leaching of Spent LIBs in Inorganic Acids
Cathode materials Leaching agent + reducing agents T (°C) S/L ratio(g/L) Time (min) Leaching rate (%) Literature
LiCoO2 2 M H2SO4 + 10 vol % H2O2 70 30 60 98.5% Co Chen and Ho103
99.8% Li
LiCoO2 2 M H2SO4 + 5.0 vol % H2O2 80 50 60 >99% Co Sun and Qiu78
>99% Li
LiCoO2 2 M H2SO4 + H2O2 25 20 240 98.3% Co Takahashi et al.93
50 20 240 98.4% Co
LiCoO2 5 M HCl 95 10 70 ∼99% Co Guzolu et al.87
98% Li
LiCoO2 3 M HCl + 3.5v % H2O2 80 5 60 >89% Co Shuva and co-worker86
>89% Li
LiCoO2 1 M HNO3 + 1.7 vol % H2O2 75 10 30 ∼99% Co Lee and Rhee94
∼99% Li
LiCoO2 H3PO4 (2%v/v) + 2 vol % H2O2 60 8 90 99% Co Pinna et al.95
88% Li
LiCoO2 HF (15% (v/v)) 95 20 120 98% Co Suarez et al.97
80% Li
LiCoO2 2 M H2SO4 + 2.0 vol % H2O2 60 33 120 96.3% Co Zhu et al.104
87.5% Li
LiCoO2 2 M H2SO4 + 5.0 vol % H2O2 75 100 60 70.0% Co Jha et al.105
99.1% Li
LiCoO2 2 M H2SO4 + 8 vol % H2O2 75 50 60 98% Co Bertuol et al.106
LiCoO2 1 M H2SO4 95 50 240 66.2% Co Meshram et al.81
93.4% Li
LiCoO2 2 M H2SO4 + 6 vol % H2O2 60 100 60 98% Co Jingu et al.107
97% Li
LiCoO2 4.0 M HCl 80 − 120 99% Co Li et al.31
97% Li
LiCoO2 0.7 M H3PO4 + 4 vol % H2O2 40 50 60 99.7% Co Nayaka et al.108
99.9% Li
LiCoO2 6 vol % H2SO4 + 5 vol % H2O2 65 20 60 95% Li Dorella and Mansur34
80% Co
LiCoO2 2 M H2SO4 + 5 vol % H2O2 75 100 30 94% Li Swain et al.109
93% Co
leaching process at 70 °C for 120 min. Sun et al.78 recovered reducing agents to recycle the spent LIBs. The optimum
cobalt and lithium from spent LIBs by using both vacuum conditions for leaching of lithium and cobalt was found to be 3
pyrolysis and a hydrometallurgical technique. More than 99% M HCl, S/L ratio = 1:20 mg/mL, 80 °C, 60 min, and H2O2 3.5
of cobalt and lithium were recovered under experimental vol %. It is reported that 89% of Co and Li were leached at
conditions of 2 M H2SO4 at 80 °C and a solid/liquid ratio of optimized conditions. The dissolution efficiency of LiCoO2
50 g/L for 60 min. They also state that this technology is an increased with increasing the temperature, concentration of
environmental friendly process that is also cost competitive HCl, time, and solid/liquid (S/L) ratio. Lee and Rhee94
and feasible to be scaled up. Takahashi et al.93 reported all reported that the leaching efficiency increases with increasing
three steps such as grinding, leaching, and solvent extraction temperature and leaching agent HNO3 concentration, and Li
with different leaching agents such as H2SO4, HCl, and HNO3 and Co were leached with over 95% recovery rate with the
and reducing agent H2O2 to enhance cobalt recovery from addition of 1.7 vol % H2O2. The optimum condition to recover
LIBs. The reaction condition was maintained at pH 3−5, Co and Li was found to be 1 M HNO3, 10−20 g L−1 initial S/
temperature of 25 and 50 °C, time of 240 min, and a solid− L ratio, 75 °C temperature, and 1.7 vol % H2O2 addition. The
liquid ratio of 1/5. Recovery rates of 98.3% for Li and 98.4% dissolution process was explained on a reduction mechanism of
for Co were reported at pH 3, S/L = 1/5, and 25 and 50 °C. Co3+ to Co2+. They also calculated the activation energies of
The Co leaching efficiency was increased to 98.8% in the Co and Li and found them to be 12.5 and 11.4 kcal/mol,
oxidative medium. The energy consumption and pollution respectively. Pinna et al.95 studied the dissolution process of
during the recovery of Li and Co from spent LIBs were LiCoO2 metal oxide using phosphoric acid (H3PO4) and
reduced by ultrasonic washing, acid leaching, and the reducing agent hydrogen peroxide (H2O2). The optimum
precipitation method. Guzolu et al.87 recovered 98% of Li condition to recover Co and Li from spent LIBs was found to
and nearly 99% of Co under optimum conditions of a 5 M HCl be H3PO4 (2%v/v), H2O2 (2 vol %), solid−liquid (S/L) ratio
solution, temperature of 95 °C, reaction time of 70 min, and = 8 g/L, 90 °C, and 60 min. It was reported that 88% Li and
solid to liquid ratio S/L of 10 g/L. The precipitation reaction 99% Co were recovered due to efficient dissolution of LiCoO2
was conducted using NaOH at pH 12.5 for 1 h at 55 °C. It was to form high purity CoC2O4 and Li3PO4 as final products. The
found that Co and Li were recovered at rates that exceed 99%. effect of changing certain parameters such as reaction time,
Shuva and co-woker86 used HCl and H2O2 as leaching and leaching temperature, solid−liquid ratio, and concentrations of
K https://doi.org/10.1021/acs.energyfuels.1c02489
the leaching agent (H3PO4) and the reducing agent (H2O2) due to the low pH of the solution, the extraction of metal from
were discussed in this paper. They found that the dissolution of solution may be difficult in some cases. Environmentally
the sample increased with increasing phosphoric acid friendly and green recycling processes have been of great
concentration up to 2% (v/v), above which the LiCoO2 interest in the recent years.110 Organic acids such as citric
dissolution remains constant. Suarez et al.97 used hydrofluoric acid,59,69 malic acid,77 lactic acid,46 and maleic acid26 can be
(HF) acid leaching to recover Li and Co metals. The used as leaching or chelating agents and have similar leaching
dissolution parameters such as temperature, reaction time, efficiencies like inorganic acids/mineral acids. Today, organic
solid−liquid ratio, stirring speed, and concentration of HF acids play key roles in the leaching process due to
were studied in this experiment. The results indicated that an biodegradable properties, ease of processing, and since they
increase in the HF concentration, temperature, and reaction do not emit toxic gases. The leaching efficiency of the organic
time can favor the leaching reaction of the LiCoO2. The acids depends mainly on the acidic nature and unique chelating
recovery rates of Co and Li reached 98% and 80%, respectively. coordination properties. Acidity of the organic acid depends
The chemical behavior of the metal in different oxidation mainly on their functional groups and acid dissociation
states plays a major role in obtaining high purity cobalt and constant (pKa value).11
lithium products from the cathode material of LIBs. Zhu et Chen and co-workers111,112 and Horeh et al.113 reported the
al.104 separated cobalt and lithium by acid leaching cathode- advantages of organic acids such as being ecofriendly and
active materials in 2 M H2SO4 and H2O2 (2 vol %) and efficient leaching agents, no harmful gases emitted, and
precipitated as cobalt(II) oxalate dihydrate (CoC2O4·2H2O) recycling the remaining acid after the leaching process.
microparticles by addition of di-ammonium oxalate Additionally, Deng29 in his comparative study between organic
(NH4)2C2O4. Results showed that up to 96.3% of Co and and inorganic acids claimed that organic acids are thermally
87.5% of Li can be recovered in this process. Acid leaching stable, have no significant negative impacts on the environ-
with 2 M H2SO4 with the addition of 5 vol % H2O2 reducing ment, and are strong chelates, but they are considered weak
agent at a S/L ratio 100 g/L at 75 °C resulted in the recovery oxidants compared to inorganic acid. Li et al.,22 Fan et al.,23
of 99.1% lithium and 70.0% cobalt in 60 min as per the Chen et al.,24 and Zheng et al.25 revealed that organic acids
reported results by Jha et al.105 show the same leaching efficiency like inorganic acids and
Recently, researchers started to look at supercritical fluids for additionally are less harmful to the environment. This section
leaching cobalt. Bertuol et al.106 performed leaching tests with attempts to discuss the reported work on recycling processes
supercritical CO2 and cosolvents, as well as under conventional using organic acids as efficient leaching agents.
conditions. It was reported that more than 95% Co can be Citric Acid: Citric acid is a weak organic acid that is difficult
extracted using supercritical conditions with the reduction of to dissolve fully in water; thus, this may limit its leaching
reaction time. Meshram et al.81 recovered nickel and capabilities. The reaction between citric acid and LiCoO2
manganese along with lithium and cobalt by a sulfuric acid produce Co3+, which is very difficult to dissolve in water and
leaching process. Results showed that 93.4% Li, 66.2% Co, decrease the efficiency of the leaching process of cobalt metal.
96.3% Ni, and 50.2% Mn were recovered when the cathode- Therefore, many researchers22,25 used H2O2 as a reducing
active material was leached in 1 M H2SO4 at 95 °C and a 50 g/ agent with citric acid to form Co2+ ions in water, which can
L pulp density (S/L ratio) for 240 min. Kang et al.107 easily dissolve in water and increases the leaching efficiency.
recovered cobalt sulfate by reductive leaching and solvent Zheng et al.25 studied the leaching process using organic
extraction with Cyanex 272. Cobalt was reductively leached in citric acid and the kinetic process of cobalt leaching. The
60 min by stirring with 2 M H2SO4 and 6 vol % H2O2, at 60 °C leaching reaction was conducted using citric acid, water, spent
using a S/L ratio of 100 g/L. Here, 98% Co and 97% Li were LiCoO2 powder, and H2O2 solution in a reactor. Leaching
recovered using the above-mentioned optimal conditions. efficiency was investigated by changing certain parameters such
Recovering cobalt from spent LIBs can be done by a as the mole ratio of LiCoO2 to citric acid, H2O2 concentration,
combination of pretreatments such as crushing, ultrasonic solid-to-liquid ratio, temperature, and time. It was reported
washing, acid leaching, and precipitation to improve the that 99.07% of cobalt was recovered using citric acid (4M), S/
recovery efficiency and reduce energy consumption and V ratio of 15g/L, and H2O2 (1.0 vol %) in 5 h at 90 °C. They
pollution. For example, Li et al.31 used a combined recovery concluded that the leaching process using citric acid at 90 °C
process to recover Co metal from LIBs. They prepared a represents the optimum temperature for extraction of cobalt
leaching solution with 4 M HCl and continued the leaching and lithium from spent LIBs. The SEM analysis showed
reaction for 120 min at 80 °C. Results showed that 97% Li and irregular and agglomerated morphology of the spent LiCoO2.
99% Co can be recovered at these conditions. Nayaka et al.108 XRD analysis showed two different phases, LiCoO2 and
recovered the valuable metals using a sustainable recycling Co3O4, which indicates the decomposition of LiCoO2. Li et
process and mild phosphoric acid. It was reported that 99.7% al.22 also used citric acid and hydrogen peroxide as leaching
Co and 99.9% Li were recovered when the cathode-active and reducing agents, respectively, to recycle the lithium and
material was leached in 0.7 M H3PO4 and 4 vol % H2O2 at 40 cobalt from spent LIBs. In this work, both the mechanical
°C for 60 min. The leaching kinetics and activation energy separation process and acid leaching process were done
were calculated for Co and Li and estimated to be 7.3 and 10.2 consecutively to extract cobalt and lithium. The metal leaching
kJ/mol, respectively. Table 3 reports a few works on acid process was conducted by changing the citric acid concen-
leaching using inorganic acids as leaching agents. tration, S/L ratio, temperature, and H2O2 concentration. The
3.3.1.2. Organic Acid Leaching Process. Research has been results showed that up to 90% Co and 100% Li can be
diverted toward the organic acid leaching process due to the recovered by varying the concentration of citric acid, time, and
negative impact on the environment like generation of toxic temperature as well as the S/L ratio. The effect of temperature
gases such as CO2, SO2, Cl2, ethane, phosphorus, and NOx that and time on leaching efficiency of cobalt and lithium was
form during the inorganic acid leaching process. Additionally, studied at 1.25 M citric acid, 1.0 vol % hydrogen peroxide, and
L https://doi.org/10.1021/acs.energyfuels.1c02489
Figure 7. Effect of leaching temperature and leaching time on the leaching of waste LiCoO2 with 1.25 M citric acid (H2O2 = 1 vol %, S: L = 20 g
L−1 and agitation speed = 300 rpm). (a) Leaching efficiency of Co and (b) leaching efficiency of Li (Li et al., reproduced with permission).22 (c)
Systematic structure design of leaching reaction and possible complex formation during leaching process of metal in Citric acid solution (Meng et
al., reproduced with permission).114
a S/L of 20 g L−1. Figure 7(a) and (b) shows the increase of 100 °C, the efficiency of leaching Li and Co showed almost no
metal leaching efficiency with increasing temperature and time, change. This could be partially linked to the dissociation
but a significant effect was not observed after a 30 min reaction process of citric acid. It was observed that 100% Li and 90%
time. Results also indicate that cobalt (8%)/lithium (15%), Co were recycled from the spent LIBs using 1.25 M citric acid,
cobalt (74%)/lithium (84%), and cobalt (91%)/lithium (99%) 1.0 vol % hydrogen peroxide, and and a S/L ratio of 20 g/L at
were leached at 25, 80, and 90 °C, respectively. However, at 90 °C and for 30 min. Meng et al.114 reported a simple and
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Figure 8. (I) XRD patterns of (a) cathodic materials after calcination and grinding but before leaching and (b) black residues after leaching. (II)
Effect of reaction time and temperature on leaching efficiency of (a) Co and (b) Li. (III) Leaching reaction and possible reaction products in the
succinic acid leaching process (Li et al., reproduced with permission).9
economical leaching process to recycle the cathode materials alternative for metal leaching showed good results. A new
from industrial waste LIBs. The leaching experiment was green recycling process is now on demand to recycle cobalt
conducted using citric acid with the addition of reductants and lithium from the cathodes of spent batteries by using citric
H2O2 and ascorbic acid (AA). The concentration of citric acid acid as a leaching agent and also to study the photocatalytic
(0.25−2.0 mol/L), S/L ratio (20−100 g/L), reaction time (5− effect of synthesized Co3O4 and LiCoO2 mixtures. Santana et
180 min), and temperature (50−90 °C) were used in the al.116 used citric acid to develop an ecofriendly recycling route
recycling process. SEM and XRD were used to study the for spent LIBs. The main contribution is to produce valuable
morphology and crystal structure of leaching residues. The materials through an effective recycling process with photo-
leaching process and different complex structure formation at catalytic properties from spent Li-ion batteries without
the time of the citric acid reaction with different metals are disturbing the environment. A simple and efficient method
shown in Figure 7(c). Effects of temperature and time, acid was investigated by Yu et al.117 to recover the valuable
concentration, S/L ratio, H2O2 concentration, and ascorbic cathode-active materials from spent LIBs by a direct leaching
acid during leaching process are well described in this paper. In process in citric acid solution without a pretreatment process.
addition, the kinetic study was performed to understand the This work discussed the effect of citric acid concentration,
relationship between the metal leaching and leaching H2O2 concentration, reaction temperature, reaction time and
parameters. Authors were able to recover 91.0% of Li, 90.9% solid-to-liquid ratio on the leaching efficiency. It was observed
of Co, 94.1% of Ni, 88.6% of Mn, 19.5% of Cu, and 26.9% of that about 99% of Co and 99% of Li were recovered using 1 M
Al using citric acid (0.5M) and a S/L ratio of 80 g/L at 90 °C citric acid in the presence of 8 vol % H2O2 and 40 g/L S/L
in 80 min without reductant. They also found that there was ratio in 70 min at 70 °C. The results showed that the leaching
no significant increase in the metal leaching efficiency by efficiency increased substantially when the citric acid
addition of H2O2. concentration increased from 0.1 to 1.0 M and immediately
Almeida et al.115 used citric acid (2M) as leaching agents declined after reaching 2M. Further, the authors also noticed
and H2O2 (0.25M) to evaluate the chemical composition in that the leaching efficiency increased with the increasing
cathode-active materials of different spent Li-ion batteries. The concentration of the hydrogen peroxide, reaction temperature,
use of 2.0 mol L−1 citric acid as an environmentally friendly solid−liquid ratio, and reaction time. Aaltonen et al.118
N https://doi.org/10.1021/acs.energyfuels.1c02489
Figure 9. (a) Possible products of leaching reaction of waste LiCoO2 with ascorbic acid (Li et al. ,reproduced with permission).67 (b) Possible
products observed during leaching reaction of LiCoO2 with citric acid (C6H8O7), D,L-malic acid (C4H6O5), and L-aspartic acid (Li et al.,
reproduced with permission).123 (c) Possible complexation of Li and Co with IDA and MA during dissolution (Nayaka et al., reproduced with
permission.)108 (d) Possible leaching process of LiCoO2 materials in glucose and phosphoric acid solution (Meng et al., reproduced with
permission).125 (I) SEM micrographs of (a) dismantled cathode material from spent LIBs and (b) leach residues, (Li et al., reproduced with
permission).67 (II) SEM images of different cathode materials: (a) dismantled cathodic material from a spent LIB, (b) cathodic material after
treatment with NMP, (c) cathodic material after dismantling and calcination at 700 °C for 5 h, and (d) leach residues (Li et al., reproduced with
permission).85 (III) Possible multiphase reaction of the D,L-malic acid acid solution and LiCoO2 particles (Li et al., reproduced with permission).85
(IV) Possible multiphase leaching reaction of LiCoO2 particles and organic acid solutions (Li et al., reproduced with permission).123
O https://doi.org/10.1021/acs.energyfuels.1c02489
investigated leaching process at room temperature using citric and a solid-to-liquid ratio of 25 g L−1. They proposed this
acid (1M) and 1 vol % H2O2, with 50 g/L pulp density in 24 h. reaction method which can be scaled up at industrial scale to
This process allows for recovery up to 97% of Co, 89% of Li, recycle Co and Li from spent LIBs. The detailed structural
98% of Mn, and 93% of Ni. information, reaction mechanism, and possible structure
Citric acid is an excellent acid for selective metal dissolution formation of the leaching product are presented theoretically
compared to sulfuric acid. Ma et al.119 observed from the and thermodynamically in Figure 9(a). The valuable
experiment they conducted on spent LIBs that the citric acid information was observed in the morphology analysis (SEM
with reducing agent H2O2 shows a significant Co and Ni metal images, Figure 9(I(a, b)). Xu et al.121 predicted product (b) in
leaching process but slows dissolution of other metals such as Figure 9(I), i.e., C6H6O6Co which is more stable during
Mn, Fe, and Zn. Musariri et al.120 studied a 1−1.5 M citric acid leaching process. The leaching reaction is as follows:
solution for the leaching process to recover lithium, cobalt, and
nickel from LIBs. The increase of citric acid concentration 4C6H8O6 + 2LiCoO2 = C6H6O6 + C6H6O6 Li 2
from 1 to 1.5 M strongly influences the metal leaching rate. It + 2C6H6O6 Co + 4H 2O (1)
was reported that 98% of Co, 96% of Li, and 99% of Ni were
recovered using 1.5 M citric acid and 2 vol % H2O2 at 95 °C in It was reported that 94.8% Co and 98.5% Li were recovered
30 min. Fan et al.23 reported an economical and environ- by using 1.25 M ascorbic acid concentration with a S/L ratio of
mentally friendly leaching process using 1.25 M citric acid and 25 g/L at 70 °C for 20 min. Additionally, it was reported that
1 vol % H2O2 solution to recover metals from LiCoO2 the efficiency of the acid leaching process was affected by
cathode-active materials. Nearly 90.2% and 98% recovery several factors, such as leaching temperature and time, acid
rates for Co and Li, respectively, were achieved using citric acid concentration, and S/L ratio.121
(1.25 M) and 0.9 vol % H2O2, with a 60 g L−1 S/L ratio in 35 D,L-Malic Acid (C4H6O5)/Oxalic Acid (C2H2O4): Many
min at 90 °C. researchers have reported a leaching process using oxalic acid
Succinic Acid: Succinic acid, a natural weak organic acid, and D,L-malic acid due to their strong acidity and reducibility
has been used for recycling of Co and Li metals from LIBs due properties. de Oliveira Demarco et al.50 focused on an
to low energy consumption, no air emissions, complete ecofriendly and effective leaching process using three organic
recovery of valuable components with high purity, and for acids such as malic acid, citric acid, and formic acid at
being among the most cost-effective leaching processes. Li et concentrations of 2 M to recover cobalt, lithium, and
al.9 discussed the recycling process of valuable Co and Li manganese metals from spent LIBs. They used mechanical,
metals from LIBs using succinic acid as a leaching agent and thermal, and leaching processes in their experiment. They
H2O2 as a reducing agent. After several trials, the experiment carried out several experimental conditions, but the effective
was conducted under optimal conditions, 1.5 M succinic acid, one was D,L-malic acid (2M), 6 vol % H2O2, S/L ratio 20 g/L,
4 vol % H2O2, and a 15 g/L S/L ratio at 70 °C for 40 min. The 95 °C, and reaction time of 60 min. In this condition, Co
morphology and structural integrities of the cathode-active (90.57%), Li (93.22%), and Mn (99.53%) were recovered.
materials before and after the leaching experiment were well Additionally, citric acid and formic acid showed good leaching
reported in Figure 8(I). Leaching efficiencies of cobalt and efficiencies at 65 °C. Li et al.85 used a biodegradable,
lithium were studied with the increase in temperature and time environmental friendly, and efficient leaching agent (D,L-
and showed remarkable leaching of Co and Li in succinic acid malic acid) to recover Co and Li from spent LIBs. The
(1.5M), S/L of 15g/L, and H2O2 (4 vol %) at 70 °C. The leaching process was conducted under variable conditions and
graph (Figure 8(II(a, b)) indicates that the Co and Li leaching different concentrations of D,L-malic acid (0.5−3.0 M), H2O2
efficiencies reached 82.27% and 80.55%, respectively, at 50 °C (0−2.5 vol %), solid/liquid ratio (33−17 g/L), temperature
and 10 min and further increased to 99.83% and 94.65% for (20−100 °C), and reaction time (10−50 min). They
cobalt and lithium, respectively, with increasing temperature concluded that more than 90% of Co and nearly 100% Li
and time (70 °C for 40 min), and finally maintained a can be recovered at 1.5 M D,L-malic acid, 2.0 vol % hydrogen
negligible change with further increases in the reaction time. peroxide, a leaching temperature of 90 °C, a S/L ratio of 20 g
The stepwise leaching reaction of LiCoO2 in succinic acid L−1, and a time interval of 40 min. Different steps involved in
leachant is shown in Figure 8(III). They identified theoretically the recycling process, morphology of cathode materials before
two possible leaching products containing Co(II) that was and after leaching, and reaction mechanism between LiCoO2
C4H4O4Co and C8H10O8Co. However, Xu et al.121 and Li et and D,L-malic acid are presented in Figure 9(II) and (III).
al.67 reported thermodynamic calculations of the leaching Sun et al.76 reported vacuum pyrolysis, oxalate leaching, and
product and showed that C4H4O4Co is the only product that a precipitation process to recover Co and Li and reported that
forms during the leaching reaction. They further explained the this process is environmentally friendly. They used oxalate as
nature of the reaction of the symmetrical structure of the leaching reagent and precipitant which leaches and
C4H4O4Co; this molecule is more stable and easier to precipitates cobalt from LiCoO2 and CoO directly as
generate, which leads to the increase in the leaching efficiency. CoC2O4·2H2O. The optimal condition was achieved with 1.0
Ascorbic Acid: Ascorbic acid can act as both leaching agent M oxalate solution, a S/L ratio 50 g/L, temperature of 80 °C,
and reducing agent at the same time to dissolve metals and and leaching time of 120 min. The authors reported that more
reduce high-valent metals like Co(IIII) to Co(II) oxidation than 98% of LiCoO2 was obtained under this optimum
states. Li et al.67 executed a recycling process using a condition.
combination of ultrasonic washing, calcination, and ascorbic Most of the organic acids present a similar reaction
acid leaching. Cobalt and lithium recovery efficiency was mechanism to citric acid, but oxalic acid follows a different
improved substantially using organic acid and a reducing agent. reaction mechanism. Due to the complication in the
The leaching reaction was conducted under a condition of conventional process combined with leaching, precipitating,
ascorbic acid (1.25M), temperature of 70 °C, time of 20 min, and filtering to recover cobalt and lithium from spent LIBs,
P https://doi.org/10.1021/acs.energyfuels.1c02489
Table 4. Summary of Some Research Results for Leaching of Spent LIBs Using Organic Acids
Cathode T S/L ratio Time Leaching rate
materials Leaching agent (°C) (g/L) (min) (%) Literature
LiCoO2 4 M citric acid +1 vol % H2O2 90 15 300 99% Co Zheng et al.25
LiCoO2 1.25 M citric acid +1 vol % H2O2 90 20 30 90% Co Li et al.22
100% Li
LiNiCoMnO2 0.5 M citric acid 90 80 80 90.9% Co Meng et al.114
91.0% Li
LiCoO2 2 M citric acid + 0.25 M H2O2 80 20 120 ∼99% Co Almeida et al.115
∼99% Li
LiCoO2 1 M citric acid + 8 vol % H2O2 70 40 70 99% Co Yu et al.117
99% Li
LiCoO2 1 M citric acid +1 vol % H2O2 RT 50 1440 97% Co Aaltonen et al.118
89% Li
LiCoO2 1.5 M citric acid + 2 vol % H2O2 95 − 30 98% Co Musariri et al.120
96% Li
LiCoO2 1.25 M citric acid + 0.9 vol % H2O2 90 60 35 90.2% Co Fan et al.23
98% Li
LiCoO2 1.5 M succinic acid + 4 vol % H2O2 70 15 40 100% Co Li et al.9
<96% Li
LiCoO2 1.25 M ascorbic acid 70 25 20 94.8% Co Li et al.67
98.5% Li
LiCoO2 1.5 M D,L-malic acid (C4H5O6) + 2 vol % H2O2 90 20 40 <90% Co Li et al.85
∼100% Li
LiCoO2 2 M D,L-malic acid + 6 vol % H2O2 95 20 60 90.5% Co de Oliveira Demarco et al.50
93.2% Li
LiCoO2 1.5 M oxalate + H2O2 80 50 120 <98% Co Sun and Qiu76
<98% Li
LiCoO2 1.0 M oxalate 95 15 150 97% Co Zeng and Shen74
98% Li
LiCoO2 2 M citric acid + 1.25 vol % H2O2 60 30 120 81.5% Co Golmohammadzadeh et al.122
92.5% Li
LiCoO2 2 M citric acid + 1.25 vol % H2O2 60 30 300 96.4% Co Golmohammadzadeh et al.122
99.8% Li
Zeng et al.74 proposed a novel recovery process, only constant in all leaching media. The ultrasonic-assisted leaching
combined with oxalic acid leaching and filtering. The oxalic process with organic acid was adopted to increase the
acid was used as the reductant and leachant, and the leaching effectiveness of the process and to mimic the friendly nature
efficiencies of Co and Li were achieved at 97% and 98%, of the leaching environment. They used both inorganic and
respectively. The reaction mechanism is described as organic acids such as sulfuric acid, hydrochloric acid, and citric
acid along with H2O2 as a reducing agent in the leaching
4H 2C2O4 + 2LiCoO2 → CoC2O4 ↓ + LiHC2O4
process. It was reported that leaching of Co and Li is more
+ 2CO2 ↑ +4H 2O (2) efficient with organic acid (citric acid) than inorganic acid
(H2SO4, HCl). More than 96% of Co and nearly 100% Li were
The optimal condition for leaching process is controlled at recovered in citric acid leaching condition, whereas less than
150 min, 95 °C temperature, 15 g/L solid/liquid ratio, and 400 80% Co was recovered in inorganic acid leaching condition.
rpm rotational speed. Golmohammadzadeh et al.122 studied However, Li leaching was maintained above 90% with
four different organic acids (D,L-malic, oxalic, citric, and acetic
inorganic acids. The optimal citric acid leaching condition
acids) and found that the best sequence is citric acid > D,L-
was 0.5 M citric acid with 0.55 M H2O2, solid-to-liquid ratio of
malic > acetic > oxalic acid in terms of their efficiency to
recover Co and Li from spent LIBs. They reported that 81.5% 25 g/L, temperature of 60 °C, leaching time of 5 h, and
of Co and 92.5% of Li were recovered at the optimum leaching ultrasonic power of 90 W. The high leaching efficiency was
condition of 60 °C, S/L 30 g/L, 2 M citric acid concentration, observed in the citric acid optimal condition, and ultrasonic-
1.25 vol % H2O2 concentration, and 120 min leaching time. assisted technology could be due to the unique cavitation
Furthermore, ultrasonic agitation enhanced the recovery of Li action of the ultrasonic waves. Using citric acid, malic acid, and
and Co. These recovery rates can be increased to 96.4% for Co aspartic acid along with H2O2 reducing agent to recover Co
and 99.8% for Li when the leaching time increased to 300 min, and Li from spent LIBs was reported by Li et al.123 XRD
while maintaining the other conditions at their levels discussed diffraction and SEM were used to analyze the complete
above. Table 4 reports few works on acid leaching using structure and morphology of leaching materials. They varied
organic acid as leaching agents. the parameters such as temperature, time, leachant, H2O2
3.3.1.3. Mixed Acid Leaching Process. Li et al.68 reported concentrations, and S/L ratio to understand the Co and Li
that the leaching efficiency of Co in citric acid is higher than optimal recovery conditions. It was reported that citric acid
HCl and H2SO4, and the leaching efficiency of Li is almost and malic acid showed leaching efficiency of 90% for Co and
Q https://doi.org/10.1021/acs.energyfuels.1c02489
Table 5. Summary of Some Research Results for the Leaching of Spent LIBs in Mixed Acids
Cathode T S/L ratio (g/ Time Leaching rate
materials Leaching agent (°C) L) (min) (%) Literature
LiCoO2 0.5 M H2SO4 + 0.55 M H2O2 60 25 300 47.6% Co Li et al.68
97.2% Li
LiCoO2 0.5 M HCl 60 25 300 76.4% Co Li et al.68
95% Li
LiNiCoMnO2 0.5 M citric acid + 0.55 M H2O2 60 25 300 96.1% Co Li et al.68
98.4% Li
LiCoO2 0.1 M citric acid + 0.02 M ascorbic acid 80 − 360 80% Co Nayaka et al.92
100% Li
LiCoO2 0.4 M tartaric acid + 0.02 M ascorbic acid 80 − 300 97% Co Nayaka et al.91
100% Li
LiCoO2 0.1 M iminodiacetic acid + 0.02 M maleic acid + ascorbic acid 80 − 360 91% Co Nayaka et al.108
99% Li
LiCoO2 0.5 M glycine + 0.02 M ascorbic acid 80 − 360 95% Co Nayaka et al.124
LiCoO2 (0.5−2.0 M) citric acid/malic acid/aspartic acid + (1.0−6.0) vol % 90 20 30 100% Li Li et al.123
H2O2
90% Co
LiCoO2 3 M H2SO4 + 0.4 g/g cellulose 95 25 120 54% Co Chen et al.88
100% Li
LiCoO2 3 M H2SO4 + 0.4 g/g sucrose 95 25 120 96% Co Chen et al.88
100% Li
LiCoO2 3 M H2SO4 + 0.4 g/g glucose 95 25 120 98% Co Chen et al.88
96% Li
LiCoO2 1 M tartaric acid + 30 g/L ascorbic acid 80 − 90 84.3% Li Cheng et al.90
47.3% Co
LiCoO2 1 M tartaric acid with 20 g/L glucose 80 − 90 82.7% Li Cheng et al.90
46.6% Co
LiCoO2 1.5 M phosphoric acid + 0.02 M glucose 80 − 120 Co: 98% Meng et al.125
∼100% Li
LiCoO2 1.5 M H2SO4 + 30% H2O2/glutaric acid 90 10 120 87.85% Co Urbanska.126
99.91% Li
1.46% Ni
Li, whereas aspartic acid showed low recovery efficiency. The Nayaka et al.,108 where they used iminodiacetic acid (IDA) and
mechanism of the leaching process initiates, in conjunction maleic acid (MA) and organic acid with a reducing agent
with the dissolution of LiCoO2, an active material in the (ascorbic acid) to recover Co and Li metals from LIBs. They
presence of H2O2 followed by chelation of Co(II) and Li with also found similar observations like those they got in their
organic acids. The reduction reaction of Co(III) to Co(II), previous work,91,92 where 100% lithium and less than 95% Co
dissolution of spent LiCoO2, and chelation reaction of CO+2 dissolution occurred at 80 °C in 6 h. In their articles, Nayaka et
and Li with citrate, malate, and aspartate are shown in Figure al.108 discussed the reductive complexing dissolution mecha-
9(IV) The possible products were observed during the nism. Figure 9(c) shows the possible complex formation in
leaching reaction of LiCoO2 with citric acid (C6H8O7), and cobalt and lithium with iminodiacetic acid (IDA) and maleic
D,L-malic acid (C4H6O5) and L-aspartic acid are reported in acid (MA). Nayaka et al.124 introduced a mixture of glycine
Figure 9(b). They found that 90% of Co and nearly 100% of Li and ascorbic acid as leaching regents and observed effective Co
were recovered in 1.25 M citric acid, 1 vol % H2O2, and a 20 g/ recovery when both glycine and ascorbic acid were used. They
L S/L ratio in 30 min at 90 °C experimental conditions. recovered more than 95% Co by varying the concentration of
Nayaka et al.92 reported 100% lithium and 80% cobalt leachant and reaction time. According to the findings of this
dissolution of LiCoO2 using a mixture of citric acid and study, the optimal condition for highly efficient recovery of Co
ascorbic acid at 80 °C for 6 h. The experiment was conducted was achieved with 0.5 M glycine and 0.02 M ascorbic acid in 6
using citric acid as the chelating agent and ascorbic acid as the h at 80 °C. Many studies have been reported since the past
reducing agent. Another work was presented by Nayaka et al.91 decade on leaching of LiCoO2 cathode-active materials using
where they used a tartaric acid and ascorbic acid mixture for mild organic acids such as citric acid, malic acid, oxalic acid,
leaching process. Experiment was conducted using different aspartic acid, and succinic acid with hydrogen peroxide as the
concentrations of tartaric acid (0.1−0.5M) with constant reducing agent, and we arranged a complete reported work in
concentration of ascorbic acid (0.02M). The experiment organic acid and mixed acid sections. Environmentally friendly
condition was maintained at 80 °C for a duration of 5 h, and satisfactory results were observed using these mild organic
and samples were collected at different time periods to study acids. Many researchers used hydrogen peroxide as a reducing
the leaching percentage of cathode-active materials (LiCoO2). agent to improve the leaching efficiency. However, hydrogen
It was reported that more than 95% dissolution occurred by peroxide is unstable in the acid leaching process; hence, it is
using a 0.4 M tartaric acid and 0.02 M ascorbic acid mixture at important and essential to find an efficient and stable
80 °C in 5 h. Recently, one more work was published from alternative to hydrogen peroxide. Meshram et al.99 and Nayaka
R https://doi.org/10.1021/acs.energyfuels.1c02489
et al.124 recently used sodium hydrogen sulfite and an ascorbic Mishra et al.135 investigated a bioleaching method to recycle
acid reducing agent as alternatives for hydrogen peroxide. Co and Li from spent LIBs using chemolithotrophic and
Meng et al.125 recently focused on glucose as a reducing agent acidophilic bacteria and Acidithiobacillus ferrooxidans. Elemen-
in the leaching process of cathode-active material with tal sulfur and ferrous ions were utilized to produce metabolites
phosphoric acid. During the leaching process, glucose can be like H2SO4 and ferric ions in the leaching medium to improve
successively oxidized and decomposed with the formation of the efficiency. The formation of metabolites in the leaching
monocarboxylic acids, including gluconic acid, tartaric acid, medium helps dissolve LiCoO2 metal oxide. It is reported that
oxalic acid, and formic acid. A possible leaching process of a culture of A. ferrooxidans can produce H2SO4 to leach some
LiCoO2 materials in the glucose and phosphoric acid solution metals indirectly from LIBs andCo was leached faster than
are shown in Figure 9(d). Meng et al.125 reported that about Li.135 Xin et al.136 reported the different mechanisms for
98% Co and nearly 100% Li were leached in 1.5 M phosphoric bioleaching of LiCoO2 electrodes. The mechanism of Li and
acid and 0.02 M glucose at 80 °C in 2 h. Co dissolution in three different energy materials systems such
Chen et al.88 investigated the leaching efficiency of Co and as elemental sulfur (S), pyrite (FeS2), and a S + FeS2 mixed
Li using three different leaching systems: sulfuric acid + system are presented in the reactions below:
glucose, sulfuric acid + sucrose, and sulfuric acid + cellulose. Li dissolution in Sulfur system:
H2SO4 + glucose leaching system: 98% Co and 96% Li were S + 1.5O2 + H 2O = H 2SO4 (microbial action) (3)
leached in H2SO4 (3 M), 0.4 g/g glucose, and a 25g/L S/L
ratio in 120 min at 95 °C. H2SO4 + sucrose leaching system: Co dissolution in S + FeS2 mixed system:
96% Co and 100% Li were leached in H2SO4 (3 M), 0.4 g/g
sucrose, and a 25g/L S/L ratio in 120 min at 95 °C. H2SO4 + FeS2 + 5O2 + 4H+
cellulose leaching system: 54% Co and 100% Li were leached = Fe3 + + 2SO4 2 − + 2H 2O (microbial action) (4)
in H2SO4 (3 M), 0.4 g/g glucose and a 25g/L S/L ratio in 120
min at 95 °C. In a similar work, Cheng et al.90 prepared a FeS2 + Fe2(SO4 )3 = 3FeSO4 + 2S (chemical action) (5)
leaching solution using tartaric acid and three different
reducing agents ((glucose, ascorbic acid, and hydrogen FeS2 + 7Fe2(SO4 )3 + 8H 2O
peroxide) to recover lithium and cobalt from LIBs. They
studied the leaching efficiency of cathode-active materials using = 15FeSO4 + 8H 2SO4 (chemical action) (6)
different reducing agents with one leaching agent (tartaric
acid). They calculated that 82.4% of Li and 53.2% of Co were 2Fe2 + + 0.5O2 + 2H+ = 2Fe3 + + H 2O (microbial action)
recovered using 1 M tartaric acid with 10% H2O2 at 80 °C in (7)
90 min, and 84.3% of Li and 47.3% of Co were recovered using
1 M tartaric acid with 30g/L ascorbic acid at 80 °C in 90 min. S + 3Fe2(SO4 )3 + 4H 2O
Also, 82.7% of Li and 46.6% of Co were recovered using 1 M = 4H 2SO4 + 6FeSO4 (chemical action) (8)
tartaric acid with 20 g/L glucose at 80 °C in 90 min.
Urbanska126 recovered Co, Li, and Ni from spent LIBs using 2FeSO4 + 2LiCoO2 + 4H 2SO4 = Fe2(SO4 )3
organic and inorganic reducing agents such as H2O2 and
glutaric acid with 1.5 M sulfuric acid as the leaching agent. The + 2CoSO4 + Li 2SO4 + 4H 2O (chemical action) (9)
recovery rates of Co, Li, and Ni in both reducing agents were
analyzed. They found that the highest recovery degrees of the The authors claimed that bioleaching of Li occurs due to
investigated metals (Co, 87.85%; Li, 99.91%; Ni, 91.46%) were biogeneration of H2SO4, whereas Co dissolution is due to acid
obtained in the presence of both H2O2 and glutaric acid leaching and redox reactions involving iron and sulfur. In the
(C5H8O4) reducing agents. Natarajan et al.127 recovered presence of iron and sulfur, the metabolism of the energy
valuable metals such as Li, Co, and Mn by using acetic acid source generates H2SO4 and Fe3+ that cause direct acid
(CH3COOH) and water as lixiviants. The leaching reaction dissolution of Co2+ and redox reactions leading to the
was conducted using 3 M acetic acid and 7.5 vol % H2O2 at formation of Fe2+ which promotes the reduction dissolution
70 °C and a pulp density of 20 g/L for 40 min to recover of insoluble Co3+. Recently, some researchers started to
99.9% Li, 98.7% Co, and 99.5% Mn from the spent LIBs. In improve the bioleaching efficiency using copper ions and silver
summary, the dissolutions of LiCoO2 in different mixed acids ions as catalysts. Zeng et al.137 reported a bioleaching process
are reported in Table 5. by Acidithiobacillus ferrooxidans using copper ions and silver138
3.3.1.4. Bioleaching Process. Apart from direct acid ions as a catalyst. They observed 99.9% and 98.4% of Co
leaching, bioleaching is an interesting process to recover dissolution at a copper concentration of 0.75 g/L after 6 days
valuable cathode-active materials from spent LIBs. In this and Ag+ concentration of 0.02 g L−1 after 7 days, respectively.
process, metabolic products such as inorganic acids and The catalytic mechanism of the copper ion is reported in eqs
organic acids were released by microbial activities that are 10 and 11 and the reducing effect of iron ion in eq 12
involved in the leaching process. The leaching process can Cu 2 + + 2LiCoO2 = CuCo2O4 + 2Li+ (10)
proceed through mineral acid and organic acid depending on
the ability of bacteria and fungi. Some bacteria possess the CuCo2O4 + 6Fe3 + = 6Fe 2 + + Cu 2 + + 2O2 + 2Co2 +
ability to produce inorganic acids, and some types of fungi bacteria
metabolites can produce organic acids that promote leaching (11)
processes.128−131 Brandl and Faramarzi,132 Rohwerder et al,.133 4Fe 2+ + +
+ O2 + 4H → 4Fe3 + 2H 2O (12)
and Cerruti et al.134 reported that bioleaching processes have
gradually replaced hydrometallurgical recycling due to their Aspergillus niger fungus produces organic acid metabolites
higher efficiency, lower costs, and few industrial requirements. such as oxalic acid, citric acid, tartaric acid, and malic acid to
S https://doi.org/10.1021/acs.energyfuels.1c02489
dissolve metals from spent LIBs. Bahaloo Horeh et al.113 used

Aspergillus niger for the bioleaching process of spent LIBs
which helps secrete organic acid metabolites such as malic,
gluconic, oxalic, and citric acids. Citric acid was found to be an
effective metabolite in bioleaching process. Here, 95% of Li
and 45% of Co were recovered at a pulp density of 1% in a
spent medium bioleaching for 16 days. The industrial
application of the bioleaching process is really difficult and
also not satisfactory due to the slow leaching process, longer
treatment period, slow microbial culturing, and use of low
concentrations of metal ions, although it has considerable
advantages in terms of energy savings and environmental
protection.10
3.3.2. Solvent Extraction. Solvent extraction is a liquid−
liquid extraction method, where two immiscible liquids are
separated from each other. Solvent extraction is used to
recover Co, Li, and Cu from spent LIBs after the leaching
process of cathode-active materials. Here, di-(2-ethylhexyl)
phosphoric acid (D2EHPA), bis(2,4,4-trimethyl-pentyl) phos- Figure 10. Effect of suitable pH on the solvent extraction of different
phinic acid (Cyanex 272), trioctylamine (TOA), diethylhexyl extraction reagents (Lv et al., reproduced with permission).15
phosphoric acid (DEHPA), or 2-ethylhexyl phosphonic acid
mono-2-ethylhexyl ester (PC-88A) were used as extractants in from a sulfuric acid leaching solution. Extraction of Co2+,
the hydrometallurgy recycling process. This process recovered Mn2+, and Li+ follows the order as Mn > Co≫ Li, which is also
high percentages and high purities cobalt, nickel, lithium, and independent of taking the single Cyanex272 or PC-88A or
copper metals at easy operational conditions and low energy their mixtures as extractants. The possible extracted species
consumption. Cyanex272 is an excellent selective agent in MA2·3HA or M (OH) A·3HA for a single extractant (PC-88A
extracting Co; therefore, it has been widely investigated as an and Cyanex272 are same) and MH3A2L3 for the mixed
extractant for valuable materials in the LIBs. Swain et al.109 extractant (M2+ is Co2+ or Mn2+) and synergistic effect of
used Cyanex 272 as an extractant with 5 vol % tributyl Cyanex272 + PC-88A were reported.
phosphate (TBP) as a phase modifier and kerosene as a diluent Granata et al.142 and Zhao et al.147 presented extraction
and reported 85.42% Co extraction at pH 5. A similar type of mechanism as follows
work was reported by Jha et al.,139 where they used Cyanex
2+
272 as an extractant and isodecanol as a phase modifier. They M(Aq) + A −Org + 2(HA)2Org → MA 2·3HA Org + H+Aq
got 99.9% Co extraction efficiency at pH 5. For example, (13)
copper and manganese ions are extracted in good amounts
or
using di(2-ethylhexyl) phosphoric acid (D2EHPA) and
extractant, but its selectivity in extracting Co is poor at pH 2(HA)2Org + MOH+Aq + A −Org → M(OH)A·3HA (Org)
2.2−3.0.140 Joo et al.141 reported that the extraction efficiency
of Co with cationic extractant D2EHPA was improved with + H+Aq (14)
increasing pH of leachate. Kang et al.107 reported reductive ̅
leaching and solvent extraction with Cyanex 272 to extract Co Where, AOrg+ 2(HA) 2 Org represents the saponification
from the spent LIBs. They initially precipitated the metal ion reaction as
impurities (copper, iron, and aluminum) to hydroxide form by Na +Aq +1/2 (HA)2Org → NaA Org + H+Aq (15)
adjusting the pH (6.5) and then extracted Co from the purified
aqueous phase by equilibrating with 50% saponified 0.4 M At the same time, the solvent extraction process has some
Cyanex 272 at pH ∼ 6. Granata et al.142 used 2 g/g of H2SO4 limitations due to the high cost of the extractants, which can
and glucose as a reducing agent (excess of 50%) to perform the increase the treatment cost when it is scaled up in industry.
leaching process. Iron, aluminum, and copper (partially) were Therefore, choosing appropriate and cheap solvent extractants
removed by precipitation as hydroxides at pH 5.0. Solvent is a major challenge that R&D has to overcome to decrease the
extraction and crystallization methods were used to recover Co recycling cost.
and Li. The suitable scales of pH of different extraction 3.3.3. Chemical Precipitation. Chemical precipitation is a
reagents are summarized in Figure 10.141,143−146 Cynaex 272 simple and effective process to recover metals from spent LIBs
and P507 present good choices to separate Co and Ni at a pH rather than the solvent extraction method. This gives a high
range between 3 and 5 to avoid the corrosion of the reactors. purity product with low recycling cost if appropriate chemical
The additive can change the optimal pH of solvent extraction, precipitation agents are selected. This is based on the different
which was reported and explained in Figure 10 by Joo et al.141 solubilities of metal compounds at certain solution pH. Metal
The pH reduced to 3.5−4 when only PC-88A was used to ion impurities and transition metals precipitate at low and high
extract Co, but after addition of the phase modifier pH, respectively. Contestabile et al.148 reported the recycling
trioctylamine (TOA), the pH scale shifted between 3.5 and 5. of cathode-active materials from spent LIBs using manual
Zhao et al.147 used a mixture of bis(2,4,4-trimethylpentyl) separation, acid leaching, and cobalt hydroxide precipitation
phosphinic acid (Cyanex272, HA) and 2-ethylhexyl phosphinic processes. The dissolution process of cathode-active materials
acid mono-2-ethylhexyl ester (PC-88A, HL) in n-heptane to (LiCoO2) was conducted by using 4 M HCl at 80 °C for 1 h.
extract and separate cobalt(II), manganese(II), and lithium(I) Precipitation agents such as NaOH were used to precipitate
T https://doi.org/10.1021/acs.energyfuels.1c02489
precious cobalt metal to cobalt(II) hydroxide (Co(OH)2). In impurities, but too much electric energy is needed in this
this work, Co (OH) 2 was recovered from an acid leaching recycling method.
solution by addition of 4 M NaOH solution. The authors also Myoung et al.154 used leaching, an electrolytic method, and a
observed that precipitation of cobalt hydroxide started at pH 6 dehydration procedure to extract Co from waste LiCoO2. They
and completed at pH 8 (slightly alkaline), and Co(OH) 2 used inorganic acid and nitric acid as a leaching agent to
precipitate can be easily separated from the solution by recover cobalt ions, and then, the cobalt ion potentiostatically
filtration. Dai et al.149 found the precipitation rate of Co is over transformed into cobalt hydroxide on a titanium electrode.
97% by adding some dispersant and flocculants. They Finally, a dehydration procedure was used to collect cobalt
confirmed that ammonium bicarbonate is the best precipitator oxide. Hydroxide ion formation near the electrode via the
except for oxalic acid through a series of systematic electroreduction of dissolved oxygen and increase in the local
experiments. Shuva and co-worker86 reported a leaching and surface pH of the titanium due to nitrate ions was confirmed
chemical precipitation process to recover Co and Li from LIBs. by the observation of distinct cathodic current peaks in linear
The optimum condition to recover Co and Li from spent LIBs sweep voltammetry (voltammetry is the study of current as a
was found to be HCl (3 M), H2O2 (3.5 vol %), solid−liquid function of applied potential). Under appropriate pH
(S/L) ratio = 1/20 g/mL, 80°, and 60 min. It was reported conditions, island-shaped cobalt hydroxide is precipitated on
that around 89% Li and Co were recovered. They also found the titanium substrate, and heat treatment of the cobalt
that LiCoO2 dissolution increases with increasing temper- hydroxide results in the formation of cobalt oxide. The detailed
atures, HCl concentration, leaching time, and S/L ratio. They electrochemical reactions of the electrolytic method are as
suggested that this method can be used in a large scale due to follows
high recovery rates of metal from the spent LIBs. 2H 2O + O2 + 4e− → 4OH− (16)
Guzolu et al.87 reported that nickel, copper, iron, aluminum,
cobalt, and manganese were precipitated from a leaching NO3− + H 2O + 2e− = NO2 + 2OH− (17)
solution using NaOH, while lithium carbonate was precipitated
by addition of a saturated sodium carbonate solution.
Co3 + + e− = Co2 + (18)
Saturated diammonium oxalate (NH4)2C2O4 was used to
precipitate Co2+ in the solution and was reported by Hu et
Co2 + + 2OH−/Ti = Co(OH)2 /Ti (19)
al.150 In this work, the authors calculated the recovery rate of
Co and found it to be 96.3% when the pH value is 2, The reduction of dissolved O2 and nitrate ion, i.e., reactions
temperature 60 °C, and volume ratio of Co2+ and (NH4)2C2O4 16 and 17, could increase the local pH of the electrode. Thus,
is 1:1.5. Zhu et al.104 reported both an acid leaching and the precipitation of hydroxide films of Co(OH)2 (eq 19) under
chemical precipitation method which gives recovery rates of an appropriate pH condition is possible. Therefore, this
96.3% for Co and 87.5% for Li. They also used diammonium process provides a good way for recovering cobalt oxide from
oxalate (NH 4 ) 2 C2 O 4 in the leaching solution to get LiCoO2.
precipitated cobalt(II) oxalate dihydrate (CoC2O4·2H2O) 3.4. Direct Recycling Process. In this recycling process,
microparticles, and separated Li2CO3 precipitates by addition active materials of LIBs are recovered directly after a
of Na2CO3. pretreatment process without disturbing the original com-
3.3.4. Electrochemical Process. Nowadays, alternative pound structure. Initially, LIB elements are separated, by using
purification processes such as electrolytic methods are also physical separation methods, magnetic separation, and thermal
investigated as boosters in the hydrometallurgical recycling processing to avoid chemical breakdown of the active
processes. Zhang et al.151 reported a paired electrolysis materials. In the second step, recovered purified active material
approach for recycling spent lithium iron phosphate batteries surface and bulk defects are repaired by relithiation or
in molten salts. LiFePO4 acts as both anode and cathode, and hydrothermal processes. Recycling of NMC batteries by a
molten carbonate is the electrolyte in the paired electrolysis direct recycling process is still challenging due to the mixture
approach. The paired electrolysis converts LiFePO4 to Fe at of more than one active material. However, a direct recycling
the cathode and to Fe3O4 at the anode while releasing Li+ and approach has many advantages compared to pyrometallurgy
PO43− into the molten salt. In another reported work, Zhang et and hydrometallurgy because of the following: (a) It is a
al.152 used a green electrochemical process to recover Co and simple recycling process. (b) Cathode materials can be reused
Li from spent LiCoO2 batteries in molten salts. Lupi et al.153 directly after regeneration. (c) It is associated with lower
has adopted the electrolytic method to recycle Co and Ni from emissions and less secondary pollution.155 This relatively short,
Li-ion and Li−polymer batteries. The cathode-active materials green, and simple recycling process shows great potential for
were leached with H2SO4 and H2O2 in an appropriate ratio to commercial recycling of spent Li-ion batteries. The advantages
obtain cobalt and nickel solutions. They applied 250 A/m2, pH and disadvantages of direct recycling process are summarized
3−3.2, and 50 °C, with 87% current efficiency and 2.96 kWh/ in Table 2.
kg specific energy to recover Ni. They observed that poor Ni Shi et al.155 used a hydrothermal treatment and a short
powder was produced in 1 h with changing current efficiency annealing process to reuse cathode materials. This process is
(from 70% to 45%) by potentiostatic electrolysis. A current very simple, environmentally friendly, and effective compared
efficiency of 96% and specific energy consumption of 2.8 kWh/ to the conventional chemical leaching or solid-state synthesis
kg were obtained for Co at 250 A/m2, pH 4−4.2, and 50 °C approach. The morphology and structure of LiCoO2 particles
using a solution containing manganese and (NH4)2SO4. Co along with high specific capacity and cycling stability were
recycling as a cobaltite took place at the following conditions: maintained after the recycling process. The authors also
potentiostatic conditions, −0.9 V vs SCE, pH 4, and room proposed a greener, simpler, and more energy-efficient strategy
temperature. Compared with other technologies, Co produced to recycle and regenerate LiCoO2 cathode materials with high
by the electrolytic method has higher purity and minimal electrochemical performance. Shi et al.156 reported a non-
U https://doi.org/10.1021/acs.energyfuels.1c02489
Table 6. Direct Recycling Process to Recover Cathode Materials and Their Performances
Direct recycling process Performance Literature
Hydrothermal: 220 °C 4 h LiCoO2: 91.2% capacity retention after 100 cycles at 1C (3−4.3 V); 141.9 mAh/g at 2C Shi et
and 130.3 mAh/g at 5C al.155
Short annealing: 800 °C 4h
Hydrothermal: 220 °C 4 h NMC 111: first discharge capacity of 158.4 mAh/g at 1C and 122.6 mAh/g after 100 Shi et
cycles al.156
Short annealing: 850 °C 4h in O2 NMC 532: 128.3 mAh/g after 100 cycles
Solid phase sintering: 700 °C 8 h; doping ratio between LiFePO4: 144 mAh/g at 0.1C (2.5−4.1 V); 135 mAh/g after 100 cycles Song et
spent LFP with new LFP: 3:7 al.157
Solid phase heat treatment: 650 °C 1 h under Ar/H2 flow; LiFePO4: first discharge capacity of 147.3 mAh/g (2.5−4.2 V); 140.4 mAh/g after 100 Li et al.158
Li2CO3 as lithium source cycles at 0.2C and capacity retention 95.32%
Solid phase sintering: 850 °C; Li2CO3 as lithium source LiCoO2: first discharge capacity of 150.3 mAh/g (3.0−4.3 V) at 0.1C; 140.1 mAh/g after Chen et
100 cycles al.159
Hydrothermal: 80 °C 6 h; ultrasonic power: 600 W LiCoO2: first discharge capacity of 133.5 mAh/g; 99.5% capacity retention after 40 cycles Zhang et
al.160
destructive process to directly reuse degraded NCM cathode extensively in the industry.29 However, the valuable metals
particles to obtain new active particles. Directly regenerated used in NMC such as Co and Ni are expensive and toxic and
high performance NCM cathodes showed high specific also give a cathode with moderate specific capacity. Therefore,
capacity, good cycling stability, and high rate capability when intensive research is required to gain better understanding of
compared to the traditional hydrometallurgical methods. Song the cathode chemistry and charging/discharging mechanisms
et al.157 reported direct regeneration of cathode materials from to develop low-cost cathode materials based on Mn and/or Fe.
spent LiFePO4 batteries using a solid phase sintering method. Environmental perspectives and safety concerns suggest that
The battery capacities of regenerated LiFePO4 can reach over Co and Ni can be replaced with nontoxic and low-cost cathode
120 mA h g−1 at 0.1C discharge conditions, especially with the materials. Developing nonflammable Li-ion batteries by using
highest value of 144 mA h g−1 with a doping ratio of 3:7 at 700 aqueous electrolytes or ceramic electrolytes and all-solid-state
°C. Li et al.158 reported a green recycling process (direct batteries are other solutions toward a more sustainable future
regeneration process) of a cathode mixture material from of LIBs. Developing green batteries with low carbon footprints
scrapped LiFePO4 batteries. The high purity cathode material is another challenge for LIBs.162 Therefore, the future LIBs
mixture, anode material mixture, and other byproducts are should focus more on using biologically derived organic or
recycled at high yields. Chen et al.159 reported a simple and inorganic electrodes, biomass-based carbon and silicon, and
green recycling process to recycle spent 18650-type LiCoO2 aqueous electrolytes.
batteries. Solid phase sintering at 850 °C and Li2CO3 as the Life cycle assessment (LCA) is an important tool for the
lithium source were used for renovation of the LiCoO2 with development of the next-generation Li-ion batteries, which can
outstanding cycling stability. Table 6 shows the direct recycling contribute to a sustainable economy in the future. LCA studies
process to recover the cathode materials and the expected always help researchers develop models to evaluate the next-
performance of the new produced LIBs. generation Li-ion batteries with the goal of achieving optimized
3.5. Challenges and Life Cycle Assessment of LIBs. Li- social, environmental, and economic impacts. LCA of a battery
ion batteries (LIBs) have been used in cell phones and laptops provides full information about production, use, end-of-life
for about two decades, and technology is considered relatively treatment, and final disposal and recycling. The existing
mature based on the current battery chemistry. Nowadays, cathode materials such as LiCoO2, LiMn2O4, LiNiO2, and
LIBs have been commercialized and play a major role in LiFePO4; anode materials such as graphite and Li4Ti5O12;
electric vehicles. One of the major challenges of LIBs is their electrolytes/salts such as ethylene carbonate, diethyl carbonate,
ability to be used as competitive energy storage technology to LiPF6, LiBF4, and LiClO4; and separators such as poly-
store sustainable energy generated from renewable sources, propylene and polyethylene still require further analyses from
which requires development of next-generation LIBs at low the LCA perspectives.163 The environmental impact of battery
cost. The increasing demand for energy storage requires production is the primary concern for researchers. Three major
further improvements in the existing Li-ion batteries. However, issues need to be addressed during battery production:28 (1)
it is still considerably challenging to develop new battery environmental burden during the production of raw materials
chemistry to replace the existing Li-ion battery technology.29 or battery manufacture, (2) battery component impact on the
In order to improve the performance of batteries, researchers environment, and (3) environmental impact during develop-
have discussed large numbers of anode candidates which could ment of alternative cathode materials and anode materials. The
dramatically increase the specific energy capacities. Si- and Sn- use of suitable cathode and anode materials might reduce the
based anodes are highly attractive and are of great interest to environmental burden. Yu et al.164 studied the environmental
researchers161 and industry to develop high performance impact of LiFe0.98Mn0.02PO4/C, LiMn2O4/C, C/LiFePO4, and
batteries, but preparing Si nanomaterials on a large scale with FeF3(H2O)3/C batteries production processes by using a
low cost seems to be a little challenging for this technology. footprint family of indexes. LiFe0.98Mn0.02PO4/C batteries
Additionally, Sn-based anodes show poor cycling performance showed a higher environmental burden than that of C/
due to pulverization. The existing cathode material LiCoO2 is LiFePO4 batteries. The environmental burden of FeF3(H2O)3/
expensive and highly toxic, which partly played a role in C batteries is extremely smaller than the other batteries. This
increasing the demand of LiFePO4 and other cheaper cathode could be due to the simple and environmentally friendly
chemistries. The NMC-based cathodes developed by Argonne synthesis technology and low amounts of raw materials. They
National Laboratory are highly attractive and are used concluded that the environmental effects of Li are greater than
V https://doi.org/10.1021/acs.energyfuels.1c02489
those of Fe. Wu and Kong165 compared the cradle-to-gate addition, this process has lower recovery rates and
LCA of three batteries: Li metal anode (NCM-Li), silicon requires long leaching times. Therefore, research may
nanowire anode (NCM-SiNWs), and graphite anode (NCM- need to focus more on the recycling efficiency and
C). They found that a high specific energy anode produces less application of this novel leaching process.
pollution during battery production. They also found that a • Studies on the use of recovered cathode materials are
NCM-Li battery has a lower environmental burden than the limited, which implies the need for more work in this
other two types of LIBs they considered in this study. area to compare recycled vs virgin materials in making
current and future generation Li-ion batteries.
4. CONCLUSIONS • Potential to recycle and/or appropriately dispose of
In this electrified world, a significant and state-of-the-art role other materials such as polymers, electrolytes, current
has been played by LIBs due to their abilities to store and collector metals, and separators can lead to more
release energy in short times, to reduce energy use via higher economic advantages of the recycling process and can
roundtrip charge−discharge cycles, to reduce environmental help reduce the environmental impacts from battery
pollution in stationary, portable, and transport systems. The recycling.
■
increasing interest on using LIBs in portable electric devices
and electric vehicles (EVs) have introduced large amounts of AUTHOR INFORMATION
spent batteries in some countries (e.g., China and some
Corresponding Author
European countries), which results in a major environmental
issue; therefore, recycling of LIBs has become an urgent need Ahmad T. Mayyas − Department of Industrial and Systems
to save the environment and simultaneously reduce the Engineering, Khalifa University, 127788 Abu Dhabi, United
dependency on mined, high cost materials such as cobalt Arab Emirates (UAE); orcid.org/0000-0002-0367-
and lithium. In this review, battery chemistry, degradation 6503; Phone: +971-50-4381470; Email: ahmad.mayyas@
mechanism, pretreatment processes, and pyrometallurgical and ku.ac.ae
hydrometallurgical methods are well explained. In the leaching Authors
of cathode-active materials, LiCoO2, with inorganic acid Kishore K. Jena − Department of Industrial and Systems
produces Cl2, SO2, and NO2 gases, which have adverse Engineering, Khalifa University, 127788 Abu Dhabi, United
impacts on the environment. These gases react with moisture Arab Emirates (UAE); orcid.org/0000-0002-9941-1859
in the air to produce H2SO4, HNO3, and HCl acid molecules Akram AlFantazi − Department of Chemical Engineering and
that later form acid rain. To overcome these issues, many Emirates Nuclear Technology Center, Khalifa University,
researchers implemented organic acid leaching agents such as 127788 Abu Dhabi, United Arab Emirates (UAE);
citric acid, ascorbic acid, malic acid, succinic acid, maleic acid, orcid.org/0000-0002-4039-5110
and tartaric acid in the recycling process of Li-ion batteries and
at the same time to avoid the consumption of high acid Complete contact information is available at:
amounts. Other researchers have also used H2O2 and organic https://pubs.acs.org/10.1021/acs.energyfuels.1c02489
reducing agents to increase the dissolution process and
leaching efficiency within a short period of time. Many Author Contributions
researchers concluded that the variable operating temperatures K.K. Jena selected the topic of this review and wrote the final
and concentrations of leaching agents may not significantly draft. A.T. Mayyas supervised and did the final checking of the
impact the leaching process, but with the presence of reducing manuscript. A. AlFantazi did the final checking of the
agents, the recovery percentage could be improved to more manuscript.
than 90% for both Co and Li elements. Notes
Future Perspectives. The authors declare no competing financial interest.
• Many researchers have been working on different Biographies
leaching (acid, bioleaching, and alkaline leaching) and Dr. Kishore K. Jena is currently working as a research scientist at
separation processes to recover precious metals such as Khalifa University, Abu Dhabi, UAE. Dr. Jena received his Ph.D. in
cobalt, lithium, and nickel from spent Li-ion batteries, 2012 from IICT-CSIR, Hyderabad, India, with a specialization in
but as per our knowledge, there is a lack of research on polymer chemistry. Then, he joined the University of Hawaii at
recycling of anode materials from spent LIBs. Very few Manoa, USA, as a postdoctoral fellow. His research interests focus on
studies such as the one by Natarajan and Aravindan166 hybrid materials, polymers, coatings, functional materials for energy
reported the present status of LIB recycling in industries storage devices, and the recycling techniques for spent LIBs. He has
or research progress of graphite reuse in lab scale and published 40 research articles.
applications in energy. However, more research is Dr. Akram Alfantazi is a professor in the Department of Chemical
needed in this area to recover graphite (anode) and Engineering at Khalifa University, Abu Dhabi, UAE. He obtained his
electrolytes from Li-ion batteries and to develop high M.A.Sc.and Ph.D. in metallurgical engineering from Queen’s
performance LIBs for EVs University, Canada. Dr. Alfantazi has 200 refereed journal
• The chance of corrosion during the leaching process is publications. He is a Fellow of the NACE International and
highly possible. Instruments are used during the leaching Engineering Institute of Canada. He has received awards for his
and separation process, which indicates the need for work including the Canadian Materials Chemistry Award. He was
R&D of the advanced leaching equipment and systems. appointed a Chang Jiang Scholar at the China University of Mining
• Recent research in the bioleaching process supports its and Technology.
environmentally friendly aspects, yet the high cost may Dr. Ahmad T. Mayyas is an assistant professor of Industrial and
limit scaling of the process at industrial levels. In Systems Engineering in Khalifa University, Abu Dhabi, UAE. Before
W https://doi.org/10.1021/acs.energyfuels.1c02489
joining Khalifa University, he worked as a clean energy systems (16) Cardarelli, F.; Dube, J. Method for recycling spent lithium
analyst at the National Renewable Energy Laboratory in Golden, metal polymer rechargeable batteries and related materials. U.S.
Colorado. He is currently involved in R&D activities of renewable Patent US7192564B2, 2007.
energy systems, manufacturing of fuel cells, and Li-ion batteries. Dr. (17) Pillot, C. The Rechargeable Battery Market and Main Trends
2014−2025. In 31st International Battery Seminar & Exhibit, 2015.
Mayyas worked as a research fellow at the University of California-
(18) Ahmed, S.; Nelson, P. A.; Gallagher, K. G.; Susarla, N.; Dees,
Berkeley and Lawrence Berkeley National Laboratory between 2013− D. W. Cost and energy demand of producing nickel manganese cobalt
2015. cathode material for lithium ion batteries. J. Power Sources 2017, 342,
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733−740.
ACKNOWLEDGMENTS (19) Brodd, R. J.; Helou, C. Cost comparison of producing high-
performance Li-ion batteries in the US and in China. J. Power Sources
The authors gratefully acknowledge the support and funding 2013, 231, 293−300.
from Khalifa University, Abu Dhabi, UAE, Grant No. (20) Lv, W.; Wang, Z.; Zheng, X.; Cao, H.; He, M.; Zhang, Y.; Yu,
8474000238/FSU-2020-14, to conduct this research. H.; Sun, Z. Selective recovery of lithium from spent lithium-ion
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batteries by coupling advanced oxidation processes and chemical
leaching processes. ACS Sustainable Chem. Eng. 2020, 8 (13), 5165−
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ABSTRACT: Recycling of spent lithium-ion batteries (LIBs) is an

most of those strategies deal with cathodes rather than anodes.

1. INTRODUCTION predicted future market growth of lithium-ion batteries for

Figure 1. Summary of crystal structure and properties of diﬀerent LIB cathodes.

2. LI-ION BATTERY: TYPES, STRUCTURE, AND

High cost, nickel and cobalt (expensive

Short life span, low thermal stability,

Low speciﬁc energy and expensive

Short lifetime, low energy density

and less abundant materials)

Safety issues, high cost

Cheap abundant materials and high power, safer than Li

Long life, fast charge, wide temperature range, safest Li-

High capacity and voltage, high power densities, good

Excellent power, good lifetime and safety, abundant

cobalt, high thermal stability, enhanced safety

High performance well understood

capacity and high power

Electric powertrain (Mitsubishi i-MiEV, Honda

Medical devices, industrial, electric powertrain

E-bikes, medical devices, EVs, industrial

Fit EV), solar-powered street lighting

Power tools, medical devices, electric

graphite anode and is used in most of the portable electronics

such as mobile phones, laptops, and digital cameras. The

move from anode to cathode during the discharge mode and

reverse ﬂow from cathode to anode during the charging mode.

Some common characteristics of the LCO include high

2.1.2. Lithium Nickel Manganese Cobalt Oxide (LiNiMn-

CoO2), NMC.38 NMC is the common cathode chemistry in

electric vehicles, e-bikes, and electric scooters. Nickel provides

resistance but oﬀers a low speciﬁc energy. The strength of the

lithium nickel manganese cobalt oxide is enhanced by the

manganese metals. One-third mole of nickel, one-third mole

of manganese, and one-third mole of cobalt is used to make the

cathode (∼9% Co); anode, graphite

Battery manufacturers recently started to change the

Li2TiO3: LMO or NMC cathode;

combination of nickel, manganese, and cobalt to 5−3−2 due

to the cost of the cobalt raw material, and the evolution of

anode, Li2TiO3 (titanate)

NMC is expected to go with lesser amounts of cobalt per kWh

chemistries. The charge rate (C-rate) is 0.7−1C and charges to

Charge current above 1C may shorten the battery life. The

3. Enhanced leaching eﬃciency

Energy Fuels XXXX, XXX, XXX−XXX

Figure 4. Pyrometallurgical process ﬂowchart of spent LIBs.

dissolve metals from spent LIBs. Bahaloo Horeh et al.113 used

spent LiCoO2-based batteries in molten salts. ACS Sustainable Chem.

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