LIB (Lithium Ion Battery)

Circular Economy 1 (2022) 100015
Contents lists available at ScienceDirect
Circular Economy
journal homepage: www.journals.elsevier.com/circular-economy
Review
State-of-the-art lithium-ion battery recycling technologies

Muammer Kaya*
Department of Mining Engineering, Eskisehir Osmangazi University, 26480, Eskisehir, Turkey
a r t i c l e i n f o a b s t r a c t
Article history: Lithium (Li) is primarily found in mineral resources, brines, and seawater. Extraction of Li from mineral
Received 11 July 2022 ore deposits is expensive and energy-intensive. Li-ion batteries (LIBs) are certainly one of the important
Received in revised form alternatives to lessen the dependence on fossil fuel resources. The global demand for LIBs for portable
16 August 2022
electrical and electronic equipment (EEE) and EVs have increased significantly, and the amount of spent
Accepted 22 August 2022
Available online 15 October 2022
LIBs (S-LIBs) is rising logarithmically. S-LIBs contain both hazardous heavy metals and toxic organic
chemicals that create a serious threat to human health and the ecosystem. The current position requires
the recycling of S-LIBs indispensable for the protection of the environment and the recycling of scarce
Keywords:
Lithium recovery
raw materials from economic aspects. In this manuscript, recent developments and state-of-the-art
Spent LIBs technologies for LIB recycling were focused on and reviewed comprehensively. Pretreatment methods
Hydrometallurgy (such as discharging, dismantling, cathode active material (CAM) removal, binder elimination methods,
Pyrometallurgy classification, and separation) for S-LIBs are introduced, and all available and novel technologies that are
Pretreatment used in different physical and chemical recovery processes are summarized and compared. The pre-
Metal extraction treatment process in LIB recycling can both improve the recovery rate of the valuable components and
Recycling significantly lessen the subsequent energy consumption. Notably, pretreatment, metal extraction, and
product preparation stages play vital roles in all LIB recovery processes, based on pyrometallurgy, hy-
drometallurgy, biometallurgy, direct recycling, and mechanical treatment and water leaching. The main
goal of this review is to address the novel S-LIB materials’ current recycling research status and in-
novations for integrated, eco-friendly, economic, low carbon, and clean energy technologies. In the end,
different industrial recycling processes are compared, existing challenges are identified and suggestions
and perspectives for future LIBs recycling applications are highlighted.
© 2022 The Author(s). Published by Elsevier B.V. on behalf of Tsinghua University Press. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Lithium (Li) “white gold” New clays like hectorite resources are rare. This creates a significant
problem for scientists to develop novel approaches for efficient
Li is a soft and silvery-white element. It is highly reactive and extraction processes from existing sources. Ambrose and Kendall
flammable in its pure form. Li is present on Earth's crust in brines (2020) estimate the total global Li resource as 55e99 Mt. Accord-
and minerals. It has several uses, but its abundance in nature is only ing to the USGS, Bolivia has 21 Mt, Argentina 19.3 Mt, Chile 9.6 Mt,
18 ppm by weight. Li is relatively low in abundance throughout the USA 7.9 Mt, and Australia 6.4 Mt Li, resources globally. The major Li-
cosmos. Li is a scarce alkaline metal and has an atomic number of 3. bearing minerals are spodumene (LiAlSi2O6; 4%e7% Li), petalite
Li is the lightest solid alkaline earth element with a density of (LiAlSi4O10; 2%e4% Li), lepidolite (K[Li,Al]3[Al,Si]4O10[OH,F]2); 3%e
0.543 g/cm3. Li is an electropositive metal that has the highest 4% Li), zinnwaldite (K[Li,Al,Fe]3[Al,Si]4O10[OH,F]2), amblygonite
reactivity and high heat and electricity conductance. Li cannot be ([Li,Na]Al[OH,F]PO4; 8%e9% Li), montebrasite (LiAl[PO4][OH]),
found as an element in nature, it can be found as Liþ(aq), LiOH(s), eucryptite (LiAlSiO4; 5.51% Li), triphylite (Li[Fe,Mn]PO4), jadarite
Li(s), LiH(s), LiSO
4 ðsÞ, Li2O(s), and Li2O2(s) forms. (LiNaSiB3O7[OH]) and hectorite (Na0.3[Mg,Li]3[Si4O10]
According to Yang et al. (2018), there are about 230,000 Mt of Li [F,OH]2$nH2O) containing <1%e9.7% Li2O. Table 1 shows the sum-
dissolved in the seawater and it is present in the Earth's crust at mary of the major primary Li resource classification and Li extrac-
between 20 and 70 ppm by weight, mainly in igneous granite rocks. tion methods. Mineral deposits have 34% and brine deposits have
66% of total Li reserves excluding seawater. Solid mineral deposits
can be found in igneous (25%e35%) and sedimentary (8%e13%)
* Corresponding author. rocks and require expensive methods for Li extraction with
E-mail address: [email protected] (M. Kaya).
https://doi.org/10.1016/j.cec.2022.100015
2773-1677/© 2022 The Author(s). Published by Elsevier B.V. on behalf of Tsinghua University Press. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
2 M. Kaya / Circular Economy 1 (2022) 100015
Table 1
Major primary lithium resource classification and lithium extraction methods in 2019 (compiled from Can et al., 2021; Celebi, 2019; and Reich et al., 2022).
Mineral Ore Deposits (34%) Brines (66%) Seawater Reserve
(12.8e30.7 Mt) (21.3e65.3 Mt) (230 Bt)
Magmatic rocks (25%e35%) Sedimentary rocks (8%e13%) Brine water (52%e66%) Mine waste water Seawater
Pegmatites Volcano sedimentary rocks Salt lakes Boron process
Greisens Clay hosted Li deposits (B/Li- Petroleum reservoirs (oil fields) wastewater in the
Alkaline granites rich clays) Saline tailing pond
*Spodumene (LiAl(SiO3)2) *Hectorite (0.5%e0.7% Li) Geothermal brines (Cons: 0.1
*Lepidolite e68 mg/L Li)
Solid rocks (2%e5.5% Li) Liquid solution (0.02%e5% Li) 0.1e0.2 ppm Li
Expensive/Energy Intensive Environmental problems Cheap (30%e50% than mined ores) Easy production
Ext. 87%
Crushing, grinding, sieving, gravity, flotation, Hydro-/pyro-metallurgy/ Evaporation Membrane processes SX, IX, liquid-liquid
and magnetic separation Pressure leach/Bioleaching Direct precipitation Solvent extraction (SX) extraction, membrane
Calcination (bacteria) Sedimentation Bioabsorbent separation
Acid/alkaline treatment with H2SO4/HCl (50 Electrodialysis Sorption and ion
e250 C) or lime or gypsum (750e1000 C) Inorganic absorbent (Li-metal exchange (IX)
roasting oxides,
Ti-oxides, Al-hydroxides, Fe-oxy-
hydroxides, Li(Fe)PO4, Clay
minerals)
significant environmental problems. Aqueous brines are cheap for Table 2

Li extraction. World mine production and reserves between 2016 and 2020 according to the USGS.
Table 2 shows the world mine production and reserves between Country Mine production (t)
2016 and 2020 according to the USGS data (https://www.usgs.gov/). 2016 2017 2019 2020a Reserves
In 2019 and 2022, more than 880,000 tonnes of Li were produced.
Argentina 5800 5500 6300 2,000,000
Table 3 shows Li minerals and brine world production by country or d
Australia 14,000 18,700 45,000 40,000 64,700,000
region (https://www.usgs.gov/media/files/lithium-2019-tables- Chile 14,300 14,100 19,300 18,000 9,200,000
only-release). China 10,800 14,000 2300 3000 3,200,000
Brazil 200 200 2400 1900 95,000
Portugal 400 400 900 900 60,000
2. Li lithology and production from nature resources
Canada d d 200 d 530,000
Zimbabwe 1000 1000 1200 1200 220,000
Li has excellent heat and electrical conductivity because of its World total (round) d d 886,000 882,000 21,000,000
high reactivity. Pure/free metallic Li is never found in nature due to a
e: estimated.
its reactivity, but it is found as a compound such as Li-salts. They
can be found in ore deposits, brines, clay, seawater, geothermal
brines, and water. Although Li is used extensively, its reserves and from spodumene and Chile is the largest producer of Li from brine.
production are unevenly distributed across the globe. South Chile, Bolivia, and Argentina in South America comprise the
American nations, such as Argentina, Chile, and Bolivia, own more “lithium triangle”, named for the region's vast Li resources. Li
than 70% of the world's Li deposits in the Li triangle region (Fig. 1). production in China, which is the world's largest consumer of Li,
Australia has 43.5% of the global production and followed by Chile was 7500 tonnes in 2019 (https://newenergy.slb.com/new-
with 32.8% of global production. Argentina and China are signifi- energy-sectors/sustainable-battery-grade-lithium).
cant Li exporters in the world (Bae & Kim, 2021). Presently, Li is
mainly extracted from two natural sources: ores and salt lakes. For 3. Lithium usage
brines, the Li grade and Mg/Li ratio (0.22e21.5) are important fac-
tors that affect production cost and time. Li extraction from evap- Since there is no free Li on the Earth, Li compounds are impor-
orative salt lake brines is not efficient or adaptable that has an Mg/ tant components in many industrial applications and are used in
Li ratio greater than 6 (https://www.chemistryviews.org/details/ LIBs, ceramics, glass, cement, special LieAl alloys, lubricants, air
ezine/11138711/Selective_Extraction_of_Lithium_from_Salt_Lake_ conditioners, polymers, chemicals, and nuclear power plant in-
Brines/). The brine contains 0.02%e5% Liþ, along with other cations dustry as well as a psycho-medical pharmacy (Meng et al., 2021). In
(Naþand Kþ), and anions (Cl and SO2 4 ). 2019, global total Li usage distribution is 65% in batteries, 18% in
From the primary resources, Li is commercially extracted from ceramic & glass, 5% in grease, 3% in casting, 3% in polymers, and 6%
hard rock spodumene minerals in igneous rocks and conventional in others. Li is preferred as the battery material among all metals
LiCl salts are found in brine pools and seawater. A huge amount of because of the lightest, highest electrochemical potential, and
Li is extracted from liquid brine reservoirs that are located highest energy density. LiOH is used for LIBs, Al and steel produc-
beneath salt flats, known as salars, most of which are located in tion, and lubricants. Li2CO3 is used for LIBs, glass and ceramics
southwestern South America and China. Other Li-rich brine re- production, Al and steel production, and drag production. LiOH is
sources include oil fields and geothermal brines. Li brine deposits the weakest hydroxide and is mainly consumed in the production
are accumulations of saline groundwater, geothermal water, and of cathode materials for LIBs such as LiCoO2 and LiFePO4. LiCl is
seawater that are enriched in dissolved Li (200e1500 ppm). The used for LIBs, LieAl alloys, and air conditioners. Adding Li to the
methods of Li extraction and processing vary depending on the ceramic masse enhances the glass melt rate and diminishes pulp
source material. Li brine recovery is typically a simple but time- viscosity and melting temperature. In addition, the high thermal
consuming process. In addition, the recycling of LIBs is the ma- expansion coefficient of Li makes ceramics resilient to heat shocks
jor secondary source of Li. Australia is the largest producer of Li and improves mechanical strength. High-temperature Li grease is
M. Kaya / Circular Economy 1 (2022) 100015 3
Table 3
Lithium minerals and brine world production (t), by country or locality between 2015 and 2019.
Country Lithium mineral Brine world production (t)
2015 2016 2017 2018 2019
Australia LiAl(SiO3)2 439,514 522,181 1,706,618 1,965,944 1,616,764

Chile Li2CO3 50,418 70,831 73,563 87,029 99,300
LiCl 2069 1775 2535 3826 3000
LiOH 3888 5576 5280 6468 10,000
Brazil concentrate 5781 8804 10,547 41,000 85,000
Zimbabwe LiAlSi4O10, (K[Li,Al]3[Al,Si]4O10[OH,F]2) 50,000 50,000 40,000 80,000 80,000
Portugal K[Li, Al]3[Al,Si]4O10[OH,F]2 17,120 25,758 52,741 76,818 77,000
China LCE 20,470 25,400 37,300 37,800 57,500
Canada LiAl(SiO3)2 d d d 114,000 9000
Namibia K[Li, Al]3[Al,Si]4O10[OH,F]2 d d d 30,000 d
USA Li2CO3 W W W W W
W: Withheld to avoid disclosing company proprietary data.
useful in concentrating oil and Li additives are utilized in casting to electrolytes, etc., which contain Co, Li, Ni, Mn, Cu, Al, and other
increase fluidity. Organic Li materials are used as strong bases in valuable heavy metals. If these components are not handled
polymers to form CeC bonds. properly, they easily leak into the environment and pose a huge
threat to the ecosystem and human health (Dorella & Mansur,
4. Growing and robust Li market across borders 2007). Moreover, S-LIBs also have a certain economic value. Spe-
cifically, Co and Li are strategic scarce resources, their content in S-
Strong demand growth is expected from electric vehicle (EV) LIBs is generally significantly higher than that in ores, and their
sales and battery capacity growth. Li pricing is increasing as de- recovery through effective technology will produce huge economic
mand is expected to outstrip supply. LiOH shortages will signifi- benefits (Mishra et al., 2008; Zeng et al., 2012). Thus, it is very
cantly grow with time. Fig. 1(a) shows LiOH versus Li2CO3 demands important to do more research and development on recovering
in Mt LCE. In 2022, LiOH and Li2CO3 demand is less than 0.4 Mt. valuable metals from S-LIBs.
Fig. 1(b) shows the global Li supply and demand forecast between
2015 and 2030 for different sectors. Li-battery demand will 5. Lithium-ion batteries (LIBs)
significantly increase by 2030. There will be serious Li shortages in
the 2030s. Fig. 1(c) presents Li mega factory growth rate between At the present time, the high consumption rates of fossil fuel
2014 and 2030. There is 151 operating battery factory by the end of resources and the need to decrease their environmental impacts
2021 and 225 battery factories planned for 2030. 225 mega fac- drive consumers for developing to use sustainable and renewable
tories (4.2 TWh) operating at 100% capacity will need more than energy resources such as better batteries, solar cells, wind turbines,
3 Mt/y Li in 2030. and fuel cells. LIBs are one of the important alternatives to lessen
The Li market needs 10 to 18 times more Li production by 2030. the dependence on fossil fuel resources. LIBs structure, advantages
Li was added to the critical raw materials list in the EU for the first and disadvantages, waste sources, recycling technologies, and
time in 2020. LIBs represent one of the 21st Century's largest environmental problems are covered in detail here.
growth areas. Fig. 2 shows LIBs placed on the global market be- With the rapid development of high technology, mobile/per-
tween 2018 and 2028. The demand for Li, graphite, Ni, and Co will sonal electronic and electrical equipment (EEE) and EVs have
significantly increase until 2028. penetrated every corner of our lives. LIBs have become a portable
Because EVs greatly depend on LIBs, strategic Li supply security power source dominant in mobile phones, laptops, PCs, cameras,
for large automotive manufacturers has become a major priority for video cameras, hand-held equipment, and other advanced-life
countries, high-tech enterprises, and LIB producers. Strategic alli- appliances (Dorella & Mansur, 2007; Mishra et al., 2008; Paulino
ances and joint ventures continue were established to ensure a et al., 2008) because of their good performance compared with
reliable, sustainable, and diversified supply of Li for LIB suppliers nickel-metal hydride (NiMH) or nickel-cadmium (NiCd) batteries,
and EV manufacturers. for example, lighter, smaller, high working voltage, high energy
LIB market outlook growth potential is large because of density, long storage life, low self-discharge, and have no memory
emerging and growing technologies. Electricity will become the effect (Dorella and Mansur, 2007; Mishra et al., 2008). Thus the
primary norm for the automotive industry. Increased growth of demand and production of S-LIBs are increasing exponentially, and
mobile electronics and new additions such as wearables and IoT a large amount of production brings a lot of hazardous waste. The
enhances Li consumption exponentially, with about 10 million EVs enormous growth in the use of LIBs has generated a great amount
being sold in 2017 globally (Lie et al., 2020). The LIBs market is of S-LIBs for disposal that will cause serious environmental impacts
expected to reach $221 billion by 2024 (Hu et al., 2017; Lie et al., due to the toxic heavy metals and organic electrolytes. After the
2020). The significant increase in the demand and usage of LIBs end-of-life (EoL), this S-LIB acts both as a potential secondary
will also cause a huge generation of S-LIBs. Lie et al. (2020) and source for the recovery of critical metals and simultaneously
Harper et al. (2019) estimated that 250,000 tonnes of S-LIBs were possess a threat to the environment. So they need to be recycled
generated by the end-of-life (EoL) EV LIBs that were sold in 2017 properly to gain economic benefits.
alone. In 2040, about 340,000 t/y LIBs from EVs will be available for LIBs are not homogeneous and contain multi-metallic com-
recycling. Due to the high accumulation of S-LIBs in the waste pounds that are rich in Li, Co, Ni, Cu, Al, and Mn. One of the cathode
streams, it is very important to recycle them in an eco-friendly active material (CAM) of S-LIBs is lithium cobalt oxide (LCO)
process. The relatively short life span of LIBs leaves a huge (LiCoO2) which presents the principle and most important con-
amount of LIBs for disposal. These S-LIBs are composed of cathode stituent for batteries. The chemical composition of LIBs largely
and anode active materials, organic solvents, separators, shells, changes depending on their application areas. S-LIBs are a kind of
Fig. 1. (a) LiOH versus Li2CO3 demands in Mt LCE between 2018 and 2030 (https://about.bnef.com/blog/will-the-real-lithium-demand-please-stand-up-challenging-the-1mt-by-
2025-orthodoxy/). (b) Global Li supply and demand forecast between 2015 and 2030 for different sectors (https://about.bnef.com/blog/will-the-real-lithium-demand-please-
stand-up-challenging-the-1mt-by-2025-orthodoxy/). (c) Li mega factory growth between 2014 and 2030 (https://about.bnef.com/blog/will-the-real-lithium-demand-please-
stand-up-challenging-the-1mt-by-2025-orthodoxy/)
Fig. 2. LIB is placed on the global market until 2028 (https://www.neometals.com.au/products-and-markets/battery-recycling/).
hazardous waste EEE. If they are handled improperly, they will compatible operations (Joulie et al., 2014; Mylarappa et al., 2017).
cause serious harm to human health and the ecosystem (Xin et al., Fig. 5 shows waste LIB sources and estimated global amounts along
2009). However, there are also a number of valuable critical metals with lifetimes. A typical LIB structure is normally composed of
in the waste LIBs, such as Co (5e20 wt %), Li (5e7 wt. %), Ni, Cu, and anode materials, cathode materials, an organic solid/liquid elec-
Mn. (Contestabile et al., 1999, 2001). Therefore, recycling LIBs can trolyte, and a porous polymer (PE/PP) separator (Li et al., 2010a;
bring huge economic benefits (Lee & Rhee, 2003). Then S-LIBs Nan et al., 2006). The anode, cathode, and separator are laminated
recycling is necessary both for environmental conservation and by compressing them together which makes up the electrical
valuable metal recovery. Improper disposal of LIBs creates envi- connection achievable. The anode typically consists of a Cu-foil that
ronmental hazards. Landfilling can generate toxic metal leachates is coated with a porous graphite mixture, a conductor, and an
and incineration creates toxic gases to the environment (Fig. 3). electrolyte with a binder. The binder consists of polyvinylidene
fluoride (PVDF). The cathode contains porous CAMs (Li, Co, Ni, Mn,
6. Charging and discharging LIBs Fe, etc.) with a binder. Some of the LIBs materials, such as heavy
metals, toxic electrolytes, and hazardous organic separators and
Fig. 4 shows the charge and discharge details of LIBs. While binders, can constitute a significant threat to human health and
charging LIBs, Li ions go from the cathode to the anode through the ecosystems. Thus, it is necessary to safely recycle S-LIBs to recover
porous separator. Electrons flow from the cathode to the anode. their major valuable constituents.
During discharging, Li ions in the anode go back to the cathode and LIBs have a shorter lifespan than other batteries. A LIB can last
electrons flow from the anode to the cathode. up to 3 years in a small electrical and electronic device, and from 5
to 10 years in a larger device; NiCd batteries last from 15 to 20 years,
and lead-acid batteries (LABs) last from 5 to 10 years. At present,
7. Waste LIBs
80% of LIBs are used for small EEEs, with EV and solid-state elec-
trolyte (SSE) applications accounting for less than 20%. In 2012, LIB
Since the 1990s, LIBs have been extensively used in portable
disposal was estimated to be 10,700 tons. This value has increased
small EEEs (>80%), large EVs, and energy storage devices (>20%)
progressively each year up to 250,000 tons in 2020. Global waste
because of their small volume, lightweight, high energy voltage and
LIB amount will be 464,000 t in 2025. Waste battery collection rate
density, long cycle life, low self-discharge efficiency, non-memory
was only 2%e5% in the EU, USA, and Australia by government and
effect, wide temperature ranges, and advantages in eco-friendly
Fig. 3. Environmental hazards of improper LIB disposal and burning.

Fig. 4. Charge and discharge of LIBs.
Fig. 5. Waste LIB source types and global amounts.
manufacturer-driven collection (Bae & Kim, 2021). The reason for 9. LIB recycling
this low collection rate is the lack of consumer awareness of recy-
cling, the collection habit of consumers, and the tendency to resell LIB recycling has been continuously researched in the last
electronics. Even though it may vary by country, there is still a lack three decades and has recently gained significant importance.
of legal regulations and physical collection infrastructure for effi- However, most researchers focused on the extraction of the
cient, safe, and economical transportation of S-LIBs. Significant expensive Co than Li. Thus, little importance has been placed on
enhancements are necessary to significantly improve the collection extracting Li from disposed of S-LIBs. Co is the most expensive
rate. material in a LIB; thus, there has been considerable research in-
terest in diminishing the Co content or replacing it with Fe, Mn,
8. LIBs are the backbone of electrical vehicle transportation and Ni in LiFePO4 or LiNi1/3Mn1/3Co1/3O2. However, Li is an irre-
placeable main component in LIBs, and it is used in the cathode,
In the transition to a low-carbon future under climate change, anode, and electrolyte. Thus, an extensive review of Li recycling
electrification is a main key element. Globally transportation by EVs from S-LIBs is necessary.
is becoming popular; worldwide more than 1 million EVs were sold Harmless treatment for S-LIBs is vital for Li sustainability.
in 2020, and that number is expected to increase 20 times in 2030. Additionally, S-LIBs have a high economic value because they
Therefore, the demand for rechargeable LIBs will be rising rapidly. contain a significant amount of valuable/critical metals, some with
Since 2020, the growth in LIBs demand has caused product re- even higher grades than natural ores. S-LIBs usually contain 5%e
quirements to rapidly change. In 2027, demand will exceed 1 Mt of 20% Co; 5%e7% Li; 5%e10% Ni and other metals (such as Cu, Mn, Al,
lithium carbonate equivalent (LCE) (https://newenergy.slb.com/ Fe, etc.); 15% organic compounds, and 7% polymer separators. LIB
new-energy-sectors/sustainable-battery-grade-lithium). compositions differ depending on the battery producers and the
types. Valuable metals such as Li, Ni, Co, Cu, Al, and Mn recovery Recycling is no more optional for many countries to support
from S-LIBs cause significant economic gains if they can be recycled circular economic principles.
properly. Fig. 6 shows recycling LIB market growth from 2018 to
2030. There will be a recycling boom until 2030. Discarded LIBs are
likely to create a new global market for Li. The market will be more 10. LIB structure
than 1.5 MMt after 2029. As demand grows, LIBs recycling will
become an increasingly valuable secondary source of Li and Co A LIB is mainly made of an anode, a cathode, an electrolyte, and a
metals. porous separator. The cathode materials of LIBs are usually Li
The current LIB recycling ratio is very low and has the following intercalation oxides, like LiCoO2 (LCO), LiNiO2 (LNO), LiMn2O4
drawbacks: (LMO), LiFePO4 (LFP), LiNixCoyMn1xyO2 (NMC), etc. NMC cathode
materials have become the most promising CAM for EV LIBs due to
There is no mature technology to recycle LIBs yet, the low cost, large discharge capacity, good cyclic performance, and
Environmentally unfriendly, stable structure advantages. Portable electronics generally have
Produce extensive liquid and toxic waste by-products, LCO cathodic materials. Heavy Ni and Co metals in cathode mate-
Medium to low-grade products, rials pose a threat to the ecosystem and human health.
Complex processing and purification steps, The electrolyte of a LIB usually includes both mixture of organic
Low Li and Co recovery with little to no recovery of remaining solvents, like dimethyl sulfoxide (DMSO), propylene carbonate (PC),
metals, and and diethyl carbonate (DEC), and inorganic solutes, such as LiPF6,
Large consumption of reagents and energy. LiClO4, and LiBF4. LiPF6 is one of the most common inorganic sol-
utes used in LIBs. Electrolytes can be corrosive and produce haz-
Therefore, there is an urgent global need for novel LIB recycling ardous gas such as HF, Cl2, CO, and CO2 when heated/burned. The
technologies. porous separator prevents short-circuiting because of direct con-
tact between the cathode and anode. LIB separators are made of
usually single-layer or multi-layer polyethylene (PE) or poly-
9.1. Reasons of the LIBs recycling propylene (PP). Polyvinylidene fluoride (PVDF) and polytetra-
fluoroethylene (PTFE) binders are used to bond electrode active
As the LIB demand for EVs and electronic industries grows the materials to the Al/Cu foil and each other and can produce haz-
need for sustainable and circular LIB recycling will become in- ardous HF gas when heated. The cathode is an Al-foil with a CAM
crease. Currently, stockpiling, landfilling, and exporting LIBs is a no (like LiCoO2) combination, an electrical conductor, a PVDF binder,
longer acceptable choices. Because of: and additives. A separator is placed between two electrodes to help
in preventing a short circuit between them (Fig. 7).
Waste and scrap LIBs are considered hazardous waste in many Recycling processes of the S-LIBs include mechanical/physical,
countries (restricted to export to other countries according to chemical, or physicochemical processes. The mechanical processes
the Basel Convention) and pose fire and explosion risks during are the pretreatment methods while the extraction methods refer
storage and transportation. to the chemical processes. The LIBs contain several heavy metals,
Once liberated and extracted, LIB constituent materials are some organic chemicals, and plastics. 25%e35% of the LIB by weight
economically valuable and there is a serious shortage of these is cathode material, 10%e19% anode material, 9%e15% electrolyte,
materials in the world. Most of these materials are produced in and 1%e12% separator. The heavy metals mainly include 5%e20%
conflicted areas. Co, 5%e10% Ni, 5%e7% Li and there are about 15% of organic sub-
For most countries, national domestic supply chains can be met stances and 7% of plastics (Table 4). The most expensive parts of the
by secondary resource recycling only. S-LIBs are cathode and anode active materials.
Hydrometallurgical LIB recycling supports electrification with a Recently, the primary Li resources are depleting and Li is
decreased greenhouse gas footprint at reasonable material re- regarded under low to medium supply risk, concerning supply and
covery rates; and demand (Meshram et al., 2015; Munir et al., 2020). According to
Fig. 6. S-LIB recycling market capacity between 2018 and 2030.

Fig. 7. Illustration of the cylindrical and mobile phone's conventional LIB internal and external structures.
Zhao et al. (2019), the amount of Li content in the S-LiBs is about ten 11. Advantages and disadvantages of LIBs
times higher than in a primary spodumene ore and is thirty times
higher than in brines. Apart from critical Co and Li, LiBs also contain Table 6 shows the pros and cons of LIBs. The life span of the LIBs
economically desirable levels of non-ferrous metals like Cu, Al, Mn, is between 3 and 5 years if not in use and 1e3 years when in use. Li-
and Ni (Sethurajan et al., 2016; Simate et al., 2010; Zhang and ion technology is dominant in the rechargeable battery market for
Cheng, 2007). When considering them as alternative secondary electronics because of its small size, lightweight, high energy
resources for metals, the proper management and recycling of S- density, low discharge rate, no memory effect, etc. High cost, safety
LIBs become even more important. It was found that by the end of concerns, aging, and transportation problems are some of the
2020, 0.5 Mt of S-LIBs and 25 billion units were generated only in disadvantages.
China (Li et al., 2011; Yun et al., 2018). The worldwide LIB cathode
market was a $7 billion market in 2018 and is expected to reach 12. State-of-the-art S-LIB recycling technologies
about $59 billion by 2024 (https://www.researchandmarkets.com/
reports/4745669/lithium-ion-battery-cathodes-market-shares). S-LIBs contain not only highly valuable and scarce Li, Co, and Ni
Table 5 shows the comparison of the LIB cathode types (such as metals; but also Fe, Cu, Al, P, and other elements with low con-
LCO, LFP, LMO, NCA, and NMC), chemistry structure, year of intro- centrations. From the economic point of view, the recovery of S-LIBs
duction, energy and power densities, life span, performance, cost, mainly focuses on recycling highly valuable Co, Li, and Ni metals
and market share. Portable electronics and EVs contain different from CAMs; the recovery of graphite-containing anode materials
cathode types. Portable consumer electronics use LCO-type cath- and the electrolyte is hardly stated. Current metal-recycling pro-
odes which becomes obsolete soon. Electric bikes, buses, and large cesses for S-LIBs are pyrometallurgy, hydrometallurgy, bio-
vehicles use LFP-type cathodes. EVs use the cheap base metal-rich metallurgy, and direct recycling. State-of-the-art metal recycling
NMC and NCA types of cathodes which deliver strong energy processes from S-LIBs can be divided into three processes: namely,
density for the extended driving range. LCO has layered, LFP olivine, pretreatment, metal extraction, and end product preparation pro-
LMO spinel, NCA and NMC are layered type structures. cesses. Pretreatment is not required for the pyrometallurgical
Table 4
Composition of commercial LIBs estimated material costs and mass percent of battery components.
Battery components Material Mass (%) Estimated costs (%)
Container/housing/packaging foil Steel or Al 20e25 2

Positive electrode/cathode LCO, NMC, NCA, LFP, LMO, etc 25e35 49
Negative electrode/anode Graphite 10e19 16
Electrolyte LiPF6 dissolved in PC, EC, DMC, or DEC 9e15 6
Cathode current collector foil Al 5e7 2
Anode current collector foil Cu 4e9 5
Separator PE, PP 1e12 16
Binder PVDF d 3
Others (additives) Conducive carbon black, silicon, etc. Balance 1
process. Metal-extraction processes play the most important role in carried out. In the metal extraction stage, pyrometallurgical, hy-
the entire recovery process and involve one or both of the pyro- drometallurgical, electrometallurgical, and biometallurgical
metallurgical and hydrometallurgical methods. methods can be performed. Energy input, reagents, reductants,
The main purpose of recycling S-LIBs is to reduce or eliminate water, and bacteria/microorganisms are used in the process.
potential environmental problems and to recover valuable metals Concentrate, slag, wastewater, and waste gas are outputs of the
and cheap plastics, therefore promoting the sustainability of the Li process. The last product preparation stage includes the separation
battery industry. Even though several R&D studies have been per- and recovery of different materials and synthesis of CAMs for reuse
formed globally on S-LIB recycling, the recycling technology re- in new LIB production.
mains at the lab scale because of the heterogeneous and Manual dismantling of the individual cells is generally carried
complicated structure of the S-LIBs. out, but not many issues related to this were stated yet. (Kim et al.,
Currently, the main industrial S-LIB recycle technologies 2021). An automatic mechanical dismantling methodology for EoL
include hydrometallurgical process, hydrometallurgical process, pouch LIBs with Z-folded electrode-separator compounds (ESC)
or the combination of both, and microbial biometallurgy is still in was developed by Li et al. (2019).
the developing stage at the lab scale (Li et al., 2011). The most Changes in the types of size reduction equipment and the
frequently used industrial recycling technology for S-LIBs is py- operating conditions, like multiple comminution steps have been
rometallurgical processes. Using the above processes, Ni, Co, and made, and it was verified that these changes have a major effect on
Cu can be extracted effectively, while Li and Al are lost in the slag the yield of black mass and the flotation recovery efficiency. For
phase. However, pretreatment of S-LIBs is not used for pyromet- electrode material concentrations, various screen sizes from mm to
allurgical processes, and high energy consumption, equipment mm and the wet or dry screening conditions have been tested for
cost, and environmental pollution hinder their widespread the classification of the LIB comminution products.
application. Thus, several industrial hydrometallurgical processes
have been globally developed and are being used by various 13. Environmental problems created by LIBs
companies, such as Accurec, Toxco/Retriev, Umicore, etc. In these
companies, S-LIBs are recycled using the following steps: pre- Table 7 presents environmentally-related properties (such as
treatment, leaching, and purification by SX, and/or precipitation. vapor pressure, toxicity and hazards to water, and flammability) of
Equipment corrosion problems due to the highly acidic or alkaline materials used in industrial LIB production. Table 8 summarizes the
solutions existed in the hydrometallurgical process, but it is un- name, chemical formula, flammability limits, and flash points of
doubtedly the most suitable method for industrial application at LIBs. As seen from both tables, the ingredients can pose various
present. types of hazards to the ecosystem, particularly:
The following steps are the original route of the hydrometal-
lurgical process (Li et al., 2009; Mishra et al., 2008): Fire and explosion hazards because of high calorific, highly
volatile and self-igniting carbonate electrolytes
Discharging pretreatment to remove the excess energy Toxic effects for humans, because of gaseous, sometimes deadly
Dismantling of S-LIBs for removing the plastic and metallic decomposition products (such as HF, benzene, etc.) from LIB
covers/shells components
Size reduction by shredding and grinding The carcinogenic effect through the release of inhalable fine
Leaching with strong acid/alkaline solutions first to remove Al particle (10 mm) dusts of Ni/Co/Mn compounds
then leaching with strong acids
Separation of Li, Ni, and Co metals from pregnant leach solution Those potential health hazards should be recognized in
(PLS) handling waste LIBs during recycling. In addition, under certain
circumstances thermal runaway (for example overcharged,
The pros of hydrometallurgical processes are reduced energy external/internal short-circuit, overheat, etc.) behaviour can be
consumption and the ability to recycle Li and Al. However the cons triggered, releasing rapidly massive heat and toxic off-gases,
of hydrometallurgy processes are their complex and long process causing technical hazards and health risks.
flowsheet. This manuscript aims to review the major S-LIB recycling Depending on the battery type, charge state, ambient atmo-
methods and processes, highlight their main problems and provide sphere (air or inert Ar or N2 gas use), thermal treatment, and me-
perspectives for the future development of S-LIB recycling chanical treatment, toxic HF and/or POF3 gas emissions from LIBs
technology. are generated during the recycling process. As a result, an extensive
The general schematic of the methods and processes for recy- off-gas cleaning system is required in both thermal and mechanical
cling S-LIBs includes three stages (Fig. 8). In the pretreatment stage, treatment. The hazardous fluoride gas emissions mainly come from
discharging, dismantling, comminution, classification, and plastic, the decomposition of LiPF6 electrolyte, which is promoted by the
C, Al, Fe, and Cu separation from cathode and anode materials are presence of water/humidity based on the following reactions:
Table 5
Comparison of the LIB cathode types, chemistry, and properties.
Cathode type LCO LFP LMO NCA NMC
Chemical formula LiCoO2 LiFePO4 LiMn2O4 Li(Ni, Co, Al)O2 LiNi0.33Mn0.33Co0.33O2 (NMC111)
LiNi0.50Mn0.30Co0.20O2 (NMC532)
LiNi0.60Mn0.20Co0.20O2 (NMC562)
LiNi0.80Mn0.10Co0.10O2 (NMC811)
Structure Layered Olivine Spinel Layered Layered
Introduction year 1991 1996 1996 1999 2008
Safety 2 5 4 3 3
Energy density 4 3 3 5 5
Power density 3 4 4 4 3
Lifespan 3 4 4 4 4
Cycle lifespan 3 4 3 4 3
Performance 4 4 3 4 4
Cost 1 4 4 3 3
Market share obsolete e-bikes, small steady NMC111>NMC532>NMC622>NMC811 growing to without Co presence
buses, and large vehicles
LIB cathode chemistry 5 (excellent) 4 3 2 1 (poor)
Table 6
Pros and cons of LIBs.
Pros Cons
Smaller and lighter than others Cost

Li has the greatest electrochemical potential Protection required
High energy density Ageing
Low self-discharge rate (5%e10%) Transportation
Low maintenance Immature technology
Fast charging Safety concerns
No priming The internal resistance of LIBs is high as compared to other batteries
Availability of different prices Due to overcharging and high-temperature capacity will diminish
Reduced use
Shape and size variations
No memory effect
Fig. 8. Main stages in S-LIB active material recycling process.
LiPF6 / LiF þ PF5 (1) 14. Pretreatment methods for S-LIBs
PF5 þ H2O / POF3 þ2HF (2) The pretreatment process has been used from the starting stage
of LIB recycling research, and several research articles that focused
LiPF6 þH2O / LiF þ POF3 þ2HF (3) on the S-LIB pretreatment methods have emerged in the last
Table 7
Environmental problems related to the materials used in commercial LIB.
Materials Properties
Ethylene Carbonate (EC, C3H4O) Vapor pressure: 21 Pa (20 C).

Toxicity and hazard to water:
- Causes serious eye irritation
- Slightly hazardous to water (German water hazard class: WGK 1)
Propylene Carbonate (PC, C4H6O3) Vapor pressure: 4 Pa (20 C), 130 Pa (50 C).
- Causes serious eye irritation
Dimethyl Carbonate (DMC, C3H6O3) Highly flammable, highly volatile

Vapor pressure: 5300 Pa (20 C).
- Irritant effects, nausea, intoxication, unconsciousness, respiratory stop
Diethyl Carbonate (DEC, C5H10O3) Highly flammable, highly volatile

- Low toxicity
Ethyl Methyl Carbonate (EMC, C4H8O3) Highly flammable, highly volatile

- rritant
Lithium Hexafluorophosphate (LiPF6) Toxicity and hazard to water:

- Causes severe skin burns and eye damage
- Highly hazardous to water (German water hazard class: WGK 3)
Lithium Cobalt Dioxide (LiCoO2) At high temperatures, exothermic decomposition reaction with the release of oxygen
- Irritant, hazardous to health
- Cobalt salts can lead to cardiomyopathy (heart muscle disease)
- Possibly carcinogenic
LithiumeNickeleManganeseeCobalt Oxide Li(NixCoyMnzO2) Toxicity and hazard to water:

- Toxic, Co, Ni in the compound
- Hazard to water: no information
LithiumdTitanate (Li4Ti5O12) Toxicity and hazard to water:

- Slightly irritating to the respiratory tract
- Nanocrystals can be toxic due to their small size
decade. Thus, it will be convenient to cover various novel methods some remaining power. To prevent short-circuiting, burning, ex-
in the pretreatment process and summarize the related literature in plosion or spontaneous combustion, firstly S-LIBs should be dis-
the present stage. The aim and the order of the pretreatment pro- charged. In addition, because LIBs contain various types of
cesses can be categorized into discharge, dismantling, size reduc- materials in their electrodes, it is not efficient to treat the batteries
tion, classification, separation, dissolution, and thermal treatment directly. Thus, a pretreatment process is essential before hydro-
stages (Kim et al., 2021). The technological development and the metallurgical treatment. S-LIBs can be pretreated and separated
current status of each category are highlighted extensively here. safely only when they are almost fully discharged. Otherwise, the
battery can burst, burn or emit hazardous gases because of short-
14.1. Discharging circuiting between anode and cathode. Electronic techniques and
conductive liquids/metals can be used for discharging batteries.
Determination of the residual power of an S-LIB is not easy. Even LIBs can be discharged to a safe voltage (0.3e1.0 V) by connecting
after the depleting charge of the LIB, the battery might still have with a load (halogen bulb or resistor) (Widijatmoko et al., 2020;
Table 8
Lower/upper flammability limit (LFL/UFL) and flashpoint of LIB electrolytes.
Electrolyte Name Formula LFL, %vol (in the air) UFL, %vol (in the air) Flashpoint, C
EC Ethylene carbonate C3H4O3 3.6 16.1 143

DMC Dimethyl carbonate C3H6O3 4.22 12.87 18
EMC Ethyl methyl carbonate C4H8O3 2 NA 23
DEC Diethyl carbonate C5H10O3 1.4 NA 33
PC Propylene carbonate C4H6O3 1.7 21 123
EA Ethyl acetate C4H8O2 2.2 9 4
DE Diethyl acetate C4H10O 2 36 45
THF Tetrahydrofuran C4H8O 1.5 12 17
AN Acetonitrile C2H3N 3 16 2
DMSO Dimethyl sulfoxide C2H6OS 2.6 42 89
DME Ethylene glycol dimethylether C4H10O2 1.6 10.4 5
g-GBL g-Butyrolactone C4H6O2 3.6 16 98
Zhan et al., 2018). S-LIBs are unfolded to separate anode, cathode, 14.2. Dismantling
separator, and other components under the fume hood to prevent
toxic organic solvents (EC or EMC). Immersion of the S-LIBs in a Individual battery cells are often disassembled by hand for
conducive salt (NaCl) solution is the most common and popular laboratory experimental purposes, but manual disassembly is
discharging method used on the lab scale. expensive for industrial processing. Automatic/robotic disassembly
There is still ongoing research on the discharge and corrosion can be developed for industrial-scale operations, although the large
rates of other conductive liquids and/or solids. Unlike other batte- variety of battery cell designs makes that challenging. Thus, most
ries, LIBs often explode during the recycling process because of processing flowsheets proposed for small LIBs involve shredding,
radical oxidation, which is caused by the mechanical shock of Li and then different components are separated before materials can
metal produced from battery overcharge from exposure to the air. be recovered. The Al-and Cu-foils holding the electrode active
Considering the current crushing and grinding processes, this poses materials are usually separated by sieving at 212 mm. However, a
a great danger. Therefore, before the crushing and grinding pro- portion of the active material may still stick to the foils. Therefore,
cesses, S-LIBs should be soaked in unsaturated (10%) salt water (like screening from 38 mm achieves better Li and Co liberation and
NaCl, KCl, NaNO3, MgSO4, MnSO4, and FeSO4) and the energy inside extraction than Al and Cu foils. The evaporation step of organics
them should be discharged (Pra zanova et al., 2022). Xiao et al. removes the binder and reduces the quantity of active material
(2020) found that overall discharge efficiency decreased in the or- stuck to the foils.
der of MnSO4 < FeSO4 < NaCl. This process is the most popular Li et al. (2019) proposed the automatic disassembly technology
stabilization method and decreases the short-circuiting generation for the recycling of pouch-type LIBs, which were named Z-folded
and exothermic reaction occurrence in the anode. For instance, the electrode-separator compounds. The proposed electrode sorting
response of Li to oxygen (air) and water (humidity) causes the strategy extracted the cathode and the anode sheets without
inflammation of the highly combustible organic electrolyte sol- applying any destructive forces. By automatically stretching and
vents. Therefore, preliminary discharging treatment of S-LIBs feeding the Z folded separators, the cathode and the anode sheets
before hydrometallurgical recycling is necessary (Contestabile attached on the opposite sides of the separators were scraped off
et al., 1999). The physical discharge in solid media using Cu and using specialized toolsets.
graphite powder may be an adequate large-scale discharge method.
But because of the contact problem, the easily oxidized metal sur- 14.3. Pretreatment methods
face, and the graphite dust bursting risk cannot make this method
be used extensively. Thus, Kim et al. (2021) suggested FeSO4 be the Pretreatment methods to separate the CAM and/or anode active
most ecofriendly discharge solution. material from the disposed of S-LIBs after discharging can be
The industrial Batrec company generally uses a mechanical broadly categorized as alkaline dissolution, ultrasonic-assisted
treatment to recycle S-LIBs. First of all, the batteries are size operation, SX, mechanical separation, and calcination treatment
reduced in an inert CO2 gas atmosphere. Thereby, the volatile separation. The pros and cons of various pretreatment methods are
organic electrolyte evaporates by heat and is collected as conden- compared in Table 9.
sate without any usage. Then, S-LIBs are dismantled by hand or
mechanically separated. Manual dismantling is generally carried 14.3.1. Mechanical pretreatment
out to separate the cathode material, anode material, and other The disassembled LIBs require size reduction by crushing and
components. Manual dismantling is not suitable for industrial- grinding to liberate the electrode active materials, and this size
scale. Graphite particles are weakly attached to the anodic Cu reduction stage is especially important for the hydrometallurgical
current collector electrode and LiCoO2 particles are strongly process. Selective liberation depends on the comminution tech-
attached to the cathodic Al current collector electrode by a binder nique being used. Liberation can be provided by impact, shear,
(Dai et al., 2019). Therefore, graphite generally contaminates LiCoO2 abrasion, etc. Attrition scrubbing induces impact and shearing ac-
in mixed materials. It is difficult to remove/liberate binder from tion between particles which promotes surface abrasion and pro-
CAMs mechanically. The CAM is generally bonded to Al-foil via the duces fine particles. Inert silica sand was used as an abrasion media
PVDF or PTFE binder, which makes it difficult to separate the CAM by Widijatmoko et al. (2020). Mechanical pretreatment methods
from the foil. To effectively separate the CAM from the Al-foil, are effective processes that involve physical size reduction (crush-
solvent dissolution, NaOH dissolution, ultrasonic-assisted separa- ing by shredders, blade crushers, etc., and grinding by hammer
tion, thermal treatment, and mechanical methods have been pre- mills) and classification (by sieving and separation) of the dis-
viously tested (Zheng et al., 2018). charged S-LIBs. Different parts of the S-LIB have different
mechanical properties, thus a shredder/mill which can uniformly like crushing, sieving, and magnetic separation; next, LiCoO2 and
crush/grind all the parts is required. Generally, a closed-circuit gas- small pieces of Al-foil were separated by finely ground the LiCoO2-
tight grinding is used. enriched particles. The efficiency of the desired metal recovery can
Batenus hydrometallurgical process, which is one of the first be enhanced by mechanical separation processed before the hy-
large-scale battery recycling facilities, shredded mixed types of drometallurgical process. The main disadvantage of mechanical
batteries in a gastight unit (Fro€hlich & Sewing, 1995). The Recupyl methods is that the components of S-LIBs cannot be fully liberated
process has two-step crushing in an inert gas atmosphere (Pinegar and then separated from each other; in addition, the decomposition
and Smith, 2019). In the first step of crushing, a low-speed two- of electrolyte components, such as LiPF6, DEC, and PC, during me-
blade rotor crusher without a sieve, and in the second step of chanical processes causes a serious threat to the ecosystem. Despite
crushing, a high-speed hammer mill with a 5 mm sieve was used different pretreatment methods that have been suggested by many
for the simultaneous recycling of the LIB, NiMH, and the primary Li researchers, challenges still exist regarding the pretreatment of S-
batteries (Granata et al., 2012). The second step fine crushing in- LIBs.
creases the black mass yield from 60% to 75% in the absence of the There are two types of LIBs crushing and grinding: dry and wet.
impurities from the Al and the Cu current collectors (Kim et al., Dry crushing is carried out in a gastight unit in an inert gas (N2, Ar,
2021). etc.) atmosphere (Kim et al., 2021). Generally, dry crushing can be
After crushing and grinding, the cathode/anode active material carried out in two stages (i.e. firstly shear crushing for chopping and
and Al/Cu-foils are separated by using the differences in size (by secondly impact crushing) after at least 24 h soaking in brine water
dry/wet sieving), density (by gravity separation like heavy media and chopping into small pieces. Over-crushing is less in the dry
separation), and magnetic susceptibilities (by magnetic separa- crushing than in the wet crushing route (Kim et al., 2021). One-
tion). Zhang et al. (2018) generated small battery pieces by shred- stage cutting mill crushing provides poor liberation. Second-stage
ding from NaCl solution immersed S-LIBs. They used impact milling can achieve the selective liberation of LCO. Wet crushing
crushers fitted with blade crushers and ground the battery for 20 s can be performed with a blade crusher with water addition. Li et al.
at 3000 rpm. The crushed pieces were classified into four size (2019) found that crushing to 12 mm achieved maximum Co con-
groups by dry sieving. The coarse pieces of plastic, Cu, and Al were tent and minimum total impurity (Al, Cu, and Fe) contamination in
separated from the CAM and anode active materials at 75 mm. After the black mass. The wet shredding can be conducted at room
removing the floating hydrophobic hydrocarbon (HC) material on temperature, so the water can act as both a scrubbing agent and a
the water surface, LiCoO2 and graphite were separated by reverse temperature controller. The shredder output slurry contains both
froth flotation. Due to simplicity and scalability, mechanical pre- hydrophobic plastics floated on the water surface and can be
treatment is the most widely used method of S-LIB separation. removed by scrapping manually and the electrode active materials,
However, setting up a stable classification setup is essential, and which can be separated via the sieving operation. The dry crushing
this method can cause noise, dust, and harmful gas production. selectively crushes LCO and graphite electrode materials to liberate
Additionally, it is not easy to ensure the perfect separation of all them from the Cu and Al-foils without over-crushing (Kim et al.,
materials using this method. 2021). CAMs and anode active materials laminate that has been
The comminuted LIB products contain three parts: An Al- detached from its current collector and is still held together by the
enriched coarse (>2 mm) fraction, a CueAl-enriched medium binder. This type of particle comes as aggregate for particle sizes
(0.25e2 mm) fraction, and a Co, Li, and a graphite-enriched fine 38e850 mm. Guan et al. (2017) suggested that the mechanochem-
(<0.25 mm) fraction. It seems that the 212 mm screen is sufficient ical reduction process via planetary ball mill enhanced the Li and Co
for Al and Cu foil removal from fine electrode mixture materials. Al leaching efficiency.
and Cu can not be separated from each other by size (Widijatmoko Widijatmoko et al. (2020) firstly used a shredder for anode and
et al., 2020). The mineral phase analysis and the chemical compo- cathode layers to cut into 5 mm 12 mm. Retsch SM2000 cutting
sition analysis revealed that the CAMs obtained from the <0.25 mm mill with 8 mm screen size was used for the first stage liberation.
fine fraction remained in their original crystalline structure and 2.5 min attrition scrubbing with 2360e850 mm low Fe silica sand at
chemical composition in LIBs. However, the surface of these fine 1000 rpm was performed as a secondary liberation. The pulp
powders was coated with a layer of binder HCs, leading to difficulty density was around 70% and S-LIBs/silica media ratio was 10%.
in separation by froth flotation. The valuable black mass is in fine 2.5 min attrition scrubbing was sufficient for fine CAMs production
fractions, whereas large fractions generally contain less valuable with wet sieving from 212 to 38 mm screens.
components, such as Al/Cu current collector foils, metallic/plastic The grinding-assisted flotation process for the separation and
cell cases/shells, and plastic separators. Shin et al. (2005) proposed recovery of LCO and graphite from the S-LIBs is proposed by Yu
a combined process to recover metals from S-LIBs that used me- et al. (2018). The anode and cathode strips were firstly crushed to
chanical separation for the collection of CAMs, followed by a hy- 74 mm by an impact crusher. The resulting mixed electrode powder
drometallurgical treatment for metal extraction. Enriched particles was ground in a ball mill for 5 min. The lamellar graphite structure
of LiCoO2 were obtained through a series of mechanical treatments slides, flakes, and exposes a large number of new fresh hydrophobic
Table 9
Advantages and disadvantages of different pretreatment methods.
Pretreatment method Advantages Disadvantages
Alkaline NaOH dissolution Simple treatment, high separation rate. Al recovery is difficult; alkali wastewater discharge.
Ultrasonic-assisted operation The operation is simple, no gas High noise pollution, high capital investment.
emission.
Solvent extraction (SX) High separation efficiency Solvents are expensive, environmental hazards are high.
Thermal treatment (Calcination Simple treatment, high capacity. Energy consumption is high, high device investment,
process) toxic gas emissions.
Mechanical methods Simple, suitable operation. Toxic gas emissions, cannot separate mixed and all kinds of electronic components in
LIBs
surfaces under the horizontal shear force generated by the grinding treatment was achieved at 450 C for 15 min by Wang et al. (2018).
media. The organic binder film-coated LCO particles are partially At these conditions, LCO outer layer was eliminated and graphite
worn down to restore the original hydrophilic surfaces. With the was protected from combustion which resulted in a 97.7% Co re-
action of the vertical rolling pressure, the adhesion of LCO and covery rate. Zhang et al. (2020) used optimum pyrolysis condition
graphite could occur and finally become an important separation at 550 C using 10 C/min and pyrolysis time for 15 min. The
problem. Even though the adhesion behaviour in the 5-min cathode grade was slightly improved from 94.7% to 94.9%, but its
grinding process may lead some LCO concentrate to follow hydro- recovery was enhanced from about 84% to 91%, which supports that
phobic graphite into the froth phase to reduce the flotation re- the wet-ball grinding can remove the residual pyrolytic carbon on
covery efficiency. High wettability difference between LCO and the surface of the CAM efficiently. Two-stage pyrolysis treatment
graphite results in a good flotation concentrate grade. Clean LCO is enhanced the flotation process and upgraded LCO grade to 98%.
obtained from flotation tailing. Grinding-assisted flotation (Liu et al., 2020; Yu et al., 2018; Zhan
et al., 2018; Zhang et al., 2020) destroy the lamellar structure of
14.3.2. Flotation hydrophobic graphite, generating fresh surfaces, and abrasion of
Reverse froth flotation separates fine hydrophobic anodic the organic film coating the hydrophilic LCO particles cause their
graphite from hydrophilic cathodic LiCoO2 (Zhan et al., 2018). original surface. Creating a great wettability difference between
Kerosene (1e2 kg/t) is used as a collector and MIBC as a frother in LCO and graphite leads to very good flotation selectivity. It was
flotation. 3 min conditioning for the collector and 2 min condi- reported that fine grinding could produce a purer product than the
tioning for frother are enough. For a better flotation result, 212 mm coarse grinding at the same recovery.
particle size and 1%e2% w/w solid slurry are used. Before flotation, Liu et al. (2020) used froth flotation with single-stage cryogenic
fine materials can be rinsed with distilled water to remove excess ball milling. Liquid N2 gas was used for cooling recovery and the
electrolytes on the surfaces. 4 min flotation time was sufficient for grade of the LCO concentrates was enhanced after 9 min of cryo-
more than 95% graphite recovery in the froth phase. Valuable genic grinding that removes the hydrophobic organic binding
tailing should contain CAMs with minimum graphite contamina- material from the surface of the LCO and graphite. Flotation
tion. Kerosene dosage increases CAM contents at the expense of its improvement of LCO and graphite by using cryogenic grinding is
recovery. Without kerosene, CAM recovery is high but CAM content achieved by graphite adherence to the air bubbles for flotation and
is low. There are only a few studies on LIBs material flotation. Before hydrophilic LCO remains in the slurry phase. In the flotation pro-
flotation, binders should be removed by burning off for one hour at cess, kerosene, MIBC, NaOH, and amylum were the best collectors,
500 C. Then flotation is employed. Flotation behaviour of anode, frother, pH regulators, and depressants (Shin et al., 2020; Zhao and
cathode and mixed new and S-LIBs material are different. There are Zhang, 2020). Wang et al. (2019a) also investigated cryogenic ball
many benefits of using flotation in LIBs recycling. Firstly, physico- milling for recovering CAM from LCO-based S-LIBs. Liquid N2 pre-
chemical separation process of flotation effectively preserves the treatment at 196 C for 5 min and grinding 30 s enhanced peel off
functional integrity of electrode materials during the recycling fine cathode material from Al-Foil up to 87.3%. PVDF glass transition
process. As a result, CAMs can be regenerated through a lithiation temperature is about 38 C. Liu et al. (2020) combined cryogenic
process and reused in new batteries (Chen et al., 2016). Secondly, ball milling using liquid N2 with froth flotation for LCO and graphite
flotation separates fine materials according to chemistry. This separation.
significantly increases the energy efficiency of downstream pro-
cesses while minimizing greatly secondary waste. Flotation pro- 14.3.3. NaOH dissolution method for Al removal
duces metal reach products that can be used as a high-value He et al. (2019) used an aqueous exfoliating and extracting so-
feedstock for the hydrometallurgical or pyrometallurgical pro- lution that included NaOH salts without strong acid and alkali for
cesses. Finally, flotation beneficiation of S-LIB materials is easily and the recycling of the LIBs that contained LFP and NMC. The cathode
economically applicable for full plant-scale production. materials could be peeled off from the Al-foil by dissolving the Al-
Fenton reagent (including H2O2 þ FeSO4) was used to modify foil. The resulting recovery efficiencies of the Al-foil and the elec-
the surface of the crushed electrode materials for the recovery of trode materials were almost full. In many proposed recycling pro-
LCO and graphite in reverse froth flotation (He et al., 2017). Fenton cesses, the cathode materials are separated from the Al-foil by
reagent removes the organic hydrophobic binder layer and assists leaching the cathode with an alkaline NaOH solution, which works
flotation. First of all, the electrode materials from the S-LIBs were to separate the materials because of the amphoteric property of Al,
immersed in the Fenton reagent to remove the organic binder outer which can react with both an acid and a base. In their process to
layer from particles. Optimum conditions of 1:120 Fe2þ/H2O2 ratio recover the CAM, Nan et al. (2005) used a 10 wt% NaOH solution to
and a 1:75 S/L ratio eliminated most of the organic binder layers separate the LCO-based CAM from Al-foil. Using a NaOH solution
coated on the surface of the electrode materials. After being with a 100 g/L S/L ratio, 5 h reaction time, at room temperature,
modified by the Fenton reagent, the original wettability of hydro- about 98% of the Al-foil was dissolved. When a NaOH solution is
philic LCO and hydrophobic graphite was regained thus the reverse used to dissolve the Al-foil of the cathode, two substances are
froth flotation could be used for the selective separation of LCO and dissolved: the protective layer covering the surface of the collector
graphite. After Fenton treatment, electrode particles are wrapped and the Al. Following reactions occur between Al and Al2O3 and
with an inorganic hydrophobic Fe(OH)3 layer which leads to poor NaOH in the presence of water:
flotation (sink). Yu et al. (2017) determined the effect of the sec-
ondary product of semi-solid phase Fenton on the floatability of 2Al þ2NaOH þ 6H2O / 2Na[Al(OH)4] þ 3H2 (4)
LCO electrode material from S-LIBs. They used 500 mL 0.8 M H2O2,
33.3 mL 0.1 M FeSO4, and 7 g LCO sample in 20 min Fenton treat- Al2O3 þ 2NaOH þ3H2O / 2Na[Al(OH)4] (5)
ment. After filtration and drying, flotation with 300 g/t kerosene as
a modifier and 150 g/L 2-octanol as frother addition after 6 min This NaOH dissolution method has the advantages of both
conditioning time was performed. Pyrolysis at 500 C and ultra- simplicity and high separation efficiency. However, the recovery of
sonic treatment can clean the surface of particles to increase Al is difficult because of the ionic form of Al. In addition, NaOH
floatability. Ultrasonic-assisted flotation improved LCO grade from wastewater is very environmentally harmful to disposal. Molten
67.3% to 93.9% and recovery from 74.6% to 96.9%. Optimum roasting salt AlCl3eNaCl mixture can also be used for Al dissolution.
14.3.4. Solvent dissolution pretreatment for binder elimination foil. Zhang et al. (2014) dissolved the PTFE binders in the NMC-
Unfortunately, some liberated electrode active materials are still based LIBs with trifluoroacetic acid (TFA), which is a strong car-
attached to the current collectors while other detached active boxylic acid with a relatively low boiling point (71.8 C). The opti-
materials are agglomerated by the organic binders after the clas- mum TFA concentration was 15 vol%, S/L ratio 1/8 g/mL, the
sification and the separation operations. Thus, the dissolution of reaction time 180 min, and temperature 40 C in the presence of
the binders or the Al-foils is generally performed with suitable agitation.
solvents. Solvent pretreatment utilizes solutions and solvents to
separate the LCO and graphite from the Al- and Cu-foils/films in the 14.3.5. Ultrasonic-assisted separation for binder elimination
S-LIB. This method eliminates the additive binder material that It is not easy to remove CAM from Al-foil during the S-LIBs
strengthens the foil contact with the active materials, thereby recycling due to the strong bonding force of the PVDF binder.
separating the active materials. By stripping off or dissolving the Ultrasonic-assisted treatment is considered to be one of the effec-
binder, the active material can be separated from the metal foil. A tive methods for stripping CAM from Al-foil because of its strong
commonly used method is to immerse the electrode plate into an cavitation effect (He et al., 2015; Li et al., 2015; Zhang et al., 2013).
organic solvent N-methyl-2-pyrrolidine (NMP) at 100 C to remove Cavitation breaks the intermolecular bonds. When studying the
the PVDF binder by dissolving and separating the Al- and Cu-foils. effects of both agitation and ultrasonic treatment on the separation
He et al. (2019) discharged the LIB by immersing it in an unsatu- of CAMs, Li et al. (2015) discovered that most of the CAMs
rated NaCl solution and separated the battery manually using pli- continued to adhere to the surface of the Al-foils when mechanical
ers. After separating the plastic, metal case, electrode plate, and agitation alone was used. When ultrasonic treatment alone was
separator, the cathode was cut into small pieces. The cathode pieces used, only parts of the CAMs were separated. However, when both
were inserted in NMP solution at 80 C for 2 h, thereby dissolving methods were used at the same time, almost all of the CAMs could
the organic binder and separating the Al-foil and CAM. Most bat- be stripped from the foils. This may be because of the cavitation
teries use a PVDF binder to attach the active materials, however, effect of ultrasonic treatment, which can generate higher pressure
some use PTFE binders, which require different organic solvents to to destroy insoluble materials and disperse them in solution. The
use around 100 C, which increases the operating cost and creates rinsing effect of mechanical agitation further promotes the sepa-
toxic waste products. Table 10 presents previously used solvents for ration of CAMs from Al-foils. He et al. (2015) attributed the mech-
binder dissolutions. anism by which CAMs were separated from Al-foil by ultrasonic
Liu et al. (2006) used N, N-.dimethylacetamide (DMAC), which treatment to the dissolution of the binder and the cavitation effect
also dissolves PVDF that is about 10%, for the separation of the LCO produced by the sonication. Depending on this mechanism, the
CAM from the Al-foil because of its economic edge over NMP. When stripping efficiency of the CAM reached 99% with NMP at 70 C,
the S/L ratios were controlled between 1:4 and 1:5, the CAM was 240 W ultrasonic power, and 90 min processing time. CAM that was
separated from the Al-foil, which was followed by the filtration of separated from the Al-foil by ultrasonic treatment exhibited a low
LCO and graphite conductive agents from the solvent. Because the degree of agglomeration, which significantly facilitated subsequent
boiling point of DMAC is 165 C, DMAC can be evaporated by leaching processes.
heating it at 120 C for 12 h. Zhou et al. (2010), Song et al. (2013; For the separation of the LCO material from Al foils, NMP is the
2014), and Xu et al. (2014) used N, N-dimethylformamide (DMF) to best solvent for PVDF or N, N-dimethylacetamide (DMAC), DMF,
separate the LCO and NMC CAMs from the Al-foil. The cathode NeN- dimethyl sulfoxide (DMSO), ethanol, or molten salt of
scrap materials were immersed in DMF or a mixture of DMF and AlCl3eNaCl can also be used. The peel-off efficiency in any of the
ethanol at 70 C. solvents did not surpass 10% with an S/L ratio of 1:10 g/mL at 60 C
Wang et al. (2019b) achieved the separation of the CAMs and the for 30 min. However, the peel-off efficiency increased by at least six
Al-foil using a low-temperature AlCl3eNaCl molten salt system, times with the assistance of the ultrasound in the increasing order:
which had a better peeling-off performance than the commonly ethanol < DMSO < DMF < DMAC < NMP. 100% peeling off was
used NaOH or nitrate systems. The optimum performance was achieved (Liu et al., 2006). Ultrasonic treatment along with solvent
achieved with an S/L ratio of 1:10 g/mL at 160 C for 20 min. The dissolution is one of the best solutions for cathode material
heat storage of the phase transformation of the AlCl3eNaCl molten removed from Al-foil.
salt caused the melting of the PVDF organic binder for the sepa-
ration of cathode active material and Al-foil. Specifically, when the 14.3.6. Thermal (heat treatment)/Pyrolysis/Calcination
heating temperature exceeds the phase transformation tempera- pretreatment for binder elimination
ture of 153 C, the AlCl3eNaCl molten salt mixture is converted The binder materials that bind the active materials and the
from a solid to a liquid compound by absorbing a large amount of conductive carbon together and fix them to the current collectors
heat. If the temperature continues to rise to 160 C, PVDF melts, can be also eliminated by heat treatment. The thermal treatment
which results in the efficient separation of the CAMs from the Al- uses high-temperature binder decomposition to decrease the
Table 10
Solvents used for binder dissolutions in S-LIB recycling.
Solvent Binder Temp./Time/ Material Material remained Reference

S/L removed
NMP PVDF (Solubility: 200 g/kg solvent; boiling point: 200 C; <100 C/1h LiCoO2 and Al and Cu metals by Contestabile et al. (2001)
price: 5e6 $/kg) /10% graphite filtration
DMAC PVDF (Boiling point: 165 C; price: 21.5 $/kg) d LiCoO2 Al-foil Liu et al. (2006)
DMF Suitable for PVDF 60e70 C/ NMC/LCO Al-foil Song et al., 2013; Xu et al., 2014; Zhou
Not suitable for PVDF (Price: 0.9e2.4 $/kg) / et al., 2010
TFA PTFE acetic acid 15 v%, L/S: 8 mL/g with agitation (Boiling 40 C/3 h/d NMC Al-foil Zhang et al. (2014)
point: 71.8 C)
AlC
3 NaCl PTFE, 1/10 g/mL (price: 10e25 $/kg) 160 C/ Cathode Al-foil Wang et al. (2019b)
molten salt PVDF 20 min/d material
bonding force between particles of cathode/anode active material metals and generate a high-intensity eddy current in an alternating
that can then be easily separated by screening. Calcination pre- magnetic field, they could be separated in the particle size range of
treatment occurs in the temperature range of 150e650 C to 2.0e20 mm. Cu and PE separators and NMC active material and Al-
remove conductive carbon, acetylene black, and organic material foil can be separated by gravity separation. In the commercial-scale
from the S-LIB. In addition, by calcination at 250 Ce350 C, the Recupyl process, non-magnetic materials are separated based on
organic PVDF binder can be removed, thereby reducing the density differences (Pinegar and Smith, 2019). For the þ2.0 mm
adherence of the active materials on the Al- and Cu-foils. Yang et al. fraction, Al-shell and separators can be separated by air separation.
(2016) cut the cathode parts into small pieces and placed them in a For 2.0 þ 0.5 mm size fraction, AleCu and separator can be
tube furnace in an inert N2(gas) atmosphere at 550e650 C. Then, separated by electrostatic separation. For 0.5 þ 0.075 mm size
the CAM and the Al-foil were easily separated using gravity sepa- fraction, grinding and dry sieving from 0.075 mm is
ration. However, calcination pretreatment requires expensive fur- performed. þ0.075 mm size fraction is sent to the electrostatic
naces, is an energy-intensive process and can emit hazardous gases separation and 0.075 mm is sent to the froth flotation which is
(Bae & Kim, 2021). carried out after surface modification to separate LiCoO2 and
The LCO CAMs were separated using a thermal treatment of the graphite (Gratz et al., 2014; Kim et al., 2021). Surface modification
S-LIBs in two steps. After drying at 60 C for 24 h, the first thermal can be achieved by either Fenton-assisted flotation (Yu et al., 2017)
pretreatment was performed at 300e500 C for 1e2 h to eliminate or roasting-modified flotation. Fenton-assisting flotation increased
carbon, PVDF binder, and the organic additives in the CAMs. The LiCoO2 grade to 60% from 55.6% with direct flotation. Treatment
second thermal treatment was conducted at 700e900 C for with Fenton reagents removes the organic hydrophobic binder
1.5e2 h to remove carbon by burning off the residual unburned from both graphite and CAMs. Hydrophobic graphite floats and
organics. PVDF and the carbon powder in the anode materials were hydrophilic LCO sink during flotation. The roasting-modified
removed with the high temperature calcining after LCO was flotation exhibited an 89.6% LCO concentrate grade with the high-
initially separated from the Al-foil (Li et al., 2010a, 2013; Liu et al., est selectivity between tailings and concentrate (Zhang et al., 2018).
2006; Meng et al., 2017; Natarajan et al., 2018; Zhang et al., 2014).
A vacuum pyrolysis method to separate CAM was proposed by 16. Metal-extraction processes for S-LIBs
Sun and Qiu (2011). The electrolyte and binder were evaporated or
decomposed, which reduced the adhesion between the CAM and Metal extraction from S-LIBs is an important part of the whole
Al-foil during the process of pyrolysis, If the pyrolysis temperature recycling process. This recovery process focuses on changing the
was lower than 450 C, the CAMs did not peel away from the Al- solid metals into their alloy form or solution form, which facilitates
foils. When the temperature was between 500 and 600 C, the the subsequent separation and recovery of metal components.
separation efficiency improved with an increase in the tempera- There are four main different extraction processes including pyro-
ture. However, the Al-foil became fragile at temperatures above metallurgy, hydrometallurgy, biometallurgy, and direct recovery.
600 C, making it difficult to separate the CAM from the Al-foil. A From these approaches, hydrometallurgy has become a promising
reducing thermal treatment process to separate the CAMs from the novel process because of its attractive recovery rates and the high
Al-foil collectors was proposed by Yang et al. (2016). It was shown purity of the final products.
that controlling the reduction reaction temperature allows the Although most of the previous researchers so far have firstly
CAMs to be separated from the Al-foils. Besides, this process concentrated on the recovery of expensive CAMs and secondly Al-
changes the CAMs molecular structures, which enhances the and Cu-foils, it is also possible to recover anodic graphite and even
leaching of metals during the leaching steps. Thermal treatments electrolytes using low-temperature processes. Both graphite and
are straightforward operations and have high throughputs. How- electrolytes, of course, burn in a smelter, supplying some of the
ever, they generate toxic gas emissions during the thermal treat- process fuel energy. Plastic polymeric separators (thin porous film)
ment process. also burn in the smelter. There is no suggested process proposal for
recovering separators. Polymeric plastics could be recovered, but
14.3.7. Classification they are cheap. Recovery of anode material (graphite) using simple
After comminution, classification can be performed by sieving physical separation processes has been proved as part of direct
or zigzag air classifier. Air separation in a zigzag classifier can be recycling; anode material is cheaper and weakly attached to the Cu-
utilized after two-stage of crushing of the discharged cells from the foil than CAM but must be separated to obtain useable CAM.
S-LIB. Screening from 212 to 38 mm significantly separates Li & Co Different methods of separating the black mass into anode and
from Al & Cu. The finer the screen size the better the separation. cathode fractions have been studied, including heavy media gravity
separation using toxic bromoform and froth flotation. Gravity
15. Separation separation between LiCoO2 (4.9 gr/cm3) and graphite (2.26 gr/cm3)
can also be used for further purification of flotation tailing. Anode
After the classification of the S-LIB comminution products, the material could also be recovered using hydrometallurgical pro-
physical/mechanical/physicochemical separation based on the cesses. Graphite is not soluble in acids, which would remain as a
particle size, density, magnetic susceptibility, electrical conductiv- solid residue while the CAM dissolves. The anode material could
ity, and surface chemistry properties (such as gravity, magnetic, then be recovered by filtration, but its quality becomes low. Gaines
eddy current, electrostatic, and froth flotation separation) are (2018) investigated the recovery of the Li-salt-containing electro-
employed. Magnetic separation has been often used for the lyte, by extraction of breached cells with supercritical CO2 and SX.
removal of the Fe and steel casing, in the S-LIB recycling process. Even though the recovered electrolyte performed well in recycled
Shin et al. (2005) used magnetic separation after vibration sieving cells, the process is not found to be cost-effective. Interest may
to separate the CAM from the LCO and the Al-foils, the anode, the increase when large volumes of material are being processed.
steel casings, and the plastic packaging. The eddy current separa- Current research has been concentrated on the extraction of high-
tion allows the electrical conductors (Cu, Al-foils) to be separated value metals from CAMs using pyrometallurgy and hydrometal-
from the non-conductors (plastics) or the minimally conductive lurgy. Before being fed into metal extraction processes, the sepa-
materials and an eddy current separation apparatus is used for the ration of mixed materials from LIBs using low-cost and energy-
recycling of the LFP-based LIBs. Cu and the Al foils are conductive efficient methods is critical to lower processing costs, minimize
secondary waste, and increase product values. The main objective purified Li was obtained. In addition, Tra€ger et al. (2015) proposed a
of LIB recycling is to recover as many materials as possible, in a vacuum evaporation process and selective carrier gas evaporation
useful and reusable condition, and in an environmentally friendly at high temperatures to evaporate Li from S-LIBs. However, the
and economic manner. Throughout this paper, shortcomings of temperature was higher than 1400 C, which is very high. Li et al.
existing processes are highlighted for improvement of the current (2016) roasted LiCoO2 and graphite at 1000 C for 30 min under
practices. an inert N2 gas environment. The roasting products were Li2CO3,
carbon, and Co which were then water leached and separated by
magnetic separation. The concentration of the Li solution was only
16.1. Pyrometallurgy
337.4 mg/L which is low for Li recovery. Depending on previous
studies, a novel method to recover S-LIBs by low-temperature
A typical pyrometallurgical S-LIB process for recycling valuable
roasting under an inert Ar gas atmosphere, followed by the re-
metals is high-temperature smelting reduction in a furnace
covery of Li2CO3 from the roasting product using water leaching
without any pretreatment to produce mixed alloys. In the pyro-
was proposed by Hu et al. (2017). The results showed that the
metallurgical process, charcoal (reductant) and slag-forming agents
roasting products were Li2CO3, Ni, Co, and MnO when the cathode
(fluxes) are added in the reductive smelting. Umicore in Belgium
was reduced to 650 C for 180 min with a 19% C dosage. The
developed a combination of pyrometallurgical and hydrometal-
roasting products were then dissolved in water and fed with CO2;
lurgical processes to recycle waste battery mixtures. The plastics,
this created the conversion of insoluble Li2CO3 into LiHCO3. The
organic binders, solvents, and graphite in the LIBs provide addi-
Li2CO3 was then recovered by evaporation crystallization. The
tional excess fuel heat during combustion, while the metal com-
concentration of Li in the leaching solution reached 4.36 g/L when
ponents are reduced and converted to their alloys. The obtained
the S/L ratio was adjusted to 1/10 (g/L) the CO2 flow rate was
alloys can be further purified by H2SO4 leaching and SX to obtain
confined to 20 mL/min, and the leaching time was 120 min. Even
cobalt oxides and Ni(OH)2. Although pyrometallurgy does not
though recycling valuable metals from S-LIBs by pyrometallurgy is
require any pretreatment, it losses all Li in the slag phase. To reduce
easy, it is not ecofriendly because of its high energy consumption
the Li loss in the recycling process, a novel process that combines
and secondary pollution (Golmohammadzadeh et al., 2017; Wang
pyrometallurgy and hydrometallurgy to recycle valuable metals
et al., 2017a). Besides, the loss of Li in the slag during the recy-
from S-LIBs was proposed by researchers.
cling process is a significant problem that needs to be solved in
Pyrometallurgy uses high temperatures to remove organic ma-
pyrometallurgical treatment.
terial by evaporation and causes reactions in the CAM and anode
active materials to solubilize Li in the aqueous solution in which Li
is recovered. The CAMs were powdered and subjected to calcina-
tion above 700 C, and the lithium metal oxide of the cathode and 16.2. Hydrometallurgy
anode react to form Li2CO3 and metal oxides. The possible reactions
that occur are given in Eqs. (6)e(10). Recycling Li and Co metals from S-LIBs using hydrometallurgy
involves leaching, which dissolves the metallic fraction and recy-
C(s) þ 12LiMO2 / 6Li2O þ 4M3O4 þ CO2(g) (6) cled metal solutions for subsequent separation. Typical leaching
agents are inorganic/organic acids, alkaline solutions, and
C(s) þ 4LiMO2/ 2Li2O þ 4MO þ CO2(g) (7) ammonia-ammonium salt systems. From the mineral acids, HCl
(Barik et al., 2017; Takacova et al., 2016; Zhang et al., 1998), H2SO4
2M3O4 þ C(s)/ 6MO þ CO2(g) (8) (Chen et al., 2011; Dorella & Mansur, 2007; Ferreira et al., 2009;
Kang et al., 2010; Nan et al., 2006), HNO3 (Lee & Rhee, 2002), and
Li2O þ CO2(g) / Li2CO3 (9) H3PO4 (Chen et al., 2017; Pinna et al., 2017) were generally used as
lixiviants to leach valuable metals from S-LIBs. With the help of
2MO þ C(s) / 2M þ CO2(g) (10) reducing agents such as hydrogen peroxide (H2O2) (Chen et al.,
2011; Dorella & Mansur, 2007; Ferreira et al., 2009; Kang et al.,
Water leaching is applied to the calcined powder to dissolve the 2010; Lee & Rhee, 2002; Li et al., 2009), sodium bisulfite
Li. The metal oxide does not dissolve in the water. After water (NaHSO4) (Meshram et al., 2015), or glucose (C₆H₁₂O₆) (Pagnanelli
leaching, the filtration process separates the undissolved metal et al., 2014), Co or Mn with a high-valent state in the solid phase
oxide and the aqueous solution to produce a rich Li2CO3 solution, is reduced to easily soluble Co2þ or Mn2þ. The main factors affecting
followed by water evaporation to finally obtain Li2CO3 powder (Bae the metal leaching process include the leaching time, reaction
& Kim, 2021). Some researchers used additional acids (HNO3, HCl, temperature, leaching agent concentration, S/L ratio, and concen-
and H2SO4) during the roasting for higher Li extraction rates. Peng tration and type of reducing agents.
et al. (2019) used HNO3 to nitrate the S-LIBs and roasted them at Takacova et al. (2016) studied the Co and Li recovery from CAM
250 C for 1 h. After roasting, by water leaching, Li solution was of spent mobile phone and laptop LIBs using H2SO4 and HCl. Co, Li,
produced and with carbonation, Li2CO3 was produced with low- Ni, and Cu contents in the sample for 0.71 mm size fraction were
temperature roasting. Sulphating roasting with H2SO4 and chlori- 22.4%, 3.7%, 1.5%, and 1.3%, respectively. HCl was found as a better
nation roasting with HCl can also be used. However, the low solu- leaching reagent than using H2SO4. The optimal conditions for Co
bility (13 g/L) of Li2CO3 requires a large amount of solvent and Li recovery were: 2.0 M HCl concentration, 60e80 C temper-
consumption. Besides, the pyrometallurgical treatment requires ature, and 90 min leaching time.
complex calcination equipment and can create toxic gas emissions. The following equations describe the possible reactions of Co
A reduction smelting method to recover valuable metals from S- and Li in an H2SO4 solution, with values of DG080(kJ):
LIBs was used by Georgi-Maschler et al. (2012). Valuable Fe, Co, Ni,
and Mn metals were converted to alloys. However, Li is lost as slag 4LiCoO2 þ 6H2SO4 4 2Li2SO4 þ 4CoSO4 þ 6H2O þ O2
or dust during this process. With further slag leaching with H2SO4, DG080: 608.96 (11)
Li2O þ H2SO4 4 Li2SO4 þ H2O DG080: 306.69 (12) reducing agents, HCl provides a higher leaching efficiency due to its
Cl ions, which enhance the dissolution. Co2O3.H2O was precipitated
2Co3O4 þ 6H2SO4 4 6CoSO4 þ 6H2O þ O2 DG080: 188:42 (13) at pH: 3 with NaOH and NaClO at a purity of 99.3% and Ni(OH)2 was
precipitated at pH: 11 with NaOH at a purity of 96.4%.
Li2CO3 þ H2SO4 4 Li2SO4 þ H2O þ CO2 DG080: 126:61 (14) According to Eqs. (17) and (20), lithium and cobalt chloride and
halogen Cl2 gas are generated during the leaching process, which
CoO þ H2SO4 4 CoSO4 þ H2O DG080: 114.12 (15) may result in significant environmental issues. Therefore, some
researchers used HNO3 or H2SO4 instead of HCl to leach LCO. For
2Co2O3 þ 4H2SO4 4 4CoSO4 þ 4H2O þ O2 DG080: 94.17 (16) instance, Lee and Rhee (2002) treated LiCoO2 CAM with 1.0 M
HNO3 þ H2O2 reductant at 75 C. 75% Li and 40% Co were achieved
For H2SO4, all calculated values of DG0 are negative at all ranges in the absence of H2O2. However, the leaching rates of Co and Li
of temperatures (20e80 C). It follows that the reactions occur in exceeded 99% in the presence of H2O2 mainly because insoluble
the direction of product formation with a high probability. Co3þ was reduced into soluble Co2þ.
The following equations describe the possible reactions of Li and Chen et al. (2011) proposed a hydrometallurgical approach for
Co in an HCl solution, with values of DG080 (kJ): recycling from S-LIBs to produce cobalt oxalate (CoC2O4); this
process consists of alkali leaching, acid leaching, SX, and chemical
2LiCoO2 þ 8HCl 4 2LiCl þ 2CoCl2 þ 2H2O þ Cl2 precipitation. H2SO4 þ H2O2 were applied as the leaching agent and
DG080: 358.60 (17) as the reductant, respectively. The results showed that the leaching
rates of Co and Li were 95% and 96% under the following conditions:
Li2O þ 2HCl 4 2LiCl þ H2O DG080: 195.87 (18) 85 C temperature, 100 g/L S/L ratios, 120 min leaching time, 4.0 M
H2SO4, and 10% (v/v) H2O2 concentration. The solution pH was
CoO þ 2HCl 4 CoCl2 þ H2O DG080: 42.95 (19) adjusted to remove ionic impurities from the leachate. Co was then
extracted with the solvent extractant P507, followed by precipita-
Co2O3 þ 6HCl 4 2CoCl2 þ 3H2O þ Cl2 DG080: 34.02 (20) tion with ammonium oxalate ((NH4)2C2O4) to obtain the CoC2O4
compound, which resulted in a purity higher than 99% according to
Li2CO3 þ 2HCl 4 2LiCl þ H2O þ CO2 DG080: 28.12 (21) the leaching reaction given below:
Co3O4 þ 8HCl 4 3CoCl2 þ 4H2O þ Cl2 DG080: þ24.05 (22) 2LiCoO2 þ 6Hþ þ H2O2 / 2Liþ þ 2Co2þ þ 4H2O þ O2 (23)
For HCl, all calculated values of DG0 are negative at all ranges of It is relatively easy to achieve high metal-leaching efficiencies
temperatures (20e80 C), except for the reaction (22). It follows using mineral acids. However, these strong acids will produce
that the reactions occur in the direction of product formation with a highly acidic wastewater, Cl2, SO2, NOx, and other harmful gas
high probability. The reaction (22) with a positive value of DG0 emissions, which will create environmental pollution (Yao et al.,
probably occurs in the opposite direction. If only values of DG0 are 2015). Therefore, ecofriendly weak organic acids have been used
taken into account, neglecting kinetics, system complexity, and side as the leaching agents for metal recovery from S-LIBs; these organic
effects factors, the probability of Li and Co extraction in both acids include ascorbic acid (C6H8O6) (Li et al., 2012; Nayaka et al.,
leaching agents increases with increasing temperatures from room 2015; 2016a; 2016b), citric acid (C6H8O7) (Chen et al., 2016;
temperature to 80 C. Golmohammadzadeh et al., 2017; Li et al., 2013; Yao et al., 2015),
In the leaching process, the major aim is to obtain maximum % oxalic acid (C2H2O4) (Sun and Qiu, 2012; Zeng et al., 2015), formic
Li/Co/Ni dissolution in PLS under optimum conditions (minimum acid (CH2O2) (Gao et al., 2017; Zeng et al., 2015), acetic acid
energy and reagent consumption, maximum efficiency, and high (CH3COOH) (Gao et al., 2018; Golmohammadzadeh et al., 2017),
percent solid), while keeping the content of other impurities to a succinic acid (C4H6O4) (Li et al., 2017), tartaric acid (C4H6O6) (Zhang
minimum. Leaching can be explained as the diffusion of the desired et al., 2015), etc.
solid content into the liquid with heterogeneous reactions occur- Li et al. (2012) developed a combined process consisting of ul-
ring at the interface between solid particles and the liquid medium. trasonic cleaning, roasting, and ascorbic acid leaching to recycle
Leaching can be done with different reagents. Although strong valuable Li and Co metals from S-LIBs. C6H8O6 was chosen as the
mineral acids (like H2SO4, HCl, and HNO3) have high efficiency, their leaching agent as well as the reducing agent to increase the
wastes are harmful to nature. Weak organic acids (like citric, oxalic, leaching rate of Co. Using 1.25 M C6H8O6 and a 25 g/L S/L ratio, the
malic, ascorbic, etc.) have lower efficiency, although their wastes leaching rates of Li and Co reached 98.5% and 94.8%, respectively.
are not harmful to nature. During the leaching process, an H2O2 When LCO is leached under these conditions, it first dissolves to
reducing agent is usually added to convert all Co or Mn to their produce soluble C6H6O6Li2; the insoluble Co3þ in LCO is converted
divalent states, which are easily leached out by acid solution. to the easily soluble Co2þ by the ascorbic acid, and the C6H8O6 is
Table 11 shows some of the previous LIB leach performances using oxidized to C6H6O6. The leaching reaction can be given as follows:
organic and inorganic acids.
The leaching of NCA cathodes in H2SO4, HCl, and HNO3, was 2LiCoO2 þ 4C6H8O6 / C2H6O6Li2 þ 2C2H6O6Co þ C6H6O6 þ
investigated by Joulie et al. (2014). It was found that HCl provides 4H2O (24)
the best leaching efficiency and the nature of the acid has a sig-
nificant effect on the leaching rate of the metals. The optimum An economically efficient method for metals recycling from S-
conditions for HCl leaching are 4.0 M concentration, 90 C tem- LIBs that combined reduction leaching with selective precipitation
perature, 18 h leaching time, and 5 g/L S/L ratios. Almost 100% of the was developed by Chen et al. (2016). C6H8O7 was used as the
valuable metals in the CAM could be dissolved under experimental leaching agent, and D-glucose was selected as the reducing agent to
conditions. Leaching Co3þ from the NCA cathode without a dissolve the waste CAM. About 99% of the Li, 94% of the Mn, 92% of
reducing agent is generally very difficult because of the conversion the Co, and 91% of the Ni were dissolved using 1.5 M C6H8O7 con-
of Co3þ to Co2þ. As a result, when H2SO4, HNO3, or HCl is used, HCl centration, 20 g/L S/L ratios, 0.5 g/g reducing agent, 120 min reac-
should be chosen as the leaching agent in the absence of other tion time, and 80 C temperature. The selective precipitation
Table 11
Previous S-LIB leaching optimum conditions.
Reagent-acid Oxidant T ( C) T (min) S/L (g/L) Recovery (%) Reference
1.25M citric 1% H2O2 90 30 20 Li: 100%; Co: 90% Li et al. (2010b)

1.5M Citricþ0.5 g/g D-glucose d 80 120 20 Li: 99%; Co: 92%; Ni: 91%; Mn: 94% Chen et al. (2016)
1.5M DL-malic 2% H2O2 90 40 20 Li: 100%; Co: 90% Li et al., 2010a
1.0M oxalate d 80 120 50 LiCoO2 98% Sun and Qiu (2012)
1.25M Ascorbic d 70 20 25 d Li et al. (2012)
4M HCl d 80 120 Li: 97%; Co: 99% Li et al. (2009)
4M HCl (NCA) H2O2 90 1080 50 Li: 100%; Co: 100% Chen et al. (2011)
HNO3/H2SO4 10% H2O2 75 120 d Li: 99%; Co: 99% Chen et al. (2016)
1M H2SO4 (LCO) d 85 d d Li: 96%; Co: 95% Chen et al. (2011)
4M H2SO4 CoC2O4Y
method was then used to separate and recycle the valuable metals. residual organic PVDF binder. Li et al. (2010b)'s results showed that
It was also decided that the residue leachate after precipitation nearly 100% Li and more than 90% Co were leached by using a
could be reused as a leaching agent, which revealed about 98% 1.25 M C6H8O7 solution containing 1.0 vol% H2O2 reductant,
similar leaching performance when compared with the fresh leaching at 90 C temperature for 30 min period and the S/L ratio of
leaching agent. 20 g/L.
A thermal treatment or pyrolysis was also suggested for the full
24LiNi1/3Co1/3Mn1/3O2 þ 24H3Cit þ C6H12O6 / 6CO2 þ (8/3) recovery of the CAMs. The organic PVDF binders generally
Ni3(Cit)2 þ (8/3)Co3Cit(2) þ (8/3)Mn3Cit(2) þ 8Li3Cit þ 42H2O (25) decompose at above 500 C and the volatilization of the electrolyte
occurs at lower temperatures and the C conductive agents are burnt
Organic trichloroacetic acid (TCA), which is a biodegradable off at higher temperatures. Thermal treatment is harmful to the
leaching agent and reducing agent H2O2, was used to selectively environment. The inorganic acid leaching of S-LIBs has previously
leach LiNi1/3Co1/3Mn1/3O2 (Zhang et al., 2015) Under optimum been investigated using H2SO4, HCl, and HNO3 by many researchers
conditions (3.0 M TCA concentration, 50 g/L S/L ratios, 4 vol% H2O2 (Takacova et al., 2016; Wang et al., 2016; Zhang et al., 2014; Zhou
concentration, 60 C leach temperature, 30 min leaching period), et al., 2010). It was reported that the leaching rate of Co is higher
the leaching rates of Li, Co, Ni, and Mn were 99.7%, 91.8%, 93.0%, and when the existence of Na2S2O3 is compared with H2O2 and the
89.8% respectively, whereas the leaching rate of Al was only 7.0%. In absence of a reducing agent (Guo et al., 2016; Shin et al., 2005).
addition, the leaching rate of Al could be further controlled Industrial Li recovery from batteries is limited. Today, most in-
depending on the use of the leachate. Currently, the CAM used for dustrial plants (Xstrata, Umicore, Accurec, Recuply, OnTo, Dowa,
leaching is obtained from waste LIBs by manual dismantling or in Sony, AEF, etc.) recover Li by hybrid
the form of cathode scraps from battery production plants, that (pyro þ hydro þ electrometallurgy) processes with all types of
have higher purity. Industrial raw materials recovered from S-LIBs mixed and various sizes of batteries (NiCd, NiMH, LIBs, etc.). The
recycling are usually more complex than the cathode scraps from current LIB recycling ratio is very low and has the following
LIB production processes, and the cathodes that are obtained after drawbacks: Environmentally unfriendly; Produces extensive liquid
pretreatment usually contain heterogeneous metal components. and toxic waste by-products; Medium to low-grade end products;
Leaching the CAM using acid may not manifest ideal selectivity; the Complex processing and purification steps; Low Li and Co recovery
leachate generally contains many ionic impurities, which increases with little to no recovery of remaining metals, and large con-
the difficulty of downstream purification and separation. Thus, sumption of reagents and energy. Table 12 shows the possible
ammonia (NH3)-ammonium sulfate ((NH₄)₂SO₄) is used as the impurities and their consequences on the hydrometallurgical
leaching lixiviate and Na₂SO3 is used as the reducing agent to refining process. For the hydrometallurgical flowsheet, ionic spe-
selectively leach valuable Li, Co, and Ni metals from LiNi1/3Co1/ cies in the PLS must be separated from each other once they are in
3Mn1/3O2 (Zheng et al., 2017). Optimum operating conditions were solution. The most commonly applied methods cover precipitation,
searched, and it was found that in the presence of 4.0 M NH3, 1.5 M SX, electrochemical processing, membrane separation, etc. (Gaines,
(NH₄)₂SO₄, 0.5 M Na₂SO3, 500 rpm mixing speed, and 10 g/L S/L 2018).
ratio, the leaching rates of Li, Ni, Co, and Al were 95.3%, 89.8%, Biometallurgical processes, with simple operation and mild re-
80.7%, and 4.3%, respectively. During the leaching process, the total action conditions, have the benefits of being cost-effective; less
selectivity of Li, Ni, and Co was more than 98.6%. It was also pollution and corrosion; but, their drawbacks are the difficulty in
observed that Mn from LiNi1/3Co1/3Mn1/3O2 was co-leached into the bacteria development, long leaching time due to the slow kinetics,
PLS during the leaching process and then precipitated from the and poor leaching efficiency. Also, very low percent solid is used in
solution in the form of (NH4)2Mn(SO3)2H2O. bioleaching operations.
A combined process of dismantling, size reduction, physical
dissolution, thermal treatment, and organic acid leaching was used 16.3. Precipitation
by Li et al., 2010a; b). Firstly, both the plastic and steel cases that
cover the batteries were manually dismantled from the S-LIBs. The precipitation method utilizes the difference in the solubility
Once dismantled by hand, the cathode and anode were manually of metal compounds, which is dependent on the specific pH and
uncurled and separated, followed by soaking in N-methyl- medium temperature. Precipitation is the most commonly used
pyrrolidone (NMP) at 100 C for 60 min period. According to Or purification method for separating Li from leached PLSs. Materials
et al. (2020), NMP dissolution is not polar; therefore, it can not be with low solubilities, such as transition metal hydroxides, carbon-
used for electrodes that contain a poly (tetrafluoroethylene)-based ates, or oxalates, are easily precipitated. Thus, NaOH, Na2CO3, and
binder. The CAMs were effectively separated from their Al- and Cu- Na3PO4 types of precipitants are mainly used to precipitate other
foils. Secondly, after being dried at 60 C for 24 h, the separated dissolved metals in the PLS, followed by Li extraction in the form of
CAMs were calcined at 700 C for 300 min to remove the C and Li2CO3, LiOH, or Li3PO4. For instance, Li2CO3 has a higher tendency
Table 12
Impurities and their consequences for hydrometallurgical purification refining (adapted from https://accurec.de/publications-downloads?lang¼en).
Accompanying material Problem formation in hydrometallurgy Troubleshooting
Electrolyte (EMC, DMC) Formation of organochlorine compounds, toxic gases, increased acid consumption, costs for pre-wash Evaporation/decomposition by
required thermal pretreatment
PVDF (Adhesive; 100% in AM) Insoluble in acids and remains in the filter cake, increases disposal costs Decomposition by thermal
pretreatment
LiPF6 (conducting electrolyte The HF(g) formation, fast corrosion to the equipment; LiF formation, thus, Li depletion in aqueous and Decomposition by thermal
salt; 100% in AM) metal-containing phase pretreatment
Mn Increased operating costs because of necessary precipitation and disposal, as well as cross- Slagging Pyrometallurgy
contamination in Fe and Al fraction, more difficult recycling opportunity
Al and Fe Increased operating costs because of necessary precipitation and disposal of waste. Al reduces filtering Slagging Pyrometallurgy
efficiency.
Plastic residues (separator, Additional filter expenditure; disposal costs for incineration Decomposition by thermal
sleeve, cable covers, etc.) pretreatment
Graphite (100% in AM) Foam formation with an impact on the plant construction and cost of process additives Reducing agent Pyrometallurgy
LiFePO4 (100% in AM) Formation of stable Ni and Co PO4's, hazardous wastewater with PO4, corrosion because of gas Slagging Pyrometallurgy
formation, HF favouritism, basic safety concerns, filtration difficulties
Silicon (LiB Gen. Si Anode) Gel formation increased filtration efforts and high waste disposal cost Slagging Pyrometallurgy
to form low-solubility Li2CO3 under high pH conditions because of 16.6. Direct recycling
the formation of carbonate ions. Also, the Li2CO3 solubility de-
creases at higher temperatures (12.9 g/L at 25 C, 10.8 g/L at 40 C), For direct recycling, the CAM and anode active materials must
which makes precipitation easier. Compared to other Li compounds be separated from each other without changing the particle
(LiOH e 129 g/L, LiCl e 815 g/L at 25 C) Li2CO3 has a substantially morphology using physical/mechanical separation processes.
lower solubility, which makes it easier to precipitate. The precipi- Heavy media separation and froth flotation can be used. The most
tation method is the safest, cheapest, and most efficient refining efficient methods to separate single/mixed batch cathode and
process for hydrometallurgical treatment. Table 13 summarizes the anode from each other, and to remove Al/Cu-foils should be
previous results of some studies. Detailed results are given by Bae determined before direct recycling. For mixed batch, the CAMs
and Kim (2021). must be separated from each other to obtain the highest possible
For fine-tuning of the precipitation methods, operating condi- production value. Although there is a patent for magnetic sepa-
tions (such as medium pH, Li concentration, temperature etc.) ration, it may not be economical, and it is unknown whether
should be studied more to produce the required property products. similar formulations (like two different NMCs) could be separated
from each other. Methods for separating cathodes from each other
16.4. Solvent extraction (SX) or for using a mixed product would open up possibilities for direct
recovery of high-value cathode products (Gaines, 2018).
SX uses a two-liquid phase system to separate Li from the After disassembly, shredding, screening and physical anode and
leached CAM. It utilizes relative solubility to separate ions from electrolyte materials separation, Li2CO3 is added to the depleted
polar and nonpolar liquids. Nonpolar extractants are mainly used to NCM black mass powder in direct recycling. Calcination produces
separate valuable metals (Co, Ni, and Mn), and Li is separated from regenerated CAM for new batteries. In this method, Li is replen-
the stratified aqueous solution. Non-aqueous solutions dissolve ished (i.e. relithiation) with the thermal treatment.
Co3þ, Ni3þ, and Mn3þ while aqueous solutions dissolve Liþ. Cyanex There are many differences between direct recycling and hy-
272, PC-88a, Cyphos IL-101, and D2EHPA can be utilized to separate drometallurgical processes. Direct recycling retains the cathode
Co, Ni, and Mn. Table 14 shows previous SX conditions and results crystal morphology, while hydrometallurgy uses strong mineral
for LiCoO2 CAM. acids to dissolve the CAM into its constituent ions. Working with
inorganic acids increases process costs and complexity. There are
16.5. Selective adsorption some attempts for using weak and biodegradable organic acids.
After leaching with acid, the dissolved constituents can be sepa-
Selective adsorption separates Li-ions using a Li-ion sieve to rated from each other and reused to manufacture new CAM in the
absorb the dissolved Li. Spinel-structured Mn-type Li-ion sieves are LIBs. Several stages of SX are generally used to separate the Co and
inorganic bead-type adsorbents that are extremely selective for Li- Ni ions, which have very similar properties and are thus difficult
ions in a Li-containing PLS and originate from the technology used to separate from each other (Gaines, 2018). Worcester Institute of
to extract Li from brines. Since Li is the smallest metal ion, Li-ion Technology used the mixture without separation by adding suf-
sieves use a vacancy to allow only Li-ions. LieMn oxide spinel has ficient virgin materials to obtain relative proportions suitable for
the highest selectivity, capacity, and stability among the inorganic the production of the desired CAM formulation (Gratz et al., 2014).
solvents. Because of the low toxicity, it is the most commonly used For most CAM chemistries, the constituents in the PLS have some
material. Wang et al. (2017b) leached Li from S-LIBs using an intrinsic value, and their recovery after leaching makes economic
NH3eH2OeNH4HCO3 solution in the presence of an H2O2 reduc- sense. However, for LFP and LMO materials, the constituent value
tant. An Mn-type Li-ion sieve can be used to selectively adsorb Li is so low that hydrometallurgy does not pay. BYD Co. claimed an
with the leached Li, Co, and Ni solutions. The Li-adsorbed Li-ion economical direct recovery of LFP in China. Direct recovery of LFP
sieve can be separated and dissolved with HCl. Then, NaOH and has been also reported by Li et al. (2017).
Na2CO3 can be added to separate Li2CO3. Li-ion sieves are quite
costly and requirement of an additional HCl leaching process to 17. Current situation of Li extraction worldwide
separate the Li combined with MnO2. Currently, there are some
patents for bead-shaped Li-ion sieves. Demand is very high but supply is inadequate.
Table 13
Some previous precipitation test conditions and results.
Electrode material Leach reactive and conditions Temp. Precipitant References

( C)
/Time
Li0.3Ni0.3Mn0.3Co0.3O2 2.0 M formic acid þ H2O2 reductant 70/d NaOH and NH4OH for Co, Mn, Mn Gao et al. (2017)
(OH)Y
Saturated Na2CO3 for Li2CO3Y
98.2% Li efficiency,
99.9% Li purity
LiFePO4 calcined before leaching, ball- milled with DEDTA- 0.6 M H3PO4 (50 g/L) 90/9h 5.0 M NaOH FePO4YþLi3PO4Y Yang et al. (2017)
2Na Mechanochemical activation 20 min 82.6% Li efficiency,
96.5% Li purity
LCM 3.5 M CH3COOH (40 g/L) þ 4 vol % 60/d (NH4)2S for CoSY Natarajan et al.
H2O2 Na2CO3 for Li2Co3 (2018)
Anode active material (graphite) Two-stage calcination d Na2CO3 for Li2CO3Y Yang et al. (2018)
1.5 M HCl leach 100% Li
Li, Co, and Ni are not distributed homogenously throughout the Industrial-scale recyclers: > 1000 t/y (commercialized)
world. Pilot-scale recyclers: < 1000 t/y (a few hundred tons/y)
Secondary resources (such as LIBs) should be recycled efficiently (commercialized)
and ecofriendly as much as possible. Lab-scale recyclers: small-scale trials (some grs or kgs), or
The consequence is the increased pressure on EVs. sometimes pilot-scale trials (some hundred kgs or more) but not
Higher LIB prices will demotivate people to replace fossil fuel commercialized yet
(oil or kerosene) based transportation systems.
For our climate security, it is essential to replace fossil fuel-based The current global LIB recycling companies and their recycling
systems. technologies are compared in Table 15.
There are many environmental consequences of current Li Globally, Umicore, Sumitomo-Sony, DK Recycling und Roheisen
extraction methods. GmbH, and SNAM companies recycle batteries using the combi-
nation of pyrometallurgy and hydrometallurgy methods focusing
Everyone like Li but not mined in their own country. Mining and on recycling mainly Co and Ni metals, rather than Li. In a converse
recycling are not everything, but without mining and recycling, manner, Accurec and Retriev use both pyrometallurgy and hydro-
everything is nothing. metallurgy methods to produce Li compounds from S-LIBs.
Accurec Recycling GmbH collects both household LIB packs and
18. Energy saving from different recycling methods cells and automotive/industrial LIB packs. R&D on LIBs started in
2011. R&D on automotive LIBs started in 2013. LIB recycling facility
Energy consumption comparison between pyrometallurgical, construction in Krefeld-Germany started in 2015. The company
hydrometallurgical and direct physical recycling and without recycled 4300 t/y LIBs, 3100 t/y mixed batteries, 2200 t/y NiCd, and
recycling is given in Fig. 9. There is about 73% energy saving with 700 t/y NiMH batteries in 2021. Key characteristics of the process
direct physical recycling for an electrolyte. Anode component are (https://accurec.de/lithium?lang¼en):
recycling with hydrometallurgy and direct physical recycling saves
about 69% energy. Cu component recycling saves more than 34% of Batch-type flexible processing of each Li sub-chemistry
energy with pyrometallurgy, hydrometallurgy and direct physical No battery discharge requirement
recycling. LiCoO2 component recycling also saves more than 42% for Highest safety at processing
hydrometallurgy and direct physical recycling and 30% for pyro- No HF/F emissions
metallurgical recycling. The use of recycled material significantly Without emission of environmental hazard electrolytes
reduces cell production energy and costs. Nearly 0% of gas emissions
Low energy consumption
Energy neutral treatment
19. Prices for different cathode materials Robust process safety: no emissions of carcinogenic Co/Ni
micro-powder to workplaces
CAM prices range according to purity. LCO prices changes 40e77 Disintegration & metal transformation technology (DTM) is
$/kg, NMC prices changes 50e95 $/kg, NCA prices changes 75e107 used
$/kg, LMO prices changes 23e40 $/kg, and LFP prices changes from Comminution and multistep mechanical treatment to separate
35 to 50 $/kg. Al foil costs about 15e20 $/kg, Cu costs 4.4e4.5 $/kg materials are used to produce Al, Cu
and high carbon graphite powder costs 200e240$/kg (www. Battery active materials (BAMs), steel and stainless steel
alibaba.com). There is a significant variation in the cathode cost
constituents. Cathode cost is significantly higher than element Accurec Recycling GmbH pretreats the disposed of batteries
costs. LMO and LFO cathode material costs are lower than LCO, mechanically to separate the polymers, followed by vacuum ther-
NMC, and LMO costs. mal treatment to remove the electrolyte and solvent by evapora-
tion. The material is then size reduced by crushing, classified by
20. Some of the current industrial S-LIB recyclers in the world sieving, magnetically and air separated to remove Fe, Al, Cu, and
plastic. The pretreated material then undergoes reductive pyro-
LIB recyclers can be classified into three different categories metallurgical treatments to separate Co and Mn, followed by hy-
according to their current production capacity: drometallurgical acid leaching to precipitate LiCl.
Table 14
Previous SX results for LiCoO2 materials.
Electrode material Leach reactive and conditions SX reagent References
LiCoO2 600 C/2h PC88a Dang et al. (2018)

2.25M H2SO4 (80 C/30 min) Residue: LiSO4
Leaching: 100%, purity 99.5%
LiCoO2 0.5 M HCl(60 C) Cyphos IL-101 Xu et al. (2020)
Saturated Na2CO3 (60 C)
Residue: Li2CO3
In general, current industrial recycling processes for discarded

LIBs can be divided into four different process steps, namely
Preparation, Pretreatment, Main treatment with Pyrometallurgy
and/or Hydrometallurgy, which can be combined in different
possible orders. Currently, only two of these (Pyrolyse LIB
cells þ Pyrometallurgy þ Hydrometallurgy) and (Pyrolysis þ Me-
chanical Processes þ Pyrometallurgy þ Hydrometallurgy) have
proven their technical feasibility and industrial maturity and
compete with each other after implementation in commercial
plants. Both of them involve the sub-steps of thermal pyrolysis and
pyrometallurgy, which only appear to be disadvantageous consid-
ering their higher energy consumption. However, an active mass
(AM) obtained from only mechanical pretreatment cannot be
refined directly into the end product in a hydrometallurgy process.
Without the precleaning in the two thermal stages, its impurity
content and high load of organics and F2 may cause uneconomical
operating costs in hydrometallurgy. Besides, the widely changing
composition of the battery AMs (like LCO, NMC, LMO, LFP, NCA, etc.)
requires thermal selection and homogenization for the feed ma-
terial of the hydrometallurgical process. This minimizes the oper-
ating costs of the all-process route with relatively low losses of Co,
Ni, and Cu targeted metals and also has a positive effect on the
environment because the production and use of additional oper-
Fig. 9. Energy savings for production of a cell from recycled materials. ating materials are unnecessary. A further enhancement or varia-
tion of the possible process steps, particularly with the target of
Table 15
Some global LIB recycling plants and their recycling technologies (adapted from https://accurec.de/publications-downloads?lang¼en).
Scale Company Process
Industrial scale (>1000 t/a) Umicore (BE) Pyrometallurgy þ Hydrometallurgy

Accurec (DE) Thermal þ Mechanical þ Pyro-metallurgy þ Hydrometallurgy
Nickelhütte (DE) Thermal þ Pyrometallurgy þ Hydrometallurgy
SungEel (KR) Mechanical þ (Thermalþ) þ Hydro-metallurgy
Kyoei Seiko (JP) Pyrometallurgy
Brunp (CN) Thermal þ Mechanical þ Hydrometallurgy
GEM (CN) Mechanical þ Hydrometallurgy
Huayou Cobalt (CN) Mechanical þ Hydrometallurgy
Ganzhou Highpower (CN) Mechanical þ Pyrometallurgy þ Hydrometallurgy
Pilot scale (<1000 t/a) SNAM (FR) Thermal þ Pyrometallurgy þ Hydrometallurgy
EDI (FR) Mechanical (wet shred)
TES-AMM (Recuply) (FR) Mechanical (inert gas)
Akkuser (Fl) Mechanical þ unknown
Duesenfeld (DE) Mechanical þ Hydrometallurgy
Promesa (DE) Mechanical þ (wet shred) þ unknown
Redux (DE) Thermal þ Mechanical þ unknown
Retriev (US) Mechanical (wet) þ Hydrometallurgy
Kobar (KR) Mechanical þ Hydrometallurgy
JX Nippon (JP) Thermal þ Mechanical þ Hydrometallurgy
Telerecycle (CN) Mechanical þ Hydrometallurgy
Guanghue (CN) Mechanical þ Hydrometallurgy
Laboratory scale Erlos (DE) Mechanical þ recontioning (direct recycling)
A comparison of different LIB recycling methods (i.e. pyrometallurgy, hydrometallurgy, biometallurgy, and direct recycling) from industrial applicability and product recovery
is given in Table 16. From an industrial applicability point of view, the highest total process score (5 is the best and 1 is the worst) changes in the following order:
hydrometallurgy > biometallurgy > pyrometallurgy > direct recycling; and from a product recovery point of view, the highest score order changes: direct
recycling > hydrometallurgy > pyrometallurgy.
Table 16
Comparison of different LIB recycling methods. Comparison of LIB recycling methods: Best: 5 and Worst:1.
Technology Complexity Quality of recovered Quantity of recovered Waste Energy Capital Production Total process
readiness material material generation usage cost cost score
Pyrometallurgy 5 5 1 3 2 1 1 5 23
Hydrometallurgy 4 3 3 4 3 3 3 3 26
Biometallurgy 2 3 3 3 3 4 4 3 25
Direct recycling 2 1 2 5 4 3 3 1 21
Presorting Cathode morphology Direct reuse Li Co Cu Al Mn Ni Total process

requirement preserved suitability recovery recovery recovery recovery recovery recovery score
Pyrometallurgy 5 e e 1 5 5 e 3 5 24
Hydrometallurgy 4 e e 3 5 4 5 3 5 29
Biometallurgy e e e e e e e e e e
Direct recycling 1 5 4 5 5 5 5 5 5 40
additional recycling products (Li, Co, and graphite), energy savings to brines and S-LIB recycling may generate significant alternative Li
or lowering losses, is to be technologically aimed at in the future. It resources. Li demand is expected to grow continuously and
is noted that only when the quantity of AM generated has dramatically in the coming years as different types of Li batteries
augmented to a certain extent, the installation of an overall process are the most promising candidates for powering EVs or hybrid
chain with hydrometallurgy specifically designed for the S-LIB vehicles. Li batteries include both current technologies such as Li-
sector becomes economically feasible (https://accurec.de/ ion and growing battery technologies (such as Li-sulfur or Li-air).
publications-downloads?lang¼en). Extraction of Li from primary mineral ore deposits is expensive
Neometals has developed a sustainable recycling process for the and energy-intensive. The solar brine evaporation pond process is
recovery of valuable components from LIB production scrap and EoL cheap, slow, and requires a large surface area and a large amount of
LIBs. The Neometals processing flowsheet aims at the recovery of water consumption at lower Li recovery rates. The latest promising
more than 90% of all battery materials from LIBs that might other- development of the DLE process from brines is fast and cost-
wise be disposed of in a landfill or processed in pyrometallurgical effective; has a lower water consumption, not weather dependent
recovery circuits. Specifically, the Neometals’ recycling process tar- on very high Li recovery rates. Leveraging recycling technology
gets the recovery of valuable materials from LIB with LCO cathodes, development, processing, and operational management, subsur-
Ni-rich EVs, and stationary storage batteries with NMC cathodes. face expertise, and strategic partnerships, a sustainable DLE process
Neometals aims to make revenue from the provision of recycling from brines to enable new production and supply ecosystem can be
services, licensing and sale of recovered Co, Ni, Li, Co, Fe, Al, Mn, and designed, but this process is not industrially mature yet. Therefore,
graphite into saleable products. While the use of LIB anode materials there is an urgent need for secondary resources of battery materials
generally remains constant, cathode compositions tend to differ like Li and Co from S-LIBs.
based on end-use application and performance requirements. The LIBs have been considered to be greener and cleaner energy
Neometals LIB recycling process aims at the predominant LIB storage devices than other battery types due to their higher voltage,
chemistries, with LCO and NMC/NCA cathode batteries targeted from high energy density, low self-discharge efficiency, and lower
EVs, energy storage systems and consumer electronics (https:// environmental impacts. However, LIBs still pose a threat to the
www.neometals.com.au/our-projects/core-projects/recycling/). ecosystem and human health due to the hazardous materials they
Plastics, Al- and Cu-foil are separated early. The balance of materials include. There are no simple ways and industrially mature
is recovered and refined into industrial and high purity chemicals for
sale, where possible, directly back into the LIB supply chain.
Fig. 10 shows the closed LIB value chain diagram in which the
relationship between components starts at chemical manufacture
(using recycled material feed or refined minerals) and works its
way to consumer products, disposal, and recycling to support the
notion of a “circular economy”. Therefore, the value chain of the EV
batteries should be closed for sustainability, which is a prerequisite,
not an option, in extracting and processing Li.
Most of the battery components can be recycled by more than
90% with minimum toxic waste by-products, environmentally
friendly way, and with low energy requirements. Produced valuable
metals/compounds should have a high purity for reusing in new
batteries. Therefore, the battery supply chain loop is closed and LIBs
circular economy can be realized. By recovering secondary Li, Co, and
Ni compound sources into the economy, an alternative strategic way
will be provided to the scarce resources. In this strategic way, new
employment areas will be opened in the production of Li/Co/Ni and
their compounds with high added value products.
21. Conclusions and perspectives
Increasing demand and pressure on the Li market are expected

in the future. Widening the portfolio both from primary Li deposits Fig. 10. Closed value chain of EV batteries.
technology for LIB recycling. These are varied and complicated leaching processing have been widely studied and used for the re-
products, whose design continues to evolve. LIB recycling processes covery of metals from S-LIBs. However, hydrometallurgical ap-
should be environmentally friendly and economic feasible, but proaches have an edge over their counterparts because of their easily
none of the many methods for their recycling is ideal; each has its industrial applicability and ecofriendly nature. Building on state-of-
disadvantages and advantages. Focusing on the Li market's growth the-art recycling processes, the ambition is to design and realize a
potential, LIBs recyclers should be taking a technology-driven new and environmentally friendly recycling approach for LIBs with
approach that lets researchers explore new ways to produce and the maximum recycling rate and minimum operating costs. Gener-
process high-purity Li with the entire production ecosystem in ally, the hydrometallurgy method guarantees high recovery rates
mind. This approach enables a cost-effective, sustainable, on- and does not require additional equipment, making it quite popular
demand response to the growing high-grade Battery-Li market. in the laboratory and this method is closest to industrial application.
Since Li helps the transition to a low-carbon economy, consumers However, this method requires a high acid and base reagent con-
are demanding the highest environmental standards and com- sumption proportional to the LIB for leaching, which can incur
pliancedso sustainability in the supply chain is crucial. additional chemical costs. In addition, the backend costs of disposing
While several industrial S-LIB recycling processes adopt a dis- of the used solutions can be high. In the future, there will be a global
charging/stabilization step of dismantling the S-LIBs in an inert increasing interest in LIB recycling on both laboratory- and indus-
environment using CO2, Ar or liquid N2 atmosphere, discharging trial-scales.
the LIB cells soaked in conductive unsaturated NaCl or other solu-
tions is the most common discharging method. Dismantling the Declaration of competing interest
individual battery cells is usually conducted by hand, and not many
issues have been reported related to this so far. Automated The authors declare that they have no known competing
dismantling is more suitable for industrial-scale operations. Among financial interests or personal relationships that could have
the three existing major approaches to recycling the S-LIBs, the appeared to influence the work reported in this paper.
pretreatment process is especially vital for hydrometallurgical
technologies and direct recycling. The pretreatment process can Abbreviations
improve the recovery rate of the valuable metals from the LIBs and
decrease the energy consumption in the following processes. The AN Acetonitrile
pretreatment process can be classified as discharge, dismantling, Bt Billion tonne
size reduction, classification, separation, dissolution, and thermal EV Electrical Vehicle
treatment. Mt Million tonne
Changes in the types of size reduction equipment and their AM Active Mass (Powder)
operating conditions, such as multiple comminution steps have CAM Cathode Active Material
been tested, and it was found that these changes have a major effect CRC Concentrating, Refining, and Converting
on the recovery of black mass and the flotation performance. DE Diethyl Acetate
Various screen sizes from mm to mm and the sieving conditions, DEC Di Ethyl Carbonate
such as wet or dry sieving have been tested for the classification of DLE Direct Li Extraction
the LIB comminution products. Electrode AMs are mainly concen- DMAC N,N-dimethylacetamide
trated in fine fractions, whereas coarse fractions generally contain DMC Di Methyl Carbonate
less valuable components, such as current collectors of Al and Cu- DME Ethylene Glycol Dimethylether
foils, cell cases, and plastics. A variety of physical-chemical re- DMF N, N-dimethylformamide
actions occur during the pretreatment of S-LIBs. These reactions DMT Disintegration & Metal Transformation
always produce environmentally hazardous, human-toxic, highly DMSO Dimethyl Sulfoxide
corrosive, process-relevant substances, as well as explosive gas EA Ethyl Acetate
emissions, which must be handled safely during the LIB pretreat- EC Ethylene Carbonate
ment process. EEE Electrical and Electronic Equipment
Various physical/mechanical and physico-chemical separation EMC Ethyl Methyl Carbonate
methods, that include magnetic separation, electrostatic separation EoL End-of-Life
(eddy current separation), gravity separation (heavy medium sep- ESC Electrode-Separator Compounds
aration, air separation), ultrasonic separation, and froth flotation g-GBL g-Butyrolactone
(reverse flotation), have been suggested in the S-LIB recycling IoT Internet of Thinks
process in the last decades. For the improvement of the froth IX Ion Exchange
flotation performance, additional treatments, such as ultra- LCE Lithium Carbonate Equivalent
sonication, grinding, mechanical activation, and roasting have been LCO Lithium Cobalt Oxide, LiCoO2
combined with the froth flotation process. Because most liberated Li Lithium
AMs are held together by organic binders or attached to the Al/Cu- PC Propylene Carbonate
foils, the dissolution of the PTFE and PVDF binders by NMP or other PE Polyethylene
kinds of solvent is considered as well as the dissolution of the Al- PLS Pregnant Leach Solution
foil by alkaline NaOH solutions. For the complete recovery of the PP Polypropylene
CAMs, a thermal treatment or pyrolysis can also be used. The PVDF ppm Part per million
binders are generally decomposed at around 500 C, the C LIB Li-ion Battery
conductive agents are burnt off at higher temperatures and the LFP Lithium Iron Phosphate, LiFePO4
volatilization of the electrolyte occurs at lower temperatures. LMO Lithium Manganese Oxide, LiMn2O4
To address the environmental problems, sustainable resource NCA Lithium Nickel Cobalt Aluminum oxide, LiNixCoyAlzO2
management, and enhance the circular economy, it is important to NiCd Nickel Cadmium
properly manage and recycle S-LIBs. Conventional methods based on NiMH Nickel Metal Hydride
thermal pyrometallurgical routes together with hydrometallurgical NMC N-methylpyrrolidone
NMP N-methyl-2-pyrrolidine Anderson, P. (2019). Recycling lithium-ion batteries from electric vehicles. Na-
ture, 575(7781), 75e86.
PTFE Polytetrafluoroethylene
He, L. P., Sun, S. Y., Mu, Y. Y., Song, X. F., & Yu, J. G. (2017). Recovery of lithium, nickel,
PVDF Polyvinylidene Fluoride cobalt, and manganese from spent lithium-ion batteries using l-tartaric acid as
SSE Solid-State Electrolyte a leachant. ACS Sustainable Chemistry & Engineering, 5(1), 714e721.
SX Solvent Extraction He, L. P., Sun, S. Y., Song, X. F., & Yu, J. G. (2015). Recovery of cathode materials and Al
from spent lithium-ion batteries by ultrasonic cleaning. Waste Management, 46,
TFA Trifluoroacetic acid 523e528.
THF Tetrahydrofuran He, K., Zhang, Z. Y., Alai, L. G., & Zhang, F. S. (2019). A green process for exfoliating
USGS United States Geological Survey electrode materials and simultaneously extracting electrolyte from spent
lithium-ion batteries. Journal of Hazardous Materials, 375, 43e51.
Hu, J. T., Zhang, J. L., Li, H. X., Chen, Y. Q., & Wang, C. Y. (2017). A promising approach
for the recovery of high value-added metals from spent lithium-ion batteries.
References Journal of Power Sources, 351, 192e199.
Joulie , M., Laucournet, R., & Billy, E. (2014). Hydrometallurgical process for the re-
Ambrose, H., & Kendall, A. (2020). Understanding the future of lithium: Part 1, covery of high value metals from spent lithium nickel cobalt aluminum oxide
resource model. Journal of Industrial Ecology, 24(1), 80e89. based lithium-ion batteries. Journal of Power Sources, 247, 551e555.
Bae, H., & Kim, Y. (2021). Technologies of lithium recycling from waste lithium ion Kang, J. G., Senanayake, G., Sohn, J., & Shin, S. M. (2010). Recovery of cobalt sulfate
batteries: A review. Materials Advances, 2(10), 3234e3250. from spent lithium ion batteries by reductive leaching and solvent extraction
Barik, S. P., Prabaharan, G., & Kumar, L. (2017). Leaching and separation of Co and with Cyanex 272. Hydrometallurgy, 100, 168e171, 3e4.
Mn from electrode materials of spent lithium-ion batteries using hydrochloric Kim, S., Bang, J., Yoo, J., Shin, Y., Bae, J., Jeong, J., Kim, K., Dong, P., & Kwon, K. (2021).
acid: Laboratory and pilot scale study. Journal of Cleaner Production, 147, 37e43. A comprehensive review on the pretreatment process in lithium-ion battery
_
Can, M. F., Başaran, C., Yildiz, A., & DemIrkapi, M. (2021). Lithium extraction from recycling. Journal of Cleaner Production, 294, Article 126329.
geothermal waters; a case study of Omer-Gecek€ (Afyonkarahisar) geothermal Lee, C. K., & Rhee, K. I. (2002). Preparation of LiCoO2 from spent lithium-ion bat-
area. Turkish Journal of Earth Sciences, 30, 1208e1220. SIe2. teries. Journal of Power Sources, 109(1), 17e21.
Celebi, E. E. (2019). Lithium recovery from boron industry-induced wastewaters by Lee, C. K., & Rhee, K. I. (2003). Reductive leaching of cathodic active materials from
solvent extraction. Turkey: Gebze Technical University (in Turkish). lithium ion battery wastes. Hydrometallurgy, 68, 5e10, 1e3.
Chen, X. P., Fan, B. L., Xu, L. P., Zhou, T., & Kong, J. R. (2016). An atom-economic Li, L., Chen, R. J., Sun, F., Wu, F., & Liu, J. R. (2011). Preparation of LiCoO2 films from
process for the recovery of high value-added metals from spent lithium-ion spent lithium-ion batteries by a combined recycling process. Hydrometallurgy,
batteries. Journal of Cleaner Production, 112, 3562e3570. 108, 220e225, 3e4.
Chen, X. P., Ma, H. R., Luo, C. B., & Zhou, T. (2017). Recovery of valuable metals from Li, L., Dunn, J. B., Zhang, X. X., Gaines, L., Chen, R. J., Wu, F., & Amine, K. (2013).
waste cathode materials of spent lithium-ion batteries using mild phosphoric Recovery of metals from spent lithium-ion batteries with organic acids as
acid. Journal of Hazardous Materials, 326, 77e86. leaching reagents and environmental assessment. Journal of Power Sources, 233,
Chen, L., Tang, X. C., Zhang, Y., Li, L. X., Zeng, Z. W., & Zhang, Y. (2011). Process for the 180e189.
recovery of cobalt oxalate from spent lithium-ion batteries. Hydrometallurgy, Lie, J., Tanda, S., & Liu, J. C. (2020). Subcritical water extraction of valuable metals
108, 80e86, 1e2. from spent lithium-ion batteries. Molecules, 25(9), 2166.
Contestabile, M., Panero, S., & Scrosati, B. (1999). A laboratory-scale lithium battery Li, L., Ge, J., Chen, R. J., Wu, F., Chen, S., & Zhang, X. X. (2010a). Environmental
recycling process. Journal of Power Sources, 83, 75e78, 1e2. friendly leaching reagent for cobalt and lithium recovery from spent lithium-
Contestabile, M., Panero, S., & Scrosati, B. (2001). A laboratory-scale lithium-ion ion batteries. Waste Management, 30(12), 2615e2621.
battery recycling process. Journal of Power Sources, 92, 65e69, 1e2. Li, L., Ge, J., Wu, F., Chen, R. J., Chen, S., & Wu, B. R. (2010b). Recovery of cobalt and
Dai, C. Y., Wang, Z., Liu, K., Zhu, X. X., Liao, X. B., Chen, X., & Pan, Y. (2019). Effects of lithium from spent lithium ion batteries using organic citric acid as leachant.
cycle times and C-rate on mechanical properties of copper foil and adhesive Journal of Hazardous Materials, 176, 288e293, 1e3.
strength of electrodes in commercial LiCoO2 LIBs. Engineering Failure Analysis, Li, L., Lu, J., Ren, Y., Zhang, X. X., Chen, R. J., Wu, F., & Amine, K. (2012). Ascorbic-acid-
101, 193e205. assisted recovery of cobalt and lithium from spent Li-ion batteries. Journal of
Dang, H., Wang, B. F., Chang, Z. D., Wu, X., Feng, J. G., Zhou, H. L., Li, W. J., & Sun, C. Y. Power Sources, 218, 21e27.
(2018). Recycled lithium from simulated pyrometallurgical slag by chlorination Li, L., Qu, W. J., Zhang, X. X., Lu, J., Chen, R. J., Wu, F., & Amine, K. (2015). Succinic
roasting. ACS Sustainable Chemistry & Engineering, 6(10), 13160e13167. acid-based leaching system: A sustainable process for recovery of valuable
Dorella, G., & Mansur, M. B. (2007). A study of the separation of cobalt from spent metals from spent Li-ion batteries. Journal of Power Sources, 282, 544e551.
Li-ion battery residues. Journal of Power Sources, 170(1), 210e215. Li, J. H., Shi, P. X., Wang, Z. F., Chen, Y., & Chang, C. C. (2009). A combined recovery
Ferreira, D. A., Prados, L. M. Z., Majuste, D., & Mansur, M. B. (2009). Hydrometal- process of metals in spent lithium-ion batteries. Chemosphere, 77(8),
lurgical separation of aluminium, cobalt, copper and lithium from spent Li-ion 1132e1136.
batteries. Journal of Power Sources, 187(1), 238e246. Liu, Y. J., Hu, Q. Y., Li, X. H., Wang, Z. X., & Guo, H. J. (2006). Recycle and synthesise
€hlich, S., & Sewing, D. (1995). The BATENUS process for recycling mixed battery
Fro LiCoO2 from incisors bound of Li-ion batteries. Transactions of Nonferrous Metals
waste. Journal of Power Sources, 57, 27e30, 1e2. Society of China, 16, 956e959.
Gaines, L. (2018). Lithium-ion battery recycling processes: Research towards a Liu, J. S., Wang, H. F., Hu, T. T., Bai, X. J., Wang, S., Xie, W. N., Hao, J., & He, Y. Q. (2020).
sustainable course. Sustainable Materials and Technologies, 17, Article e00068. Recovery of LiCoO2 and graphite from spent lithium-ion batteries by cryogenic
Gao, W. F., Song, J. L., Cao, H. B., Lin, X., Zhang, X. H., Zheng, X. H., Zhang, Y., & Sun, Z. grinding and froth flotation. Minerals Engineering, 148, Article 106223.
(2018). Selective recovery of valuable metals from spent lithium-ion batter- Li, J., Wang, G. X., & Xu, Z. M. (2016). Environmentally-friendly oxygen-free roasting/
iesdprocess development and kinetics evaluation. Journal of Cleaner Production, wet magnetic separation technology for in situ recycling cobalt, lithium car-
178, 833e845. bonate and graphite from spent LiCoO2/graphite lithium batteries. Journal of
Gao, W. F., Zhang, X. H., Zheng, X. H., Lin, X., Cao, H. B., Zhang, Y., & Sun, Z. (2017). Hazardous Materials, 302, 97e104.
Lithium carbonate recovery from cathode scrap of spent lithium-ion battery: A Li, X. L., Zhang, J., Song, D. W., Song, J. S., & Zhang, L. Q. (2017). Direct regeneration of
closed-loop process. Environmental Science & Technology, 51(3), 1662e1669. recycled cathode material mixture from scrapped LiFePO4 batteries. Journal of
Georgi-Maschler, T., Friedrich, B., Weyhe, R., Heegn, H., & Rutz, M. (2012). Devel- Power Sources, 345, 78e84.
opment of a recycling process for Li-ion batteries. Journal of Power Sources, 207, Li, L. R., Zheng, P. N., Yang, T. R., Sturges, R., Ellis, M. W., & Li, Z. (2019). Disassembly
173e182. automation for recycling end-of-life lithium-ion pouch cells. Journal of Occu-
Golmohammadzadeh, R., Rashchi, F., & Vahidi, E. (2017). Recovery of lithium and pational Medicine, 71(12), 4457e4464.
cobalt from spent lithium-ion batteries using organic acids: Process optimiza- Meng, F., McNeice, J., Zadeh, S. S., & Ghahreman, A. (2021). Review of lithium
tion and kinetic aspects. Waste Management, 64, 244e254. production and recovery from minerals, brines, and lithium-ion batteries.
Granata, G., Pagnanelli, F., Moscardini, E., Takacova, Z., Havlik, T., & Toro, L. (2012). Mineral Processing and Extractive Metallurgy Review, 42(2), 123e141.
Simultaneous recycling of nickel metal hydride, lithium ion and primary Meng, Q., Zhang, Y. J., & Dong, P. (2017). Use of glucose as reductant to recover Co
lithium batteries: Accomplishment of European Guidelines by optimizing me- from spent lithium ions batteries. Waste Management, 64, 214e218.
chanical pre-treatment and solvent extraction operations. Journal of Power Meshram, P., Pandey, B. D., & Mankhand, T. R. (2015). Hydrometallurgical processing
Sources, 212, 205e211. of spent lithium ion batteries (LIBs) in the presence of a reducing agent with
Gratz, E., Sa, Q. N., Apelian, D., & Wang, Y. (2014). A closed loop process for recycling emphasis on kinetics of leaching. Chemical Engineering Journal, 281, 418e427.
spent lithium ion batteries. Journal of Power Sources, 262, 255e262. Mishra, D., Kim, D. J., Ralph, D. E., Ahn, J. G., & Rhee, Y. H. (2008). Bioleaching of
Guan, J., Li, Y. G., Guo, Y. G., Su, R. J., Gao, G. L., Song, H. X., Yuan, H., Liang, B., & metals from spent lithium ion secondary batteries using Acidithiobacillus fer-
Guo, Z. H. (2017). Mechanochemical process enhanced cobalt and lithium rooxidans. Waste Management, 28(2), 333e338.
recycling from wasted lithium-ion batteries. ACS Sustainable Chemistry & En- Munir, H., Srivastava, R. R., Kim, H., Ilyas, S., Khosa, M. K., & Yameen, B. (2020).
gineering, 5(1), 1026e1032. Leaching of exhausted LNCM cathode batteries in ascorbic acid lixiviant: A
Guo, Y., Li, F., Zhu, H. C., Li, G. M., Huang, J. W., & He, W. Z. (2016). Leaching lithium green recycling approach, reaction kinetics and process mechanism. Journal of
from the anode electrode materials of spent lithium-ion batteries by hydro- Chemical Technology & Biotechnology, 95(8), 2286e2294.
chloric acid (HCl). Waste Management, 51, 227e233. Mylarappa, M., Lakshmi, V. V., Vishnu Mahesh, K. R., Nagaswarupa, H. P.,
Harper, G., Sommerville, R., Kendrick, E., Driscoll, L., Slater, P., Stolkin, R., Walton, A., Prashantha, S. C., Shravana Kumara, K. N., Siddeswara, D. M. K., &
Christensen, P., Heidrich, O., Lambert, S., Abbott, A., Ryder, K., Graines, L., & Raghavendra, N. (2017). Resource recovery and material characterization of
metals from waste Li-ion batteries by an eco-friendly leaching agent. Materials temperature molten salt. ACS Sustainable Chemistry & Engineering, 7(9),
Today Proceedings, 4(11), 12215e12222. 8287e8294.
Nan, J. M., Han, D. M., Yang, M. J., Cui, M., & Hou, X. L. (2006). Recovery of metal Wang, F. F., Zhang, T., He, Y. Q., Zhao, Y. M., Wang, S., Zhang, G. W., Zhang, Y., &
values from a mixture of spent lithium-ion batteries and nickel-metal hydride Feng, Y. (2018). Recovery of valuable materials from spent lithium-ion batteries
batteries. Hydrometallurgy, 84, 75e80, 1e2. by mechanical separation and thermal treatment. Journal of Cleaner Production,
Nan, J. M., Han, D. M., & Zuo, X. X. (2005). Recovery of metal values from spent 185, 646e652.
lithium-ion batteries with chemical deposition and solvent extraction. Journal Wang, M. M., Zhang, C. C., & Zhang, F. S. (2016). An environmental benign process
of Power Sources, 152, 278e284. for cobalt and lithium recovery from spent lithium-ion batteries by mechano-
Natarajan, S., Boricha, A. B., & Bajaj, H. C. (2018). Recovery of value-added products chemical approach. Waste Management, 51, 239e244.
from cathode and anode material of spent lithium-ion batteries. Waste Man- Wang, M. M., Zhang, C. C., & Zhang, F. S. (2017a). Recycling of spent lithium-ion
agement, 77, 455e465. battery with polyvinyl chloride by mechanochemical process. Waste Manage-
Nayaka, G. P., Manjanna, J., Pai, K. V., Vadavi, R., Keny, S. J., & Tripathi, V. S. (2015). ment, 67, 232e239.
Recovery of valuable metal ions from the spent lithium-ion battery using Widijatmoko, S. D., Fu, G., Wang, Z., & Hall, P. (2020). Recovering lithium cobalt
aqueous mixture of mild organic acids as alternative to mineral acids. Hydro- oxide, aluminium, and copper from spent lithium-ion battery via attrition
metallurgy, 151, 73e77. scrubbing. Journal of Cleaner Production, 260, Article 120869.
Nayaka, G. P., Pai, K. V., Santhosh, G., & Manjanna, J. (2016a). Dissolution of cathode Xiao, J. F., Guo, J., Zhan, L., & Xu, Z. M. (2020). A cleaner approach to the discharge
active material of spent Li-ion batteries using tartaric acid and ascorbic acid process of spent lithium ion batteries in different solutions. Journal of Cleaner
mixture to recover Co. Hydrometallurgy, 161, 54e57. Production, 255, Article 120064.
Nayaka, G. P., Pai, K. V., Santhosh, G., & Manjanna, J. (2016b). Recovery of cobalt as Xin, B. P., Zhang, D., Zhang, X., Xia, Y. T., Wu, F., Chen, S., & Li, L. (2009). Bioleaching
cobalt oxalate from spent lithium ion batteries by using glycine as leaching mechanism of Co and Li from spent lithium-ion battery by the mixed culture of
agent. Journal of Environmental Chemical Engineering, 4(2), 2378e2383. acidophilic sulfur-oxidizing and iron-oxidizing bacteria. Bioresource Technology,
Or, T., Gourley, S. W. D., Kaliyappan, K., Yu, A. P., & Chen, Z. W. (2020). Recycling of 100(24), 6163e6169.
mixed cathode lithium-ion batteries for electric vehicles: Current status and Xu, L., Chen, C., & Fu, M. L. (2020). Separation of cobalt and lithium from spent
future outlook. Carbon Energy, 2(1), 6e43. lithium-ion battery leach liquors by ionic liquid extraction using Cyphos IL-101.
Pagnanelli, F., Moscardini, E., Granata, G., Cerbelli, S., Agosta, L., Fieramosca, A., & Hydrometallurgy, 197, Article 105439.
Toro, L. (2014). Acid reducing leaching of cathodic powder from spent lithium Xu, Y. N., Song, D. W., Li, L., An, C. H., Wang, Y. J., Jiao, L. F., & Yuan, H. T. (2014).
ion batteries: Glucose oxidative pathways and particle area evolution. Journal of A simple solvent method for the recovery of LixCoO2 and its applications in
Industrial and Engineering Chemistry, 20(5), 3201e3207. alkaline rechargeable batteries. Journal of Power Sources, 252, 286e291.
Paulino, J. F., Busnardo, N. G., & Afonso, J. C. (2008). Recovery of valuable elements Yang, Y., Huang, G. Y., Xu, S. M., He, Y. H., & Liu, X. (2016). Thermal treatment process
from spent Li-batteries. Journal of Hazardous Materials, 150(3), 843e849. for the recovery of valuable metals from spent lithium-ion batteries. Hydro-
Peng, C., Liu, F. P., Wang, Z. L., Wilson, B. P., & Lundstro €m, M. (2019). Selective metallurgy, 165, 390e396.
extraction of lithium (Li) and preparation of battery grade lithium carbonate Yang, Y. X., Meng, X. Q., Cao, H. B., Lin, X., Liu, C. M., Sun, Y., Zhang, Y., & Sun, Z.
(Li2CO3) from spent Li-ion batteries in nitrate system. Journal of Power Sources, (2018). Selective recovery of lithium from spent lithium iron phosphate bat-
415, 179e188. teries: A sustainable process. Green Chemistry, 20(13), 3121e3133.
Pinegar, H., & Smith, Y. R. (2019). Recycling of end-of-life lithium ion batteries, Part Yang, Y., Zheng, X., Cao, H., Zhao, C., Lin, X., Ning, P., Zhang, Y., Jin, W., & Sun, Z.
I: Commercial processes. Journal of Sustainable Metallurgy, 5(3), 402e416. (2017). A closed-loop process for selective metal recovery from spent lithium
Pinna, E. G., Ruiz, M. C., Ojeda, M. W., & Rodriguez, M. H. (2017). Cathodes of spent iron phosphate batteries through mechanochemical activation. ACS Sustainable
Li-ion batteries: Dissolution with phosphoric acid and recovery of lithium and Chemistry & Engineering, 5(11), 9972e9980.
cobalt from leach liquors. Hydrometallurgy, 167, 66e71. Yao, L., Feng, Y., & Xi, G. (2015). A new method for the synthesis of LiNi1/3Co1/
Prazanova , A., Knap, V., & Stroe, D. I. (2022). Literature review, recycling of lithium- 3Mn1/3O2 from waste lithium ion batteries. RSC Advances, 5(55),
ion batteries from electric vehicles, part I: Recycling technology. Energies, 15(3), 44107e44114.
1086. Yu, J. D., He, Y. Q., Ge, Z. Z., Li, H., Xie, W. N., & Wang, S. (2018). A promising physical
Reich, R., Slunitschek, K., Danisi, R. M., Eiche, E., & Kolb, J. (2022). Lithium extraction method for recovery of LiCoO2 and graphite from spent lithium-ion batteries:
techniques and the application potential of different sorbents for lithium re- Grinding flotation. Separation and Purification Technology, 190, 45e52.
covery from brines. In Mineral processing and extractive metallurgy review. Yu, J. D., He, Y. Q., Li, H., Xie, W. N., & Zhang, T. (2017). Effect of the secondary
https://doi.org/10.1080/08827508.2022.2047041 product of semi-solid phase Fenton on the flotability of electrode material from
Sethurajan, M., Huguenot, D., Lens, P. N. L., Horn, H. A., Figueiredo, L. H. A., & van spent lithium-ion battery. Powder Technology, 315, 139e146.
Hullebusch, E. D. (2016). Leaching and selective copper recovery from acidic Yun, L., Linh, D., Shui, L., Peng, X. B., Garg, A., Le, M. L. P., Asghari, S., & Sandoval, J.
leachates of Tre ^s Marias zinc plant (MG, Brazil) metallurgical purification res- (2018). Metallurgical and mechanical methods for recycling of lithium-ion
idues. Journal of Environmental Management, 177, 26e35. battery pack for electric vehicles. Resources, Conservation and Recycling, 136,
Shin, S. M., Kim, N. H., Sohn, J. S., Yang, D. H., & Kim, Y. H. (2005). Development of a 198e208.
metal recovery process from Li-ion battery wastes. Hydrometallurgy, 79, Zeng, G. S., Deng, X. R., Luo, S. L., Luo, X. B., & Zou, J. P. (2012). A copper-catalyzed
172e181, 3e4. bioleaching process for enhancement of cobalt dissolution from spent lithium-
Shin, H., Zhan, R. T., Dhindsa, K. S., Pan, L., & Han, T. (2020). Electrochemical per- ion batteries. Journal of Hazardous Materials, 199e200, 164e169.
formance of recycled cathode active materials using froth flotation-based Zeng, X. L., Li, J. H., & Shen, B. Y. (2015). Novel approach to recover cobalt and
separation process. Journal of the Electrochemical Society, 167(2), Article 020504. lithium from spent lithium-ion battery using oxalic acid. Journal of Hazardous
Simate, G. S., Ndlovu, S., & Walubita, L. F. (2010). The fungal and chemolithotrophic Materials, 295, 112e118.
leaching of nickel lateritesdchallenges and opportunities. Hydrometallurgy, 103, Zhang, X. H., Cao, H. B., Xie, Y. B., Ning, P. G., An, H. J., You, H. X., & Nawaz, F. (2015).
150e157, 1e4. A closed-loop process for recycling LiNi1/3Co1/3Mn1/3O2 from the cathode scraps
Song, D. W., Wang, X. Q., Nie, H. H., Shi, H., Wang, D. G., Guo, F. X., Shi, X. X., & of lithium-ion batteries: Process optimization and kinetics analysis. Separation
Zhang, L. Q. (2014). Heat treatment of LiCoO2 recovered from cathode scraps and Purification Technology, 150, 186e195.
with solvent method. Journal of Power Sources, 249, 137e141. Zhang, W. S., & Cheng, C. Y. (2007). Manganese metallurgy review. Part I: Leaching
Song, D. W., Wang, X. Q., Zhou, E. L., Hou, P. Y., Guo, F. X., & Zhang, L. Q. (2013). of ores/secondary materials and recovery of electrolytic/chemical manganese
Recovery and heat treatment of the Li(Ni1/3Co1/3Mn1/3)O2 cathode scrap ma- dioxide. Hydrometallurgy, 89, 137e159, 3e4.
terial for lithium ion battery. Journal of Power Sources, 232, 348e352. Zhang, G. W., He, Y. Q., Feng, Y. W., Wang, H. F., & Zhu, X. N. (2018). Pyrolysis-ul-
Sun, L., & Qiu, K. Q. (2011). Vacuum pyrolysis and hydrometallurgical process for the trasonic-assisted flotation technology for recovering graphite and LiCoO2 from
recovery of valuable metals from spent lithium-ion batteries. Journal of Haz- spent lithium-ion batteries. ACS Sustainable Chemistry & Engineering, 6(8),
ardous Materials, 194, 378e384. 10896e10904.
Sun, L., & Qiu, K. Q. (2012). Organic oxalate as leachant and precipitant for the re- Zhang, G. W., He, Y. Q., Wang, H. F., Feng, Y. W., Xie, W., & Zhu, X. N. (2020). Removal
covery of valuable metals from spent lithium-ion batteries. Waste Management, of organics by pyrolysis for enhancing liberation and flotation behavior of
32(8), 1575e1582. electrode materials derived from spent lithium-ion batteries. ACS Sustainable
Takacova, Z., Havlik, T., Kukurugya, F., & Orac, D. (2016). Cobalt and lithium recovery Chemistry & Engineering, 8, 2205e2214.
from active mass of spent Li-ion batteries: Theoretical and experimental Zhang, X. H., Xie, Y. B., Cao, H. B., Nawaz, F., & Zhang, Y. (2014). A novel process for
approach. Hydrometallurgy, 163, 9e17. recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps
€ger, T., Friedrich, B., & Weyhe, R. (2015). Recovery concept of value metals from
Tra intended for lithium-ion batteries. Waste Management, 34(9), 1715e1724.
automotive lithium-ion batteries. Chemie Ingenieur Technik, 87(11), 1550e1557. Zhang, X. H., Xie, Y. B., Lin, X., Li, H. T., & Cao, H. B. (2013). An overview on the
Wang, H. Y., Huang, K., Zhang, Y., Chen, X., Jin, W., Zheng, S. L., Zhang, Y., & Li, P. processes and technologies for recycling cathodic active materials from spent
(2017b). Recovery of lithium, nickel, and cobalt from spent lithium-ion battery lithium-ion batteries. Journal of Material Cycles and Waste Management, 15(4),
powders by selective ammonia leaching and an adsorption separation system. 420e430.
ACS Sustainable Chemistry & Engineering, 5(12), 11489e11495. Zhang, P. W., Yokoyama, T., Itabashi, O., Suzuki, T. M., & Inoue, K. (1998). Hydro-
Wang, H. F., Liu, J. S., Bai, X. J., Wang, S., Yang, D., Fu, Y. P., & He, Y. Q. (2019a). metallurgical process for recovery of metal values from spent lithium-ion
Separation of the cathode materials from the Al foil in spent lithium-ion bat- secondary batteries. Hydrometallurgy, 47, 259e271, 2e3.
teries by cryogenic grinding. Waste Management, 91, 89e98. Zhan, R. T., Oldenburg, Z., & Pan, L. (2018). Recovery of active cathode materials from
Wang, M. M., Tan, Q. Y., Liu, L. L., & Li, J. H. (2019b). Efficient separation of aluminum lithium-ion batteries using froth flotation. Sustainable Materials and Technolo-
foil and cathode materials from spent lithium-ion batteries using a low- gies, 17, Article e00062.
Zhao, J. J., Qu, X., Qu, J. K., Zhang, B. L., Ning, Z. Q., Xie, H. W., Zhou, X. B., Song, Q. S., metals from cathode scrap by sodium sulphite. Waste Management, 60,
Xing, P. F., & Yin, H. Y. (2019). Extraction of Co and Li2CO3 from cathode materials 680e688.
of spent lithium-ion batteries through a combined acid-leaching and electro- Zheng, X. H., Zhu, Z. W., Lin, X., Zhang, Y., He, Y., Cao, H. B., & Sun, Z. (2018). A mini-
deoxidation approach. Journal of Hazardous Materials, 379, Article 120817. review on metal recycling from spent lithium ion batteries. Engineering, 4(3),
Zhao, C., & Zhang, X. (2020). Retracted: Reverse flotation process for the recovery of 361e370.
pyrolytic LiFePO4. Colloids and Surfaces A: Physicochemical and Engineering As- Zhou, X., He, W. Z., Li, G. M., Zhang, X. J., Huang, J. W., & Zhu, S. G. (2010). Recycling
pects, 596, Article 124741. of electrode materials from spent lithium-ion batteries. In Proceedings of the 4th
Zheng, X. H., Gao, W. F., Zhang, X. H., He, M. M., Lin, X., Cao, H. B., Zhang, Y., & Sun, Z. international conference on bioinformatics and biomedical engineering. Chengdu,
(2017). Spent lithium-ion battery recyclingdreductive ammonia leaching of China.

LIB (Lithium Ion Battery)

Uploaded by

Copyright:

Available Formats

LIB (Lithium Ion Battery)

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

LIB (Lithium Ion Battery)

Uploaded by

Copyright:

Available Formats

Circular Economy 1 (2022) 100015

Contents lists available at ScienceDirect

State-of-the-art lithium-ion battery recycling technologies

Mineral Ore Deposits (34%) Brines (66%) Seawater Reserve

(12.8e30.7 Mt) (21.3e65.3 Mt) (230 Bt)

signiﬁcant environmental problems. Aqueous brines are cheap for Table 2

Country Lithium mineral Brine world production (t)

2015 2016 2017 2018 2019

Australia LiAl(SiO3)2 439,514 522,181 1,706,618 1,965,944 1,616,764

W: Withheld to avoid disclosing company proprietary data.

Fig. 2. LIB is placed on the global market until 2028 (https://www.neometals.com.au/products-and-markets/battery-recycling/).

Fig. 3. Environmental hazards of improper LIB disposal and burning.

Fig. 4. Charge and discharge of LIBs.

Fig. 5. Waste LIB source types and global amounts.

Fig. 6. S-LIB recycling market capacity between 2018 and 2030.

Battery components Material Mass (%) Estimated costs (%)

Container/housing/packaging foil Steel or Al 20e25 2

Cathode type LCO LFP LMO NCA NMC

Smaller and lighter than others Cost

Fig. 8. Main stages in S-LIB active material recycling process.

LiPF6 / LiF þ PF5 (1) 14. Pretreatment methods for S-LIBs

Ethylene Carbonate (EC, C3H4O) Vapor pressure: 21 Pa (20 C).

Dimethyl Carbonate (DMC, C3H6O3) Highly ﬂammable, highly volatile

Diethyl Carbonate (DEC, C5H10O3) Highly ﬂammable, highly volatile

Ethyl Methyl Carbonate (EMC, C4H8O3) Highly ﬂammable, highly volatile

Lithium Hexaﬂuorophosphate (LiPF6) Toxicity and hazard to water:

LithiumeNickeleManganeseeCobalt Oxide Li(NixCoyMnzO2) Toxicity and hazard to water:

LithiumdTitanate (Li4Ti5O12) Toxicity and hazard to water:

EC Ethylene carbonate C3H4O3 3.6 16.1 143

Pretreatment method Advantages Disadvantages

Solvent Binder Temp./Time/ Material Material remained Reference

Reagent-acid Oxidant T ( C) T (min) S/L (g/L) Recovery (%) Reference

1.25M citric 1% H2O2 90 30 20 Li: 100%; Co: 90% Li et al. (2010b)

Accompanying material Problem formation in hydrometallurgy Troubleshooting

Electrode material Leach reactive and conditions Temp. Precipitant References

Electrode material Leach reactive and conditions SX reagent References

LiCoO2 600 C/2h PC88a Dang et al. (2018)

In general, current industrial recycling processes for discarded

Scale Company Process

Industrial scale (>1000 t/a) Umicore (BE) Pyrometallurgy þ Hydrometallurgy

Presorting Cathode morphology Direct reuse Li Co Cu Al Mn Ni Total process

21. Conclusions and perspectives

Increasing demand and pressure on the Li market are expected

You might also like