Perspective

Cite This: ACS Sustainable Chem. Eng. 2018, 6, 1504−1521 pubs.acs.org/journal/ascecg

A Critical Review and Analysis on the Recycling of Spent Lithium-Ion

Batteries
Weiguang Lv,†,‡,§ Zhonghang Wang,†,§ Hongbin Cao,†,§ Yong Sun,∥ Yi Zhang,†,§ and Zhi Sun*,†,§
†
National Engineering Laboratory for Hydrometallurgical Cleaner Production & Technology, Institute of Process Engineering,
Chinese Academy of Sciences, Beijing 100190, China
‡
University of Chinese Academy of Sciences, Beijing 100190, China
§
Beijing Engineering Research Center of Process Pollution Control, Beijing 100190, China
∥
Edith Cowan University School of Engineering, 270 Joondalup Drive, Joondalup, Western Australia 6027, Australia
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Recycling of spent lithium-ion batteries (LIBs) has attracted

Downloaded via CITY UNIV INTRNTL PARIS on June 24, 2020 at 05:58:12 (UTC).

significant attention in recent years due to the increasing demand for

corresponding critical metals/materials and growing pressure on the
environmental impact of solid waste disposal. A range of investigations
have been carried out for recycling spent LIBs to obtain either battery
materials or individual compounds. For the effective recovery of materials
to be enhanced, physical pretreatment is usually applied to obtain different
streams of waste materials ensuring efficient separation for further
processing. Subsequently, a metallurgical process is used to extract metals
or separate impurities from a specific waste stream so that the recycled
materials or compounds can be further prepared by incorporating
principles of materials engineering. In this review, the current status of
spent LIB recycling is summarized in light of the whole recycling process,
especially focusing on the hydrometallurgy. In addition to understanding
different hydrometallurgical technologies including acidic leaching, alkaline leaching, chemical precipitation, and solvent
extraction, the existing challenges for process optimization during the recycling are critically analyzed. Moreover, the energy
consumption of different processes is evaluated and discussed. It is expected that this research could provide a guideline for
improving spent LIB recycling, and this topic can be further stimulated for industrial realization.
KEYWORDS: Spent LIBs, Pretreatment, Recycling, Environmental impact, Hydrometallurgy

■ INTRODUCTION
The rapid growth of lithium-ion batteries (LIBs) used in
portable electronic devices and electric vehicles requires a
significant amount of metal resources, especially lithium (Li)
and cobalt (Co).1 According to the United States Geological
Survey (USGS) and the China Industry Information Network,
nearly 40% of Li and 42.46% Co were consumed in the
production of batteries in 2014.2,3 Specifically, the consumption
of Co for power batteries has increased to 13.7% in 2016 and if
the trend holds will increase to 20.3% in 2018 because of the
rapid development of electric vehicles.4 Meanwhile, worldwide
cobalt and lithium production have only increased slightly in
recent years. With the current growth rate, significant pressure
is imposed on the supply side of cobalt and lithium.5 It is
predicted that Co and Li will face a serious shortage in the
foreseeable future.
Apart from the above-mentioned resource issues, the
environmental and potential safety problems caused by spent
LIBs are also substantial. If a spent LIB is directly discarded
without proper treatment, heavy metals like Co, Ni, and Mn
would contaminate soil and underground water. The electrolyte
easily reacts with water to release harmful gas such as hydrogen
fluoride (HF).6 Furthermore, during the cycle life period, Li
tends to deposit on the anode due to overcharging or other
improper usage. The deposited Li can react with water to
release hydrogen gas (H2) and produce lithium hydroxide
(LiOH). The residual electric power tends to cause explosions
or fire accidents.7 Therefore, effective recycling of spent LIBs in
light of the environmental and safety challenges is critical to
ensure sustainable development in this field.
A single methodology is hard to be both cost-effective and
environmentally friendly due to the complexity of raw
materials. Therefore, a combination of physical and chemical
approaches is widely adopted to recycle spent LIBs. Generally,
physical methods are used to enhance the efficiency of recycling
and typically include dismantling, crushing, sieving, and thermal
and mechanochemical treatment.8 The chemical methods could
be classified into pyrometallurgy and hydrometallurgy. In
comparison with pyrometallurgical processes that are usually
undertaken at high temperature, hydrometallurgical methods
Received: October 26, 2017
Revised: December 6, 2017
Published: December 13, 2017

© 2017 American Chemical Society 1504 DOI: 10.1021/acssuschemeng.7b03811

ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

Figure 1. Supply risk, (a) circulability (CM), and (b) market value of different cathode materials based on their metal content; (c) estimation of spent
LIBs in Canada, Mexico, and the USA, 2010−2030 and the market size in North America, USA, China, and globally (supply risk is based on the
worldwide governance indicator, WGI; the quality of cathode materials only considers the quality of metals to evaluate the market value of cathode
materials; metal prices are the 1-month average price obtained from Shanghai Metals Market).13−16,25,26

have obvious advantages, such as milder reaction conditions,
more environmentally friendly, and higher recovery efficiency
of valuable metals, especially Li.1,9,10 These advantages make
hydrometallurgical methods preferable and promising ap-
proaches for processing spent LIBs.
In this paper, the current status of lithium-ion batteries and
recently developed strategies in pretreatment and metallurgical
processes are systematically addressed, focusing especially on
the hydrometallurgical processes. Furthermore, the challenges
and deficiencies are analyzed and discussed. The regulations
and legislations concerning spent LIB management are also
reviewed. The aim of this review is to provide a general
guideline for how spent LIB recycling techniques can be
improved.
Commission and Shanghai Metals Market.13−16 It demon-
strates that (1) the recycling of LiCoO2 and NCM is slightly
more important and profitable than that of other materials due
to high cobalt content, (2) the high-cost and low-circulability
metals in the cathode materials are gradually replaced by low-
cost and high-circulability ones with lower supply risks in the
last decades, (3) to decrease the pressure from supply risk, it is
necessary to enhance the circulability of Co and research new
cathode materials containing metals with little supply risk and
high circulability. The production of LIBs from 2011 to 2016
remains increasing at a fast rate and is estimated to reach
169.09 GWh in 2018.17−19 One reason is the rapid develop-
ment of electric vehicles, whose sales remain increasing
healthily in recent years.20 As important cathode materials of

■
DEVELOPMENT OF LITHIUM-ION BATTERIES
At the beginning of the 1990s, SONY manufactured the first
ever commercial rechargeable LIBs in the world, consisting of a
carbon anode and a LiCoO2 cathode.11 Since then, LIBs have
been regarded as the most promising “green battery” for their
high energy density, good design flexibility, and long lifespan in
comparison with other types of batteries.12 For the increasing
needs of developing battery-powered devices to be satisfied,
new types of LIBs have been extensively explored in recent
years, including LiCoO2, LiNiO2, LiFePO4, lithium nickel
cobalt manganese (NCM), and lithium nickel cobalt aluminum
(NCA). As seen in Figure 1(a and b), the supply risk,
circulability (CM), and market value of different cathode
materials are evaluated based on data from the European
1505
power battery, NCM, NCA, and LiFePO4 will increase
accordingly, resulting in a large amount of valuable metals
such as Ni, Co, and Li awaiting to be recycled through the
waste stream.21 The components of LIBs waste will become
much more complex without efficient classification and
management. Nevertheless, data from the USGS indicated
that at most 20% of the batteries available for recycling actually
were recycled.22 Meanwhile, the International Resources Panel
reported that less than 1% of lithium from spent LIBs was
recycled in the world.23 Contrast this with the increasing
quantity of spent LIBs around the world, which is illustrated in
Figure 1(c) and also demonstrates the market revenue of LIBs
in the USA from 2013 to 2024. Moreover, it is obvious that a
positive correlation exists between the quantity of spent LIBs
and the market size of LIBs. Therefore, from the market
revenue of LIBs, the rising tendency of spent LIBs could be
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
predicted.24,25 The recycling of spent LIBs urgently needs to be
studied to establish a more economic and eco-friendly
industrial process than current processes.
■ STATE-OF-THE-ART FOR SPENT LIBS RECYCLING
The recycling processes of spent LIBs mainly include reuse,
repair, and recovery, among which the recovery process has
drawn much attention and will be introduced in detail in this
section. In addition, the challenges of recycling processes will
be analyzed in the Discussion. A summary of currently available
treatment approaches is shown in Figure 2. Prior to processing,
Figure 2. General flow sheet of spent LIB treatment processes.
the spent LIBs should be first discharged to reduce the
existence of Li metal and minimize the risk of explosion. A
common method is using salt-saturated solutions such as NaCl
and Na2SO4 to discharge spent LIBs.27 The critical downside of
this method is the emission of HF directly triggered by leakage
of electrolyte into water, which is shown in eq 2.
LiPF6 + H 2O → LiF + POF3 + 2HF↑ (1)
Afterward, there are three recycling routes: Route 1 is the
recycling or recovery process, which is composed of pretreat-
ment (sometimes the discharging process is also regarded as a
pretreatment process), pyrometallurgical process, and hydro-
metallurgical process. Route 2 is the repairing process. Route 3
is the reusing process, which mainly focuses on reusing Cu, Al
foil, and plastic that could be directly reused after disassembly.
The profit of route 3 largely depends on the efficiency of the
disassembly process. As for route 2, the advantage of it is
shorting the recycling route to decrease the loss of valuable
metals or materials and increase the profile of technologies. The
general process is using NMP or other organic agents to
separate cathode materials from Al foil and then achieving the
repair of spent cathode materials through calcination.28−30 It is
not cost-effective to respectively recover Fe and Li compounds
from the spent LiFeO4 through conventional extraction
technologies. Through the repairing process, a green chemical
and economic technology could be established.30−32 Addition-
ally, the methods of reuse and repair are often ignored though
these processes could be very convenient and economical due
to their short and effective flows.
Pretreatment Method. For the efficiency of recycling
materials to be enhanced, either a mechanical or chemical
pretreatment process is usually applied to make the different
1506
Perspective
waste battery streams ready for subsequent processing. The
more careful the pretreatment is applied, the more convenient
the following process will be. The pretreatment processes
mainly include dismantling, crushing, screening, thermal
treatment, mechanochemical method, dissolution, and so on.
Some of valuable metals or materials, like Cu, Al, and anode,
are easy to recycle through pretreatment due to their
significantly different physical properties. Meanwhile, pretreat-
ment methods play an important role in separating cathode
materials from the Al foil and the organic binder, which will
increase the complexity of leachate or make the waste hard to
leach. For example, because of the malleable properties of
copper being much better than those of graphite, the copper
foils are easy to separate from graphite carbon particles.33
Shin et al.34 presented a single pretreatment technology in
which the spent LIBs were crushed directly into a suitable size
and then a magnetic separation was conducted to collect the
magnet. At the end of the process, fine crushing and sieving
were employed to eliminate Al foil, which will influence the
leaching process. The removal of organic binder is important in
the pretreatment process. Common solutions are thermal
treatment,35,36 ultrasonic cleaning,37 and organic reagent
dissolution.38 Granata et al.35 used two-rotor crushing and a
splitter to achieve the separation of different materials. The
organic binder was eliminated by thermal treatment at 300 °C
for 2 h. However, the decomposition of organic components
like PVDF will release toxic and hazardous gases such as HF
and heavy metal-contaminated exhaust. Hence, using a system
that consists of a cooler, a condensation chamber, carbon filters,
and bag filters as tail gas process plants to dispose gases appears
to be necessary. Considering these disadvantages of the thermal
treatment, researchers tried organic reagents to dissolve the
organic binder. For example, the mixture of N,N-dimethylfor-
mamide (DMF) and ethanol or N-methylpyrrolidone (NMP)
is used as the dissolution reagent to dissolve PVDF, whereas
the dissolution solvent itself is commonly known as toxicant.38
To offset the shortcoming of using a toxic solvent, Pant and
Dolker39 reported a green, nontoxic, and environmentally
friendly solvent: citrus fruit juice (CFJ), as dissolution reagent.
Nevertheless, the execution of the process involving CFJ
normally requires harsh conditions (over 90 °C) to achieve
effective dissolution.
In addition to mechanical processing approaches, the
mechanochemical process is also an important technology
that induces mechanically changes of raw materials to influence
their physical and chemical properties through high-energy ball-
milling of materials.40−43 Meanwhile, some chemical reactions
could be accidentally started during the grinding and rubbing.
After that, the activity of materials will be improved. Therefore,
mechanochemical technology is usually used in pretreatment
processes to change or disrupt the crystal structure of spent
materials to enhance the leaching efficiency.40 Though many
researches have focused on the research of pretreatment
methods, some technical hurdles and challenges still exist
during the pretreatment, as summarized in Table 1.
Furthermore, the disordered classification of spent batteries,
complex disassembly processes, and low efficiency of extracting
valuable metals like lithium still hinder the application of some
pretreatment processes. Therefore, to meet the goal of
recycling all valuable materials or metals in spent LIBs,
pretreatment methods need to be combined with other
physical and chemical processes.
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

Pyrometallurgical Process. The pyrometallurgical process

41,42,50,51
29,48,49
is one branch of the extractive metallurgies to dispose ore and
44,45

46,47
ref
concentrates with thermal treatment through physical and
chemical transformations to enable recovery of valuable metals.
Pyrometallurgical methods have been widely investigated in
would cause serious exhaust pollution if no exhaust purification device is
require high input of energy, cannot recover organic compounds, and recovering Zn, Ni, Cd, and other heavy metals from spent Zn−
Mn dry batteries or Ni−Cd batteries.52,53 Generally, smelt slags
cannot recycle all kinds of components in spent LIBs completely

were used in pyrometallurgical methods to separate metals in

which some metals go to the slag and target metals turn into
alloy. Except for the Umicore technology,54,55 pretreatment
high cost of organic solvent as well as device investment

processes are unavoidable for most of the pyrometallurgical

technologies. Ren et al.56 proposed a new slag system of MnO-
high energy consumption and noise problems

SiO2-Al2O3 by adding CaO+SiO2, pyrolusite, and some Al

disadvantages

shells into the pretreated spent LIBs. The mixture was then
heated to 1475 °C for 30 min. A high purity alloy with Co
(99.03%), Ni (99.30%), Cu (99.30%), and enriched slag with
MnO (47.03%) and Li2O (2.63%) were achieved by this novel
process.
In a typical pyrometallurgical process, Li will end up in the
slag phase, which has to be further extracted.15 Carbothermal
reduction methods as a pyrometallurgical method to recycle Li
and other metals have received attention in recent years.57 In
equipped

this process, the mixed spent LIBs can be converted to metal

oxide, pure metal, or lithium carbonate. In one step, lithium
carbonate is leached by water, whereas the graphite in the
leaching slag burn and leave metal oxide as the final residue.58
low energy consumption and almost no exhaust

In the subsequent step, pure metal, graphite, and lithium

enhancing the leaching efficiency of valuable
metal and making the reaction conditions

carbonate are further separated by wet magnetic separation.59

However, the pyrometallurgical technologies also currently face
challenges on reducing energy consumption and matching the
simple and convenient operation

simple and convenient operation

rigorous requirements for the treatment equipment.

Table 1. Summary of Advantages and Disadvantages of Different Pretreatment Methods
advantages

Hydrometallurgical Process. A hydrometallurgical proc-

ess mainly consists of leaching and extraction. It has many
advantages in comparison with the pyrometallurgical process,
such as high extraction efficiency, low energy consumption,
become mild

little hazardous gas emission, and low capital cost. It has a huge
emission

potential in industrial realization. However, little adaptability

for disposing raw materials is a great challenge. Figure 3 shows
a comprehensive summary of the hydrometallurgical process,
which mainly includes leaching, solvent extraction, precipita-
including density, conductivity, magnetic behavior, and so

remove organic additives and binders via thermal treatment

separate materials according to different physical properties,

tion, and the electrochemical method. Among them, a very

discording the structure of the materials using grinding

limited number of studies are reported on the disposal of spent

dissolve the adhesive substance using special organic
detail of methods

techniques
reagents
forth

dissolution process

mechanochemical
thermal process
technology

separation
mechanical

method

Figure 3. Hydrometallurgical processes for spent LIBs.

1507 DOI: 10.1021/acssuschemeng.7b03811

ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
Figure 4. (a) Connections between pH and the equilibrium concentration of metal ions in aqueous solution (25 °C); (b) E-pH diagram for the Co-
H2O and Ni-H2O systems (25 °C, Co = 0.2 mol L−1, Ni = 0.2 mol L−1).
LIBs via the electrochemical process due to its high energy
consumption, even though prior arts do suggest its feasibility
for obtaining pure Co metal or Co compounds.8,60−62
Traditional Leaching. For spent LIBs to be recycled, the
cathode materials are usually dissolved in leaching reagents
followed by separation and extraction as the main steps, which
are similar to other metallurgical processes. In early research,
inorganic acid reagents, such as HCl, HNO3, and H2SO4 were
widely used as leaching agents and were proven to be feasible
and effective, but disadvantages, e.g., the emission of secondary
pollutants and complexity of separation and purification steps,
also appeared.47,63,64 The chemical reaction of leaching using
HCl can be described as
8HCl + 2LiCoO2 → 2CoCl 2 + Cl 2 ↑ +2LiCl + 5H 2O (2)
The reaction using other monatomic acid or ployatomic acid
for leaching is similar. The leaching efficiency of Co without
reductants follows the order of HCl > HNO3 ≈ H2SO4. The
relatively high reducibility of HCl mainly contributes to this
different leaching performance.65 Therefore, the leaching
efficiency of most reagents would be unsatisfying unless
H2O2 or other reductants are added. The mechanism of the
reduction reaction can be described as (taking LiCoO2 as an
example)
3H 2SO4 + 2LiCoO2 + 2H 2O2 → Li 2SO4 + 5H 2O + 1.5O2 ↑ + 2CoSO4
(3)
The reason that reductants like H2O2 or ascorbic acid can
facilitate leaching can be explained by Figure 4(a). Although
Co2+ is much easier to dissolve than Co3+ at room temperature,
Co3+ is predominately rich in spent materials. Hence, when the
Co3+ is converted to Co2+, the leaching efficiency and reaction
kinetics will be obviously improved. Furthermore, the shadow
in Figure 4(a) may be a favorable area to separate Co3+ from
Cu2+, Mn2+, and other metal ions because of its significantly
different solubility constant among these metal ions. With
increasing in reductant concentrations, the leaching efficiency
and reaction rate would first increase accordingly and then
reach a plateau at which leaching efficiency and reaction rate
would not vary appreciably.66
Except for adding reductant, many organic leaching reagents,
such as citric acid,67 aspartic acid,67 malic acid,67 oxalic acid,68
ascorbic acid,69 and glycine,70 are extensively investigated to
solve those problems associated when using the inorganic
1508
Perspective
leaching reagents. The reaction mechanism of leaching by citric
acid could be described as71
18LiNi1/3Co1/3Mn1/3O2 + 18H3Cit + C6H12O6→
6Li3Cit + 2Ni3(Cit)2 + 2Co3(Cit)2 + 2Mn3(Cit)2 + 33H 2O + 6CO2 ↑
(4)
72
According to Li et al., the leaching efficiency of Co using
citric acid is higher than that when using HCl or H2SO4,
whereas the Li leaching efficiency remains similar among those
different leaching media. Most of organic acids present a similar
reaction mechanism to critic acid with some exceptions such as
oxalic acid. The oxalic acid could act both as reductant and
leachant, and the leaching efficiencies of Co and Li could
achieve 97 and 98%, with the reaction described as68
4H 2C2O4 + 2LiCoO2 → CoC2O4 ↓ + LiHC2O4 + 2CO2 ↑ + 4H 2O
(5)
In addition to the acid leaching system, an alkaline system
such as ammonia has also been investigated. Zheng et al.73
introduced an ammonia-ammonium sulfate system as a leaching
system with metal selectivity during leaching. Ku et al.9 used a
similar system including ammonia, ammonia sulfite, and
ammonia carbonate to leach. It was easy to separate Cu from
Co, Ni in the ammonia system, because Co and Ni in spent
LIBs were in high valence state, making them hard to dissolve.
Ammonia carbonate acted as a pH buffer to stabilize the pH of
leaching solution. Ammonia sulfite was added as reductant to
increase the leaching efficiencies of Co and Ni.
In addition, the widely employed supercritical fluid in
extracting metals offers a potential opportunity in leaching
spent batteries. Bertuol et al.74 investigated the leaching of
cobalt from the spent LIBs under a supercritical CO 2
atmosphere with sulfuric acid and H2O2. The results showed
that the reduction duration and consumption of H2O2 could
respectively drop from 60 min and 8 vol % to 5 min and 4 vol
% while achieving the same leaching performance (95.5% Co).
Liu et al. 75 used subcritical water to accelerate the
dechlorination of PVC, which was regarded as the acid source
in this experiment. Over 95% Co and closely 98% Li were
leached under the conditions PVC/LiCoO2 ratio of 3:1, solid/
liquid ratio (S/L) of 16:1 (g/L), and temperature of 350 °C.
However, the rigorous requirements of the equipment, high
temperature, and high pressure atmosphere increase the capital
cost and complexity of the operation. All of these technical
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

Table 2. Cases of Leaching Spent LIBs Using Different Leaching Reagents

leaching
efficiency (%)
raw material reagent temp (°C) time (min) Co Li ref
Inorganic Acid Leaching
spent LIBs 1.75 mol/L HCl 50 90 99.0 100.0 78
spent LIBs (LiCoO2) 4 mol/L HCl 80 30 90.6 93.1 79
LiFePO4 and LiMn2O4 6.5 mol/LHCl + 5 vol % H2O2 30 60 74.1 80
LIB industry waste (LiCoO2) 2 mol/L H2SO4+5 vol % H2O2 75 30 94.0 95.0 81
LiNixMnyCozO compounds 4 mol/L H2SO4 + 5 vol % H2O2 65−70 120 96.0 82
spent LIBs (mixture) 1 mol/L H2SO4 + 0.075 M NaHSO3 95 240 91.6 96.7 83
spent LIBs (LiCoO2) (from laptop computers) 2 mol/L H2SO4 + 5 vol % H2O2 75 60 70.0 99.1 84
spent LIBs (LiCoO2) (from mobile phones) 2% H3PO4 + 2 vol % H2O2 90 60 99.0 88.0 85
spent LIBs (LiCoO2) 0.7 mol/L H3PO4 + 4 vol % H2O2 40 60 99.0 100.0 86
spent LIBs (LiCoO2) 1 mol/L HNO3 + 1.7 vol % H2O2 75 60 95.0 95.0 87
Alkaline Leaching
spent LIBs (Li(Ni1/3Co1/3Mn1/3)O2) 4 mol/L NH3-1.5 mol/L (NH4)2SO4 + 0.5 M Na2SO4 80 300 80.7 95.3 73
Organic Acid Leaching
spent LIBs (LiCoO2) 0.4 mol/L tartaric acid +0.02 mol/L ascorbic acid 80 60 93.0 95.0 69
spent LiCoO2 and CoO 1 mol/L oxalate + 5 vol % H2O2 80 120 96.7 88
spent LIBs (LiCoO2) 2 mol/L citric acid + 0.6 g/g H2O2 (H2O2/spent LIBs) 70 80 96.0 98.0 89
spent LIBs (LiCoO2) 1 mol/L oxalic acid 95 150 97.0 98.0 68
spent LIBs (LiCoO2) 1 mol/L iminodiacetic acid + 0.02 M ascorbic acid 80 120 99.0 90.0 66
spent LIBs (LiCoO2) 1 mol/L maleic acid +0.02 M ascorbic acid 80 120 99.0 96.0 66
spent LIBs (LiCoO2) 0.5 mol/L glycine +0.02 M ascorbic acid 80 120 91.0 70
spent LIBs (LiCoO2) 1.5 mol/L succinic acid + 4 vol % H2O2 70 40 100.0 96.0 90
spent LIBs (LiCoO2and LiNi0.5Co0.2Mn0.3O2) 2 mol/L L-tartaric acid + 4 vol % H2O2 70 30 98.6 99.1 37

hurdles mentioned above have reduced the passion for applying

supercritical fluid in recycling batteries.
Table 2 provides a summary of the details of leaching
processes of spent LIBs. Though there are many reports about
leaching processes, few of them focus on explaining the
leaching mechanism based on the crystallographic method at
the molecular or atomic level. Takacova et al.76 explored the
change of spent LIBs in the HCl leaching process depending on
the change in d(003). It could be a good choice for further
investigations of the leaching process in the future. The more
mechanisms we understand for the leaching process, the more
conveniences we obtain for enhancing the efficiency of the
leaching process.
For achieving visualization of pros and cons of using different
leaching reagents, quantifying methods for leaching rates of Li
and Co are proposed in this work. The leaching rate of metal is
defined as
rM = WM × a × R /t (6) Figure 5. Spider chart for a relative evaluation index of leaching spent
LIBs with typical leaching reagents.
where rM represents the leaching rate of metal, WM (w/w %)
represents weight percentage of metal in raw materials (spent
LIB), a (%) is the leaching efficiency of metal, R (g/L) is the S/
L, and t is the leaching time. This equation allows us to and cost of organic reagent are much higher than those of
compare the leaching performance among different reagents. In inorganic reagent. However, considering the biodegradability of
general, the leaching efficiency of valuable metals can reach leaching reagent and reducing flue gas of the productive
more than 90%. However, some of them use a low S/L or long process, the advantages of organic reagent are quite obvious.67
leaching time. Assuming 1 kg of Co is leached from spent LIBs Moreover, we do not give the relevant data about GHG
by different leaching processes, greenhouse gas (GHG) emission and energy consumption of H2SO4. The leaching rate
emissions, energy consumption, and cost are also calculated of valuable metal in H2SO4 is much better than other reagents
with stoichiometric consumption of materials to evaluate for a large S/L and short reaction time. However, H2SO4 is
recycling. The relative data are gathered from the greenhouse usually obtained as a byproduct of other technologies in many
gases, regulated emissions, and energy use in transportation companies, i.e., copper smelting. Therefore, there are no data
(GREET) model proposed by Argonne National Laboratory.77 about GHG emission and energy consumption of H2SO4
As given in Figure 5, the GHG emission, energy consumption, production.77
1509 DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
In summary, leaching time, agitation speed, solid-to-liquid
ratio, temperature, and concentration of leachant and reductant
were found to be the most influential factors on the leaching
performance. The leaching process would be enhanced with
increasing temperature, leaching time, agitation speed, as well
as concentrations of leachant and reductant, whereas the
leaching efficiency and rate both obviously decrease as the
solid−liquid ratio increases. It should be noted that plateaus
would show up when these factors increase to a certain value.
These will guide future efforts in optimization of leaching
processes upon processing different types of LIBs using
different leaching media.
Biometallurgical Process. The performance of the
biometallurgical process primarily depends on the ability of
microorganisms to convert insoluble solid compounds into
soluble and extractable forms.91 Mishra et al.92 used chemo-
lithotrophic and acidophilic bacteria Acidithiobacillus ferroox-
idans as leaching bacteria. The reaction could be maintained at
30 °C with a pH of 2.5, but the leaching efficiencies of Co and
Li both were quite low even with a long leaching time and Fe2+
as catalyst. However, according to the reports from Zeng et al.
and Chen et al.,93,94 the leaching efficiency of Co could reach
98.4% within 7 days in Acidithiobacillus ferrooxidans with 0.02
g/L Ag+. Similarly, Cu2+ could also be used as catalyst during
the Acidithiobacillus ferrooxidans leaching process.95 The result
showed that the leaching efficiency of Co could reach 99.9% in
6 days with 0.75 g/L of Cu2+ added into solution. Using a
mixed culture of different bacteria in one system was trialed,
such as the system mixed with acidophilic sulfur-oxidizing
bacteria (SOB) and iron-oxidizing bacteria (IOB).96,97 Fungal
leaching is a favorable technology compared with bacterial
leaching.98 It has many advantages, including growing over a
wide pH range, tolerating toxic materials, and conducting with a
high leaching rate. Various organic acids in fungi metabolites
have been used to achieve the leaching process.98,99
Compared to the conventional methods, the biometallurgical
process occurs under mild conditions with less energy
consumption, making it an eco-friendly technology.100 Never-
theless, the slow kinetics and low pulp density are fatal
weaknesses of the biometallurgical process when it is applied to
industrial production. In one research study,101 the bioleaching
efficiency decreased from 52 to 10% for Co and from 80 to 37%
for Li when the pulp density increased from 1 to 4%. Even
though high leaching efficiencies of Co and Li may be achieved
with a high pulp density by controlling reaction temperature,
increasing the dose of mixed energy substrates, and adjusting
the pH,101 the leaching processes are still very time consuming.
Hence, the biometallurgical methods of disposing spent LIBs
are still far from industrial application, although they have
significant advantages in energy-saving.
Solvent Extraction. One of the main targets for the
recycling process is to obtain pure metal or metal compounds.
However, the coexistance of various metal ions in the leachate
will inevitably suppress the recycling of pure metal or metal
compounds. In addition, the overlap of pH range for
precipitation of different metals makes the attempt of single
step precipitation ineffective for obtaining pure metals. Hence,
the leaching solution must undergo numerous steps of
separation and extraction, e.g., solvent extraction, selective
precipitation, and electrochemical method to achieve satisfac-
tory levels of purity.
Solvent extraction is a liquid−liquid extraction method that
utilizes the different relative solubilities of compounds in two
1510
Perspective
immiscible liquids to separate them from each other. Although
facing the challenges of separating compounds with similar
functional groups, it remains reliable and is widely adopted in
the extraction of tungsten and molybdenum, copper from
minerals, nuclear reprocessing, and the production of fine
organic compounds.
The effect of equilibrium pH on the extraction of different
metals is significant in solvent extraction. For example, the di(2-
ethylhexyl) phosphoric acid (D2EHPA) is good at extracting
copper and manganese ions, whereas its selectivity in extracting
Co is poor at pH 2.2−3.0.102 When the pH of the leachate
increases, the extraction efficiency of Co with cationic
extractant D2EHPA is improved accordingly.103 The extraction
reaction follows the mechanism63,104
M2Aq+ + A −Org + 2(HA)2Org → MA 2·3HA Org + H+Aq (7)
or
+
2(HA)2Org + MOH(Aq) + A −Org → M(OH)A· 3HA (Org) + H(Aq)
+
(8)
where A −Org + 2(HA)2Org represents the saponification reaction
as
1
Na +Aq + (HA)2Org → NaA Org + H+Aq
2 (9)
The extractant PC-88A can effectively separate Co and Ni
ions from other metal ions at pH 4.5, whereas it has no
extraction efficiency when the pH is less than 3.102 Cyanex272
has been widely investigated as an extractant due to its excellent
selectivity. Swain et al.81 used Cyanex 272 as extractant, 5 vol %
tributyl phosphate (TBP) as phase modifier, and kerosene as
diluent to extract 85.42% Co from the leachate at pH 5. Jha et
al.105 also reported a similar system except that isodecanol was
used as phase modifier. The extraction efficiency of Co reached
99.9% at pH 5.0.
The suitable scales of pH of different extraction reagents are
summarized in Figure 6.79,103,106−108 It is obvious that the
suitable pH to separate Co and Ni of some reagents distributes
in the pH range between 3 and 5, which requires a good
Figure 6. Effect of suitable pH on the solvent extraction of different
extraction reagents (the pH scale of different extractants is summarized
under the same conditions including 25 °C and A:O = 1, except
Mextral 5640H (A:O = 2)).
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
performance in corrosion resistance for the reactor. For this
reason, Cynaex 272 and P507 may be a good choice. The
additive can change the optimal pH of solvent extraction. For
example, in Figure 6, when the PC-88A is used alone to
selectively extract Co, the suitable pH range falls between 3.5
and 4. The extraction efficiency of Ni is low in this range. When
TOA is added as phase modifier, the suitable pH scale will shift
between 3.5 and 5, which is higher than its previous one and
leaves more room for operational parameters to adjust.
Precipitation. The selective precipitation is a single
chemical process that has been widely investigated and applied
in extracting metals from complex systems. Sometimes, it is
hard to precipitate only one ion from solution. From the E-pH
diagram shown in Figure 4(b), the overlap between stable areas
of Co(OH)2 and Ni(OH)2 is so large that Ni2+ and Co2+ are
prone to be coprecipitated via neutralization reaction. However,
Figure 4(b) also indicates that the stable areas of Ni2+ and
Co(OH)3 have a small overlap. Thus, one possible approach is
to transform Co2+ to Co3+ to achieve selective precipitation of
Co3+ in this small area. This strategy was proven to be feasible
and effective by Joulié et al.65 With NaClO as oxidant, the
recovery efficiencies of Co and Ni were both nearly 100%. The
reaction mechanism can be expressed as
Co2 + + ClO− + 2H3O+ → 2Co3 + + Cl− + 3H 2O (10)
Co3 + + 6HO− → Co2O3 + 3H 2O (11)
It should be noted that no Mn exists in the system reported
by Joulié et al.65 When Mn2+ is oxidized to Mn4+ at pH 2, it will
form MnO2 or manganese hydroxide according to the reaction
3Mn 2 + + 2MnO4 + 2H 2O → 5MnO2 + 4H+ (12)
The dimethylglyoxime reagent (DMG, C4H8N2O2) is widely
used to precipitate Ni2+ as nickle dimethylglyoxime chelating
precipitate from Co, Ni, and Mn mixed solutions. As reported
by Chen et al.,109 nearly 96% of Ni2+ could be precipitated
within 20 min at room temperature (eq 14). The values of
pKsp for Co2+, Ni2+, and Li+ are on the order of NiC2O4 ≈
CoC2O4 ≫ Li2C2O4.39 After removing Ni2+ and Co2+, the main
metal ion in leachate is Li+, which can be precipitated efficiently
as Li2CO3 or Li3PO4 (eq 16).71
6C4 H8N2O2 + Ni3(Cit)2 → 3Ni(C4H6N2O2 )2 + 2H3Cit
(13)
(NH4)2 C2O4 + Co2 + + 2OH−
→ CoC2O4 · 2H 2O + 2NH3 (14)
Co3(Cit)2 + 3H 2C2O4 → 3CoC2O4 + 2H3Cit (15)
Li3Cit + H3PO4 → Li3PO4 + H3Cit (16)
Method of Leaching Resynthesis. Traditional separation
and extraction technologies, e.g., solvent extraction, precip-
itation, and ion-exchange, are usually not economically
justifiable to be applied in industrial production due to their
significant disadvantages, e.g., complicated recycling routes,
high chemical reagent consumption, and high waste emission.
Therefore, a short and efficient route for the recycling of spent
LIBs is the potential process and needs to be researched. To
shorten the route, avoid the problems in separating metal ions
from each other, reduce secondary pollution, and enhance the
recycling efficiencies of valuable metals, material synthesis
1511
Perspective
methods to achieve one-step fabrication from leachate to
regenerate materials were recently researched, such as the
leaching-resynthesis method.110−112 The leaching-resynthesis
method, which belongs to regeneration methods, is focused on
synthesizing the regenerated materials in short steps through
sol−gel or coprecipitation technologies.
In recent research, Sa et al.111 used the leachate as a raw
liquor to regenerate LiNi1/3Mn1/3Co1/3O2 in N2 atmosphere at
room temperature using a typical coprecipitation method. After
50 cycles, the capacity of regenerated material decreases to 80%
(120 mA h g−1) with the first cycle.111 With previous
experience of using ascorbic acid for leaching, Lu et al.113
adjusted the metal ion ratio and pH of the leachate to obtain
regenerated cathode material LiCo1/3Ni1/3Mn1./3O2 through a
sol−gel process. Zou et al.114 used similar technology to
dispose the mixed raw cathode materials and obtained
regenerated cathode materials as products with good electric
performance. Some information on the leaching-resynthesis
approaches are provided in Table 3. It can be seen that the
regenerated cathode materials present similar characteristics to
the commercial batteries in terms of rate capacity and cycle life.
Among them, the electrochemical properties of regenerated
cathode materials from the ascorbic acid leaching system are
much better than those prepared from other systems. Other
than that, the available data suggest that little difference of
electrochemical properties exists in cathode material from
different leachates.
Except for cathode materials, synthesizing other reactive
materials from the spent LIBs is also a good alternative and has
been widely developed by many researchers. Yao et al.115 used a
simple technology, including pretreatment, sulfuric acid
leaching, filtering, sol−gel, and calcination method, to obtain
sintered or hydrothermal cobalt ferrite precursor (S-CoFe2O4
or H-CoFe2O4). The products have excellent characteristics in
terms of magnetostriction coefficient (−158.5 ppm) and train
derivative coefficient (−1.69 × 10−9 A−1).115
■
CURRENT RESEARCH FOR THE RECYCLING OF
ANODE AND ELECTROLYTE
The recycling of anode and electrolyte is also important to
establish a comprehensive recovery technology of the spent
LIBs as well as to release the environmental pollution and
potential safety risks. However, because of their relatively low
value, only a little attention has been paid to this area. In the
Umicore process, the electrolyte is removed and pyrolyzed
under 300 and 600 °C, respectively.120 In hydrometallurgical
processes, the electrolyte can be reclaimed using an organic or
supercritical solvent.121 Liu et al.122 developed a process for the
recycling of spent LIB electrolyte including supercritical CO2
extraction, weakly basic anion exchange resin deacidification,
molecular sieve dehydration, and component supplement. The
electrochemical performance of the reclaimed electrolyte was
acceptable compared to that of the commercial one. The high
cost and low process capacity are the key factors limiting
further promotion of supercritical solvent.
As for the anode, it is usually separated from spent LIBs
through physical methods, including dismantling, crushing,
screening, and other mechanical processes. Guo et al.123
indicated that 30.07 mg/g of Li existed in the anode active
materials. Therefore, a traditional acid leaching method was
used to recover Li from anode active materials. Moreover, the
graphite obtained from spent anode showed a large surface area
and stable crystal structure. After removing the organic binder
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

and other organic impurities under high temperature, it could

110
111
113
116
117
118
114
119
ref
be used as a porous supporting material to synthesize new
functional materials like sorbents.124,125
initial discharge capacity (mA h g−1, 2.7−4.3 V, 0.1 C)

■ CURRENT INDUSTRIAL RECYCLING PROCESS

The recovery of spent LIBs are relatively new in comparison
with the recycling of Ni-Cd and Pb-acid batteries, and many of
197.7, 174.3, 168.3

the technologies are still in lab- or small-scale pilot stages. The

first commercial production line was established by TOXCO in
147.2 (0.5 C)
154.2 (0.2 C)

152.7 (0.2 C)

1994.126 After that, with the increased attention, more and

more technologies have been applied in commercial
139.0

155.0

160.0
258.8

production, and many companies have established a complete

line to recycle spent LIBs around the world. Current industrial
processes for the recycling of spent LIBs are summarized in
Table 4. The percentage and annual processing capacity of
spent LIBs recycled using different technologies are shown in
Figure 7 in which the data are mainly based on 30 and 12
companies, respectively.
A flow sheet of the main processes is shown in Figure 7(c).
controlled crystallization
NaOH and NH3·H2O

NaOH and NH3·H2O

Many of the commercial processes used pyrometallurgical

ammonia solution

ammonia solution

methods as secondary technologies.127 The reason is that most

precipitant

of them are not an LIB-dedicated recycling process in their

metal nitrate

oxalic acid

original design, such as Xstrata, Batrec AG, Akkuser, and so

NaOH

forth. Only Co, Ni, and Cu could be recovered effectively

Table 3. Summary of the Regeneration Approach of Cathode Materials from Spent LIBs in the Literature

through pyrometallurgical methods. Li and Al are lost in the

slag. Moreover, an alloy of cobalt and nickel also needs to be
addition reagent

processed through hydrometallurgical methods, such as

acetate salts
nitrate salts
sulfate salts
sulfate salts

sulfate salts
sulfate salts
sulfate salts

electrolyzing. Therefore, most of these companies establish a

solution

process combining pyrometallurgical and hydrometallurgical

methods. In the Umicore process, the discharging phase is
omitted, and pretreatment of spent LIBs is unnecessary, which
are the important technologies in other processes. Compared to
citric acid (+ H2O2)
leaching reagent
H2SO4 (+ H2O2)
H2SO4 (+ H2O2)

H2SO4 (+ H2O2)
H2SO4 (+ H2O2)
H2SO4 (+ H2O2)

other processes, it is simple and effective. Complex mechanical

methods are used to separate materials from each other. The
D,L-malic acid

ascorbic acid

Cu foil, Al foil, and steel are separated from other components

and reused directly in new batteries through mechanical
methods in other processes. However, they need to be further
recovered to obtain production in the Umicore process. Toxco
LiNixCoyMn1−x−yO2 (LiNi0.8Co0.1Mn0.1O2 LiNi0.5Co0.2Mn0.3O2 LiNi1/3Co1/3Mn1/3O2)

and Sumitomo-Sony processes face the issues of gas emissions

in pyrometallurgical methods and H2 emissions in wet crushing.
The processes include similar methods that also have these
issues. The Recupyl Valibat process conducts the recycling
process under low temperature, making it easy to dispose of
flue gas and H2. Handling spent LIBs under a CO2 atmosphere
also reduces the risk of mechanical treatment with discharged
LIBs. Many hydrometallurgical methods have also been
achieved in industrial applications, including the Recupyl
Valibat process, Toxco process, Accurec, and so forth. In the
final production

Recupyl process, the slag from mechanical treatment is

dissolved in H2SO4. Cobalt in solution is oxidized by NaClO
to obtain cobalt hydroxide. Lithium remaining in the solution is
precipitated by CO2 gas. In other companies, the hydro-
metallurgical processes include similar technologies, such as
Li[(Ni1/3Co1/3Mn1/3)1−xMgx]O2

leaching, solvent extraction, precipitation, and so forth. Their

long routes are the main drawback, which will result in the loss
Li1.2Co0.13Ni0.13Mn0.54O2

of valuable metal and pollution. Brump establishes a closed-

LiNi1/3Mn1/3Co1/3O2
LiNi1/3Mn1/3Co1/3O2
LiNi1/3Co1/3Mn1/3O2

LiNi1/3Mn1/3Co1/3O2

loop for the recycling of spent LIBs from waste to regenerated

LiNixMnyCozO2

cathode materials or other valuable materials, which could

achieve the recycling of spent LIBs in a short route. The details
of these hydrometallurgical processes are not available, but they
could be similar to the processes we introduced in Hydro-
metallurgical Process.
1512 DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
 Table 4. Summary of Current LIB Recycling Industrial Technologies Throughout the World120,128,129
annual capacity main end
company/process location(s) (tonnes/year) details of technology products
Umicore U.S.A. 7000 combines pyrometallurgical and hydrometallurgical technologies; spent LIBs are fed to a single shaft furnace; alloy containing Co and Ni from furnace CoCl2
(VAL’EAS) further processed through leaching; Li and Al mainly exist in the slag and need to be further treated through hydrometallurgical technologies
SNAM France 300 first stage is sortation techniques; rough crushed products then disposed by pyrolysis pretreatment, crushing, and sieving
Batrec AG Switzerland 200 spent LIBs stored and shredded under CO2 atmosphere; scrap then neutralized by moist air and further treated with hydrometallurgical process
Inmetco U.S.A. 6000 scrap processed in a rotary hearth furnace and further refined in an electric arc furnace alloy (Co/
Ni/Fe)
Sumitomo-Sony Japan 150 electrolyte and plastics removed through calcination; pyrometallurgical process used to recover alloy containing Co-Ni-Fe; hydrometallurgical process CoO
conducted to recover Co
AkkuSer Ltd. Finland 4000 two-phase crushing line is designed; magnetic and other separation methods follow it; scrap then delivered to smelting plants and leaching metal powder
Toxco Canada 4500 combines mechanical methods including shredding, milling, and screening and hydrometallurgical methods including leaching and precipitation CoO, Li2CO3
Recupyl Valibat France 110 mechanical methods used as first stage; hydrometallurgical methods then used to obtain Co(OH)2 and Li3PO4 Co(OH)2,
Li3PO4
Accurec GmbH Germany 6000 vacuum furnace used first; mechanical methods then used to separate different materials; scrap then fed to an electric furnace; slag is disposed of through Co alloy,
hydrometallurgical methods Li2CO3
ACS Sustainable Chemistry & Engineering

AEA U.K. first stage uses organic solvent to remove electrolyte, solvent, and binder; leaching of cathode carried by electrolyzing LiOH, CoO
Glencore plc. Canada/ 7000 combines pyro- and hydrometallurgical methods alloy (Co/
(former Xstrata) Norway Ni/Cu)
Onto process USA preliminary step involves discharge, electrolyte recovery, refurbishing, and ball mill; supercritical fluid used to separate different materials cathode
powder
LithoRec proces Germany combines similar mechanical and hydrometallurgical methods CoO, Li salt
Green Eco- China 20000 hydrometallurgical methods including leaching, purifying, and leaching- resynthesis used Co powder

1513
manufacture Hi-
Tech Co
Bangpu Ni/Co China 3600 hydrometallurgical methods including leaching, purifying, and leaching- resynthesis used cathode
High-Tech Co material,
Co3O4
Perspective

DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

Figure 7. Percentage of spent LIBs recycled by different technologies based on the (a) quantity of companies (30 companies) and (b) annual
processing capacity of some of these companies (twelve companies); (c) flow-sheet of main processes used in the industry.

■ DISCUSSION
First, it is very interesting to note that, in comparison with the
was much better than the traditional leaching with a high
concentration of H2SO4 and a large consumption of H2O2. In
inorganic leachants, there are relatively few organic leachants consideration of the increasing price of lithium carbonate in
recently chosen as leaching media to conduct the extraction recent years, it is a quite significant direction to research the
process even though they are regarded as green reagents. In selective extraction of Li. Of course, the best outcome is that we
most reports about solvent extraction, precipitation, or can achieve recovery of single metal element from spent LIBs
regeneration technology, the leachate are from an inorganic or other waste and leave the other metals in solid waste.15
leaching process. Among them, H2SO4 is the most frequent Second, with respect to energy consumption, data of the
leachant. Organic reagents can avoid the problems associated hydrometallurgical process, intermediate physical method from
with inorganic leachants, such as triggering air pollution, Toxco, direct physical process from OnTo Technology, and
rigorous requirements of equipment, and difficulty in recycling pyrometallurgical process from Umicore introduced by Dunn et
leaching reagents. However, the research results have shown al.134,135 have also been estimated. For simplicity, Figures 8 and
that the organic leaching can only conduct well with a low
solid-to-liquid ratio, which decreases the concentration of Li+ in
leachate and limits the treatment capacity for industrial
production. A leachate with low concentration of Li+ is difficult
to produce high-purity lithium compounds and needs to be
concentrated. Moreover, all of these leaching processes need to
be followed by solvent extraction or precipitation, in which the
loss of Li is serious, to obtain the pure production of Ni/Co/
Mn or compounds. For example, when D2EHPA is used to
extract Ni and Co, 20% Li will be coextracted.130 The loss of Li
is nearly 17% in removing Ca and Mg by NaF.118 Therefore, all
of these leaching reagents have their own limitations for
recovering valuable metals from spent LIBs in a cost-effectively
and environmentally friendly way. Selectively extracting target
metals with a hydrometallurgical process from mines or
electronic wastes has been proved to be feasible in many
prior research studies. It is regarded as a promising approach to
change the current situation in recycling spent LIBs.131 Gao et
al.132 achieved the selective extraction of Al and Li from Figure 8. Estimated energy consumption for LiCoO2 and LiMn2O4
LiNi1/3Co1/3Mn1/3O2 cathode scrap using formic acid as production via different automotive battery recycling processes
(energy consumption during virgin LiMn2O4 production in Nevada
leaching reagent. It was found that the selectivity of Al was and Chile is from Dunn et al;134 energy consumption during virgin
more than 95% with no Al(OH)3 phase existing in the Ni/Co/ LiCoO2 production is from Kushnir and Sandén136).
Mn hydroxide precipitate. Meanwhile, the relatively low
solubilities of Co(COOH)2, Ni(COOH)2, and Mn(COOH)2
compared with that of Li(COOH)2 contributes to the 9 only summarize the results of energy consumption from
spontaneous separation of Ni/Co/Mn and Li. As Zheng et Dunn et al.,134,135 in which the estimate is based on the GREET
al.73 reported, the ammonia-ammonium sulfate solution with model proposed by Argonne National Laboratory.77 Note that
reductant could also achieve the selective leaching of Li, Ni, and the energy consumption of recycling LiCoO2 through some
Co from Li(Ni1/3Co1/3Mn1/3)O2 cathode scraps. However, the processes is not directly shown in the article. The estimate of
optimal solid-to-liquid ratio in the alkali system was so small missing data follows the mechanism introduced by Dunn et
that the subsequent extraction approaches were hard to al.135 For example, the production of the intermediate recycling
conduct. Li et al.133 reported the selective leaching of Li from process is Li2CO3. We estimate the energy consumption of
spent LiFePO4 through H2SO4 at a low concentration, which LiCoO2 of the intermediate recycling process by adding the
1514 DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
Figure 9. Energy consumption (MJ/kg battery) of using recycled
aluminum, copper, cathode materials, or all of them to fabricate
batteries used in electric vehicles (solid back line is consumption of
using virgin materials134).
energy consumption of producing virgin Co3O4 and recycling
Li2CO3 following the chemical reaction of producing LiCoO2.
Figure 8 illustrates that the energy intensities of recycling
materials are less than producing virgin materials. With the
consumption of citric acid and hydrogen peroxide included in
the overall process, the energy consumption of the hydro-
metallurgical process is tremendous, whereas the process itself
is not energy intensive. Moreover, an external process of the
hydrometallurgical method, adding Mn2O3 to react with
Li2CO3 to form LiMn2O4 in the end, also makes the energy
consumption of the hydrometallurgical process more than that
of other processes. Figure 9 contains estimates of the energy
consumption and greenhouse gas (GHG) in total LiMn2O4
production with different recycled materials. It indicates that,
the more recycled materials are used in production, the less
energy will be needed in the overall process. Therefore, the
reduction of energy consumption and GHG emissions in the
Table 5. Regulations Relevant to Spent Batteries in China
regulation title
policy on pollution prevention techniques from municipal solid waste
policy on pollution prevention techniques from hazardous wastes
policy on pollution prevention techniques from waste batteries
discarded household appliances and electronic products pollution
control technology policy
auto product recovery and usage technology policy
measures for the control of environmental pollution of electronic waste
emission standard of pollutants for battery industry
technical requirement for environmental labeling products battery
policy on recycling technology of electric vehicle power battery (ask for
comment)
policy on recycling technology of electric vehicle power battery (2015)
industry norms of utilizing waste power battery from new energy
vehicles; interim measures for managing industry norms of utilizing
waste power battery from new energy vehicles
policy on pollution prevention techniques from waste batteries (ask for
comment)
Perspective
whole process to produce LiMn2O4 may be possible when
recycled LiMn2O4, Al, and Cu are used as raw materials as
shown in Figure 9.134 Furthermore, a reduction in total energy
consumption could be foreseeable if a closed-loop recycling
scenario of LIBs is achieved. Because of the lack of relevant
data, the literature seldom reports the energy consumption of
other methods, such as the regenerated and biometallurgical
methods. However, it is important to estimate the energy
consumption, which will make a difference in future work.
Third, the “3R” principles in green chemistry should be
emphasized in recycling processes. Though current research
mainly focuses on the recovery and regeneration, which are the
last principles of “3R”, it is still hard to implement recently
developed technologies in industrial production because of the
low economic benefit and secondary pollution. For easiness of
implementing the proposed process in industrial production,
how simple the process or route is plays a pivotal role. It is
widely known that a loss coefficient needs to be considered
during industrial production. The longer and more complex a
technology is, the more valuable metal will be lost and will
result in less economic benefit, such as the loss of Li in organic
phase.130 Therefore, the best method is to observe the “reuse”
principle, which requires that the waste should be reused as its
original purpose or reused as a component to fulfill a different
function. In this principle, the waste is directly recycled or
undergoes a repair process before being recycled. The reuse or
regeneration methods are all short routes to recycle materials
with little loss and low energy consumption.
With respect to legislation, successfully making “3R” ideology
into integrated utilization and recycling the valuable compo-
nents in spent LIBs not only rely on technical breakthroughs
made from industry and research organizations but also rely on
government support, public awareness of environmental
protection, manufacturing innovation, and management of
LIBs from the cradle to the grave. The recycling efficiency and
complexity of technology mainly depend on the complexity of
spent materials. With an excellent collection system and well-
known classification method, the recycling process will become
year main related content
2000 lead the development and improvement of managing and disposing municipal
solid waste
2001 lead the development and improvement of managing and disposing hazardous
wastes
2003 require manufacturers to collect spent batteries; aim to encourage the
development of managing and recycling technology of spent batteries and
reduce pollution
2006 aim to reduce the pollution of electric waste
2006 require the automobile production enterprises to establish the collection and
treatment of power batteries produced by them or send the spent power
batteries to a special company who can dispose of them
2008 cover stipulations about collecting, disposing, and managing electric waste
2013 stipulate the quantity of wastewater and gas from the industry
2013 add the requirements about design, product, and recycle process
2015 lead the development of managing and disposing spent electric vehicles power
batteries
2016 emphasize the fact that the responsibility of recycling spent power batteries
belongs to the battery manufacturers
2016 give the requirements about the factory size, equipment, technology, and energy
consumption of recycling industries
2016 enlarge the managing scope of spent batteries; encourage establishing a collecting
system and researching new recycling technology
1515 DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

much simpler. As a result, the simplified process will lead to an
improved efficiency of recovery, reduction of cost, and
increased profit margin. For a good collection system to be
established, both the collection mechanism itself and enforce-
ment of legislative policies are important. Fortunately, with the
problem of spent LIBs gaining more and more public
awareness, governments realize the importance of setting up
a comprehensive collection system. The relevant laws and
policies have been established to encourage the development of
recycling spent LIBs. As seen in Table 5, laws relevant to the
collection and disposal of spent batteries have been constantly
increasing from 2000 to now. In the early years, the regulations
spent LIBs, which are hazardous for soil, water, and living
organisms on Earth.
• Not restricting the recycling process of spent LIBs and
comprehensive and holistic views from the cradle to the grave
in designing, manufacturing, and recycling LIBs needs to be
addressed.
Last but not the least, a global homogenized mechanism in
manufacturing, classification, collection, and recycling will
significantly reduce the complexity of raw material, which in
turn minimizes the energy consumption of the recycling
process. All of these aspects have a lasting influence on
achieving economic and eco-friendly recycling of spent LIBs.

■
of recycling spent LIBs were covered as a small aspect of the
laws for disposing of solid waste. Afterward, some compre- AUTHOR INFORMATION
hensive policies about spent batteries, mainly pointing to lead
acid battery, have been established. In recent years, special laws Corresponding Author
for spent LIBs have been established, as the severity of *E-mail: zhisun@126.com; Tel: +86 10 82544844; Fax: +86 10
pollution caused by battery leakage is spreading quickly and 82544845.
widely. Given that these legislative policies have already been ORCID
nailed in, the public is less prone to ignore pollution caused by Hongbin Cao: 0000-0001-5968-9357
battery leakage.

■
Zhi Sun: 0000-0001-7183-0587
CONCLUSIONS AND OUTLOOK Notes
The authors declare no competing financial interest.
Globally, several companies, including AEA Technology
(U.K.), SNAM (France), Toxco (Canada), and Umicore Biographies
(Belgium), have established complete production lines to
recycle metals from spent LIBs.55 They are mainly focusing on
employing pyrometallurgical or hydrometallurgical methods or
a combination of them both. Concerning economic benefit,
traditional metallurgical processes (a long process including
pretreatment, leaching, and purifying) have little competitive-
ness in comparison with newer shorter processes, such as
selective extraction, regeneration, and repairing processes.
Though many reports researched the recycling technologies
of metals from spent LIBs, few of them have achieved cost-
effectiveness on an industrial scale. Meanwhile, there is no
commercial technology to achieve the recycling of waste mixed
with different cathodes. Many mechanisms of physical and
chemical changes in the recycling process need to be deeply
explored. A complete system of recycling LIBs needs to be Weiguang Lv is a doctoral student in the Institute of Process
discussed and established. For future research in the recycling Engineering, Chinese Academy of Sciences. He received his B.Sc.
of spent LIBs, we believe that it should focus on the following degree in metallurgical engineering (Central South University). His
aspects: current research focuses on efficient recovery of valuable metal from
• Whether the lab-scale technologies have industrial spent LIBs.
application prospects and how to scale them step-by-step are
of primary importance.
• The mechanisms of the leaching process are still
inconclusive. Significant work still needs to be done to guide
the selection of leaching reagent and operating conditions. For
example, changes in the crystal structure of the leaching process
need to be deeply researched. It will be very helpful for
providing insight into the reaction mechanism during leaching.
• Selective leaching of most of the valuable metals from the
spent LIBs has not been achieved yet. Relative research studies
should be strengthened in the future.
• Most studies of disposing spent LIBs only focused on the
kinetics and influence of operational parameters on leaching
process, whereas more efforts need to be paid for establishing a Dr. Zhonghang Wang is a postdoctoral researcher at the Institute of
complete evaluation system in which more critical factors, such Process Engineering, Chinese Academy of Sciences (IPE, CAS). He
as energy consumption of the whole process, could be received his B.Sc. degree in chemical engineering and technology
considered. (Central South University), and Ph. D. in chemical technology
• Furthermore, efforts also need to be concentrated on (University of Chinese Academy of Sciences). He has been working on
enhancing the collecting efficiency and reducing the landfill of electrometallurgy and molten salt electrochemistry for many years. His

1516 DOI: 10.1021/acssuschemeng.7b03811

ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
current research focuses on efficient recovery of valuable metals from
e-waste and the electroconversion of e-waste to high-value products.
Dr. Hongbin Cao is a professor at the Institute of Process Engineering,
Chinese Academy of Sciences, deputy director of the National
Engineering Laboratory for Hydrometallurgical Cleaner Production
Technology, and director of Beijing Engineering Research Center of
Process Pollution Control. His research interest is the whole process
control of industrial pollution: theory, technology, and application. Dr.
Cao has published over 100 papers and applied over 60 patents
including 5 international. He won second prize for the State
Technological Innovation Award (2013), first prize for the Environ-
mental Protection Science and Technology Award (2012), and first
prize for the Science and Technology Invention Award of Liaoning
province (2011). He is also the holder of National High-level
personnel of special support program (2013) and of the National
Science Fund for Distinguished Young Scholars of China (2014).
Dr. Yong sun is Technical Support Engineer within the School of
Engineering’s Technical Support team. He received his Ph.D. in
biochemical engineering in China and M.Sc degree of engineering
science at Monash University. His current research focuses on
expertise in Fischer−Tropsch synthesis, heterogeneous catalysis,
hydrometallurgy, gas separation and storage, and fluidization. Dr.
Sun has coauthored more than 50 publications.
Professor Zhang, working at the Institute of Process Engineering,
Chinese Academy of Sciences (CAS), is one of the chief scientists first
entering the field of green process engineering in China and is
currently engaged in fundamental and application research on green
process engineering and environmental control technology. As the
1517
Perspective
chief scientist, she had presided over the first National Sci-Tech
Project and the first 863 Project on cleaner process research.
Furthermore, she proposed a revolutionary green process for highly
efficient and clean conversion of mineral resources with submolten salt
medium. Professor Zhang has achieved second and third prizes of
National Technical Invention Awards, second and third prizes of
National Sci-Tech Progress Awards, and first prize of the Sci-Tech
Progress Awards of CAS (3 times). Professor Zhang has published
more than 170 papers and edited 9 books. She has also submitted 34
China invention patent applications with 10 granted. Under her
direction, 48 graduates have obtained their master’s or Ph.D. degrees
since 1990.
Dr. Zhi Sun is a professor at the Institute of Process Engineering,
Chinese Academy of Sciences. He received his B.Sc. degree in
metallurgical engineering (University of Science and Technology
Beijing), M.Sc. degree in chemical engineering (Chinese Acadamy of
Sciences), and Ph.D. in materials engineering (KU Leuven, Belgium).
He has been working as a postdoctoral researcher at the University of
Queensland, Australia, and as a senior researcher at Delft University of
Technology, The Netherlands. His current research focuses on
electronic waste treatment, sustainable process design for metal
recycling, and green design of electronic products. He is member of
the Chinese association of waste battery treatment. Dr. Sun has
coauthored more than 50 publications and 5 patents. He is also an
editorial board member of two international journals.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Key
Research and Development Program of China
(2017YFB0403300/2017YFB043305), Beijing Science and
Technology Program (No. Z171100002217028), the National
Natural Science Foundation of China (No. 51425405 and
L1624051), and the National Science and Technology Support
Plan Project (2015BAB02B05).
■ REFERENCES
(1) Georgi-Maschler, T.; Friedrich, B.; Weyhe, R.; Heegn, H.; Rutz,
M. Development of a recycling process for Li-ion batteries. J. Power
Sources 2012, 207, 173−182.
(2) Jaskula, B. W. Lithium. In Minerals Yearbook, Survey, U. S. G.,
Ed.; United States Geological Survey: Reston, VA, 2014.
(3) http://www.chyxx.com/industry/201611/470783.html.
(4) http://www.chyxx.com/industry/201703/500669.html.
(5) Sun, X.; Hao, H.; Zhao, F.; Liu, Z. Tracing global lithium flow: A
trade-linked material flow analysis. Resources, Conservation and
Recycling. 2017, 124, 50−61.
(6) Zeng, X.; Li, J.; Liu, L. Solving spent lithium-ion battery problems
in China: Opportunities and challenges. Renewable Sustainable Energy
Rev. 2015, 52, 1759−1767.
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
(7) Zeng, X.; Li, J.; Singh, N. Recycling of Spent Lithium-Ion Battery:
A Critical Review. Crit. Rev. Environ. Sci. Technol. 2014, 44 (10),
1129−1165.
(8) Xu, J.; Thomas, H. R.; Francis, R. W.; Lum, K. R.; Wang, J.;
Liang, B. A review of processes and technologies for the recycling of
lithium-ion secondary batteries. J. Power Sources 2008, 177 (2), 512−
527.
(9) Ku, H.; Jung, Y.; Jo, M.; Park, S.; Kim, S.; Yang, D.; Rhee, K.; An,
E. M.; Sohn, J.; Kwon, K. Recycling of spent lithium-ion battery
cathode materials by ammoniacal leaching. J. Hazard. Mater. 2016,
313, 138−46.
(10) Sun, Z.; Cao, H.; Zhang, X.; Lin, X.; Zheng, W.; Cao, G.; Sun,
Y.; Zhang, Y. Spent lead-acid battery recycling in China - A review and
sustainable analyses on mass flow of lead. Waste Manage. 2017, 64,
190−201.
(11) Nitta, N.; Wu, F.; Lee, J. T.; Yushin, G. Li-ion battery materials:
present and future. Mater. Today 2015, 18 (5), 252−264.
(12) Kraytsberg, A.; Ein-Eli, Y. Higher, stronger, better···A review of
5 V cathode materials for advanced lithium-ion batteries. Advanced
Energy Materials. 2012, 2 (8), 922−939.
(13) http://info.worldbank.org/governance/wgi/index.aspx#home.
(14) http://ec.europa.eu/growth/sectors/raw-materials/specific-
interest/critical_en.
(15) Sun, Z.; Cao, H.; Xiao, Y.; Sietsma, J.; Jin, W.; Agterhuis, H.;
Yang, Y. Toward sustainability for recovery of critical metals from
electronic waste: The Hydrochemistry Processes. ACS Sustainable
Chem. Eng. 2017, 5 (1), 21−40.
(16) https://price.metal.com.
(17) http://www.chyxx.com/industry/201704/514553.html.
(18) http://www.chyxx.com/industry/201612/475004.html.
(19) http://www.chyxx.com/research/201611/465155.html.
(20) http://www.chyxx.com/industry/201707/543308.html.
(21) http://www.chyxx.com/industry/201608/439335.html.
(22) Goonan, T. G. Lithium Use in Batteries; U.S. Department of the
Interior, U.S. Geological Survey: Reston, VA, 2012; https://pubs.usgs.
gov/circ/1371/pdf/circ1371_508.pdf.
(23) Swain, B. Cost effective recovery of lithium from lithium ion
battery by reverse osmosis and precipitation: a perspective. J. Chem.
Technol. Biotechnol. 2017, DOI: 10.1002/jctb.5332.
(24) Lithium-Ion Battery Market Analysis By Product (Lithium
Cobalt Oxide, Lithium Iron Phosphate, NCA, LMO, LTO, Lithium
Nickel Manganese Cobalt (NMC)), By Application, And Segment
Forecasts, 2014−2025; GVR-1-68038-668-4; Grand view research: San
Francisco, CA, 2017; http://www.grandviewresearch.com/industry-
analysis/thermal-energy-storage-market.
(25) https://imformed.com/li-ion-battery-recycling-no-worries-for-
raw-material-suppliersyet/.
(26) https://www.variantmarketresearch.com/report-categories/
semiconductor-electronics/lithium-ion-battery-market.
(27) Nie, H.; Xu, L.; Song, D.; Song, J.; Shi, X.; Wang, X.; Zhang, L.;
Yuan, Z. LiCoO2: Recycling from spent batteries and regeneration
with solid state synthesis. Green Chem. 2015, 17 (2), 1276−1280.
(28) Zhang, X.; Xue, Q.; Li, L.; Fan, E.; Wu, F.; Chen, R. Sustainable
recycling and regeneration of cathode scraps from industrial
production of lithium-ion batteries. ACS Sustainable Chem. Eng.
2016, 4 (12), 7041−7049.
(29) Song, D.; Wang, X.; Zhou, E.; Hou, P.; Guo, F.; Zhang, L.
Recovery and heat treatment of the Li(Ni1/3Co1/3Mn1/3)O2 cathode
scrap material for lithium ion battery. J. Power Sources 2013, 232, 348−
352.
(30) Chen, J.; Li, Q.; Song, J.; Song, D.; Zhang, L.; Shi, X.
Environmentally friendly recycling and effective repairing of cathode
powders from spent LiFePO4 batteries. Green Chem. 2016, 18 (8),
2500−2506.
(31) Bian, D.; Liu, S.; Sun, Y.; Yang, Z. Recycle of LiFePO4 cathode
materials from spent lithium ion batteries and the electrochemical
performance. Journal of the Chinese Ceramic Society. 2015, 43 (11),
1511−1516.
1518
Perspective
(32) Song, X.; Hu, T.; Liang, C.; Long, H. L.; Zhou, L.; Song, W.;
You, L.; Wu, Z. S.; Liu, J. W. Direct regeneration of cathode materials
from spent lithium iron phosphate batteries using a solid phase
sintering method. RSC Adv. 2017, 7 (8), 4783−4790.
(33) Zhu, S.; He, W.; Li, G.; Zhou, X.; Huang, J.; Zhang, X.
Recovering copper from spent Lithium ion battery by a mechanical
separation process. IEEE Shanghai,China 2011, 2, 1008−1012.
(34) Shin, S. M.; Kim, N. H.; Sohn, J. S.; Yang, D. H.; Kim, Y. H.
Development of a metal recovery process from Li-ion battery wastes.
Hydrometallurgy 2005, 79 (3−4), 172−181.
(35) Granata, G.; Pagnanelli, F.; Moscardini, E.; Takacova, Z.; Havlik,
T.; Toro, L. Simultaneous recycling of nickel metal hydride, lithium
ion and primary lithium batteries: Accomplishment of European
Guidelines by optimizing mechanical pre-treatment and solvent
extraction operations. J. Power Sources 2012, 212, 205−211.
(36) Paulino, J. F.; Busnardo, N. G.; Afonso, J. C. Recovery of
valuable elements from spent Li-batteries. J. Hazard. Mater. 2008, 150
(3), 843−9.
(37) He, L.; Sun, S.; Mu, Y.; Song, X.; Yu, J. Recovery of lithium,
nickel, cobalt, and manganese from spent lithium-ion batteries using L-
tartaric acid as a leachant. ACS Sustainable Chem. Eng. 2017, 5 (1),
714−721.
(38) Song, D.; Wang, X.; Nie, H.; Shi, H.; Wang, D.; Guo, F.; Shi, X.;
Zhang, L. Heat treatment of LiCoO2 recovered from cathode scraps
with solvent method. J. Power Sources 2014, 249, 137−141.
(39) Pant, D.; Dolker, T. Green and facile method for the recovery of
spent Lithium Nickel Manganese Cobalt Oxide (NMC) based Lithium
ion batteries. Waste Manage. 2016, 60, 689−695.
(40) Yang, Y.; Zheng, X.; Cao, H.; Zhao, C.; Lin, X.; Ning, P.; Zhang,
Y.; Jin, W.; Sun, Z. A Closed-Loop Process for Selective Metal
Recovery from Spent Lithium Iron Phosphate Batteries through
Mechanochemical Activation. ACS Sustainable Chem. Eng. 2017, 5
(11), 9972−9980.
(41) Wang, M.; Zhang, C.; Zhang, F. An environmental benign
process for cobalt and lithium recovery from spent lithium-ion
batteries by mechanochemical approach. Waste Manage. 2016, 51,
239−44.
(42) Guan, J.; Li, Y.; Guo, Y.; Su, R.; Gao, G.; Song, H.; Yuan, H.;
Liang, B.; Guo, Z. Mechanochemical process enhanced cobalt and
lithium recycling from wasted lithium-ion batteries. ACS Sustainable
Chem. Eng. 2017, 5 (1), 1026−1032.
(43) Saeki, S.; Lee, J.; Zhang, Q.; Saito, F. Co-grinding LiCoO2 with
PVC and water leaching of metal chlorides formed in ground product.
Int. J. Miner. Process. 2004, 74, S373−S378.
(44) Vanitha, M.; Balasubramanian, N. Waste minimization and
recovery of valuable metals from spent lithium-ion batteries − a
review. Environ. Technol. Rev. 2013, 2 (1), 101−115.
(45) Chagnes, A.; Pospiech, B. A brief review on hydrometallurgical
technologies for recycling spent lithium-ion batteries. J. Chem. Technol.
Biotechnol. 2013, 88 (7), 1191−1199.
(46) Hanisch, C.; Loellhoeffel, T.; Diekmann, J.; Markley, K. J.;
Haselrieder, W.; Kwade, A. Recycling of lithium-ion batteries: a novel
method to separate coating and foil of electrodes. J. Cleaner Prod.
2015, 108, 301−311.
(47) Sun, L.; Qiu, K. Vacuum pyrolysis and hydrometallurgical
process for the recovery of valuable metals from spent lithium-ion
batteries. J. Hazard. Mater. 2011, 194, 378−84.
(48) Li, J.; Zhao, R.; He, X.; Liu, H. Preparation of LiCoO2 cathode
materials from spent lithium−ion batteries. Ionics 2009, 15 (1), 111−
113.
(49) He, L.; Sun, S.; Song, X.; Yu, J. Recovery of cathode materials
and Al from spent lithium-ion batteries by ultrasonic cleaning. Waste
Manage. 2015, 46, 523−8.
(50) Tan, Q.; Li, J. Recycling metals from wastes: a novel application
of mechanochemistry. Environ. Sci. Technol. 2015, 49 (10), 5849−61.
(51) Wang, M.; Zhang, C.; Zhang, F. Recycling of spent lithium-ion
battery with polyvinyl chloride by mechanochemical process. Waste
Manage. 2017, 67, 232−239.
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
(52) Nife, A. B. S.; Landskrona, S.; Melin, A. L.; Svensson, V. H.
Process for the recovery of metals from the scrap from nickel−
cadmium electric storage batteries. US Patent 4401463, 1983.
(53) Espinosa, D. C. R.; Bernardes, A. M.; Tenório, J. A. S. An
overview on the current processes for the recycling of batteries. J.
Power Sources 2004, 135 (1−2), 311−319.
(54) Meshram, P.; Pandey, B. D.; Mankhand, T. R. Recovery of
valuable metals from cathodic active material of spent lithium ion
batteries: Leaching and kinetic aspects. Waste Manage. 2015, 45, 306−
13.
(55) Meshram, P.; Pandey, B. D.; Mankhand, T. R. Extraction of
lithium from primary and secondary sources by pre-treatment,
leaching and separation: A comprehensive review. Hydrometallurgy
2014, 150, 192−208.
(56) Ren, G.; Xiao, S.; Xie, M.; Pan, B.; Fan, Y.; Wang, F.; Xia, X.
Recovery of valuable metals from spent lithium ion batteries by
smelting reduction based on MnO-SiO2-Al2O3 slag system. In
Advances in Molten Slags, Fluxes, and Salts: Proceedings of the 10th
International Conference on Molten Slags, Fluxes and Salts; Reddy, R. G.;
Chaubal, P.; Chris Pistorius, P.; Pal, U., Eds.; Springer, Cham, 2016;
pp 211−218.
(57) Xiao, J.; Li, J.; Xu, Z. Novel Approach for in Situ Recovery of
Lithium Carbonate from Spent Lithium Ion Batteries Using Vacuum
Metallurgy. Environ. Sci. Technol. 2017, 51, 11960.
(58) Xiao, J.; Li, J.; Xu, Z. Recycling metals from lithium ion battery
by mechanical separation and vacuum metallurgy. J. Hazard. Mater.
2017, 338, 124−131.
(59) Li, J.; Wang, G.; Xu, Z. Environmentally-friendly oxygen-free
roasting/wet magnetic separation technology for in situ recycling
cobalt, lithium carbonate and graphite from spent LiCoO2/graphite
lithium batteries. J. Hazard. Mater. 2016, 302, 97−104.
(60) Garcia, E. M.; Tarôco, H. A.; Matencio, T.; Domingues, R. Z.;
dos Santos, J. A. F.; Ferreira, R. V.; Lorençon, E.; Lima, D. Q.; de
Freitas, M. B. J. G. Electrochemical recycling of cobalt from spent
cathodes of lithium-ion batteries: its application as supercapacitor. J.
Appl. Electrochem. 2012, 42 (6), 361−366.
(61) Garcia, E. M.; Tarôco, H. A.; Matencio, T.; Domingues, R. Z.;
dos Santos, J. A. F.; de Freitas, M. B. J. G. Electrochemical recycling of
cobalt from spent cathodes of lithium−ion batteries: its application as
coating on SOFC interconnects. J. Appl. Electrochem. 2011, 41 (11),
1373−1379.
(62) Garcia, E. M.; Santos, J. S.; Pereira, E. C.; Freitas, M. B. J. G.
Electrodeposition of cobalt from spent Li-ion battery cathodes by the
electrochemistry quartz crystal microbalance technique. J. Power
Sources 2008, 185 (1), 549−553.
(63) Granata, G.; Moscardini, E.; Pagnanelli, F.; Trabucco, F.; Toro,
L. Product recovery from Li-ion battery wastes coming from an
industrial pre-treatment plant: Lab scale tests and process simulations.
J. Power Sources 2012, 206, 393−401.
(64) Ferreira, D. A.; Prados, L. M. Z.; Majuste, D.; Mansur, M. B.
Hydrometallurgical separation of aluminium, cobalt, copper and
lithium from spent Li-ion batteries. J. Power Sources 2009, 187 (1),
238−246.
(65) Joulié, M.; Laucournet, R.; Billy, E. Hydrometallurgical process
for the recovery of high value metals from spent lithium nickel cobalt
aluminum oxide based lithium-ion batteries. J. Power Sources 2014,
247, 551−555.
(66) Nayaka, G. P.; Pai, K. V.; Manjanna, J.; Keny, S. J. Use of mild
organic acid reagents to recover the Co and Li from spent Li-ion
batteries. Waste Manage. 2016, 51, 234−238.
(67) Li, L.; Dunn, J. B.; Zhang, X. X.; Gaines, L.; Chen, R. J.; Wu, F.;
Amine, K. Recovery of metals from spent lithium-ion batteries with
organic acids as leaching reagents and environmental assessment. J.
Power Sources 2013, 233, 180−189.
(68) Zeng, X.; Li, J.; Shen, B. Novel approach to recover cobalt and
lithium from spent lithium-ion battery using oxalic acid. J. Hazard.
Mater. 2015, 295, 112−118.
(69) Nayaka, G. P.; Pai, K. V.; Santhosh, G.; Manjanna, J. Dissolution
of cathode active material of spent Li-ion batteries using tartaric acid
1519
Perspective
and ascorbic acid mixture to recover Co. Hydrometallurgy 2016, 161,
54−57.
(70) Nayaka, G. P.; Pai, K. V.; Santhosh, G.; Manjanna, J. Recovery
of cobalt as cobalt oxalate from spent lithium ion batteries by using
glycine as leaching agent. J. Environ. Chem. Eng. 2016, 4 (2), 2378−
2383.
(71) Chen, X.; Fan, B.; Xu, L.; Zhou, T.; Kong, J. An atom-economic
process for the recovery of high value-added metals from spent
lithium-ion batteries. J. Cleaner Prod. 2016, 112, 3562−3570.
(72) Li, L.; Zhai, L.; Zhang, X.; Lu, J.; Chen, R.; Wu, F.; Amine, K.
Recovery of valuable metals from spent lithium-ion batteries by
ultrasonic-assisted leaching process. J. Power Sources 2014, 262, 380−
385.
(73) Zheng, X.; Gao, W.; Zhang, X.; He, M.; Lin, X.; Cao, H.; Zhang,
Y.; Sun, Z. Spent lithium-ion battery recycling - Reductive ammonia
leaching of metals from cathode scrap by sodium sulphite. Waste
Manage. 2017, 60, 680−688.
(74) Bertuol, D. A.; Machado, C. M.; Silva, M. L.; Calgaro, C. O.;
Dotto, G. L.; Tanabe, E. H. Recovery of cobalt from spent lithium-ion
batteries using supercritical carbon dioxide extraction. Waste Manage.
2016, 51, 245−51.
(75) Liu, K.; Zhang, F. Innovative leaching of cobalt and lithium from
spent lithium-ion batteries and simultaneous dechlorination of
polyvinyl chloride in subcritical water. J. Hazard. Mater. 2016, 316,
19−25.
(76) Takacova, Z.; Havlik, T.; Kukurugya, F.; Orac, D. Cobalt and
lithium recovery from active mass of spent Li-ion batteries: Theoretical
and experimental approach. Hydrometallurgy 2016, 163, 9−17.
(77) https://greet.es.anl.gov/.
(78) Barik, S. P.; Prabaharan, G.; Kumar, L. Leaching and separation
of Co and Mn from electrode materials of spent lithium-ion batteries
using hydrochloric acid: Laboratory and pilot scale study. J. Cleaner
Prod. 2017, 147, 37−43.
(79) Zhang, P.; Yokoyama, T.; Itabashi, O.; Suzuki, T. M.; Inoue, K.
Hydrometallurgical process for recovery of metal values from spent
lithium-ion secondary batteries. Hydrometallurgy 1998, 47 (2−3),
259−271.
(80) Huang, Y.; Han, G.; Liu, J.; Chai, W.; Wang, W.; Yang, S.; Su, S.
A stepwise recovery of metals from hybrid cathodes of spent Li-ion
batteries with leaching-flotation-precipitation process. J. Power Sources
2016, 325, 555−564.
(81) Swain, B.; Jeong, J.; Lee, J.-c.; Lee, G.-H.; Sohn, J.-S.
Hydrometallurgical process for recovery of cobalt from waste cathodic
active material generated during manufacturing of lithium ion
batteries. J. Power Sources 2007, 167 (2), 536−544.
(82) Gratz, E.; Sa, Q.; Apelian, D.; Wang, Y. A closed loop process
for recycling spent lithium ion batteries. J. Power Sources 2014, 262,
255−262.
(83) Meshram, P.; Pandey, B. D.; Mankhand, T. R. Hydro-
metallurgical processing of spent lithium ion batteries (LIBs) in the
presence of a reducing agent with emphasis on kinetics of leaching.
Chem. Eng. J. 2015, 281, 418−427.
(84) Jha, M. K.; Kumari, A.; Jha, A. K.; Kumar, V.; Hait, J.; Pandey, B.
D. Recovery of lithium and cobalt from waste lithium ion batteries of
mobile phone. Waste Manage. 2013, 33 (9), 1890−1897.
(85) Pinna, E. G.; Ruiz, M. C.; Ojeda, M. W.; Rodriguez, M. H.
Cathodes of spent Li-ion batteries: Dissolution with phosphoric acid
and recovery of lithium and cobalt from leach liquors. Hydrometallurgy
2017, 167, 66−71.
(86) Chen, X.; Ma, H.; Luo, C.; Zhou, T. Recovery of valuable metals
from waste cathode materials of spent lithium-ion batteries using mild
phosphoric acid. J. Hazard. Mater. 2017, 326, 77−86.
(87) Lee, C. K.; Rhee, K.-I. Preparation of LiCoO2 from spent
lithium-ion batteries. J. Power Sources 2002, 109 (1), 17−21.
(88) Sun, L.; Qiu, K. Organic oxalate as leachant and precipitant for
the recovery of valuable metals from spent lithium-ion batteries. Waste
Manage. 2012, 32 (8), 1575−1582.
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering
(89) Chen, X.; Luo, C.; Zhang, J.; Kong, J.; Zhou, T. Sustainable
recovery of metals from spent lithium-ion batteries: a green process.
ACS Sustainable Chem. Eng. 2015, 3 (12), 3104−3113.
(90) Li, L.; Qu, W.; Zhang, X.; Lu, J.; Chen, R.; Wu, F.; Amine, K.
Succinic acid-based leaching system: A sustainable process for recovery
of valuable metals from spent Li-ion batteries. J. Power Sources 2015,
282, 544−551.
(91) Ijadi Bajestani, M.; Mousavi, S. M.; Shojaosadati, S. A.
Bioleaching of heavy metals from spent household batteries using
Acidithiobacillus ferrooxidans: Statistical evaluation and optimization.
Sep. Purif. Technol. 2014, 132, 309−316.
(92) Mishra, D.; Kim, D. J.; Ralph, D. E.; Ahn, J. G.; Rhee, Y. H.
Bioleaching of metals from spent lithium ion secondary batteries using
Acidithiobacillus ferrooxidans. Waste Manage. 2008, 28 (2), 333−338.
(93) Zeng, G.; Luo, S.; Deng, X.; Li, L.; Au, C. Influence of silver ions
on bioleaching of cobalt from spent lithium batteries. Miner. Eng. 2013,
49, 40−44.
(94) Chen, S.; Lin, J. Enhancement of metal bioleaching from
contaminated sediment using silver ion. J. Hazard. Mater. 2009, 161
(2−3), 893−899.
(95) Zeng, G.; Deng, X.; Luo, S.; Luo, X.; Zou, J. A copper-catalyzed
bioleaching process for enhancement of cobalt dissolution from spent
lithium-ion batteries. J. Hazard. Mater. 2012, 199−200, 164−169.
(96) Xin, B.; Zhang, D.; Zhang, X.; Xia, Y.; Wu, F.; Chen, S.; Li, L.
Bioleaching mechanism of Co and Li from spent lithium-ion battery by
the mixed culture of acidophilic sulfur-oxidizing and iron-oxidizing
bacteria. Bioresour. Technol. 2009, 100 (24), 6163−6169.
(97) Xin, Y.; Guo, X.; Chen, S.; Wang, J.; Wu, F.; Xin, B. Bioleaching
of valuable metals Li, Co, Ni and Mn from spent electric vehicle Li-ion
batteries for the purpose of recovery. J. Cleaner Prod. 2016, 116, 249−
258.
(98) Ren, W.; Li, P.; Geng, Y.; Li, X. Biological leaching of heavy
metals from a contaminated soil by Aspergillus niger. J. Hazard. Mater.
2009, 167 (1−3), 164−169.
(99) Bahaloo-Horeh, N.; Mousavi, S. M. Enhanced recovery of
valuable metals from spent lithium-ion batteries through optimization
of organic acids produced by Aspergillus niger. Waste Manage. 2017,
60, 666−679.
(100) Horeh, N. B.; Mousavi, S. M.; Shojaosadati, S. A. Bioleaching
of valuable metals from spent lithium-ion mobile phone batteries using
Aspergillus niger. J. Power Sources 2016, 320, 257−266.
(101) Niu, Z.; Zou, Y.; Xin, B.; Chen, S.; Liu, C.; Li, Y. Process
controls for improving bioleaching performance of both Li and Co
from spent lithium ion batteries at high pulp density and its
thermodynamics and kinetics exploration. Chemosphere 2014, 109,
92−98.
(102) Wang, F.; Sun, R.; Xu, J.; Chen, Z.; Kang, M. Recovery of
cobalt from spent lithium ion batteries using sulphuric acid leaching
followed by solid−liquid separation and solvent extraction. RSC Adv.
2016, 6 (88), 85303−85311.
(103) Joo, S.-H.; Shin, D.; Oh, C.; Wang, J.-P.; Shin, S. M. Extraction
of manganese by alkyl monocarboxylic acid in a mixed extractant from
a leaching solution of spent lithium-ion battery ternary cathodic
material. J. Power Sources 2016, 305, 175−181.
(104) Zhao, J. M.; Shen, X. Y.; Deng, F. L.; Wang, F. C.; Wu, Y.; Liu,
H. Z. Synergistic extraction and separation of valuable metals from
waste cathodic material of lithium ion batteries using Cyanex272 and
PC-88A. Sep. Purif. Technol. 2011, 78 (3), 345−351.
(105) Jha, A. K.; Jha, M. K.; Kumari, A.; Sahu, S. K.; Kumar, V.;
Pandey, B. D. Selective separation and recovery of cobalt from leach
liquor of discarded Li-ion batteries using thiophosphinic extractant.
Sep. Purif. Technol. 2013, 104, 160−166.
(106) Darvishi, D.; Haghshenas, D. F.; Alamdari, E. K.; Sadrnezhaad,
S. K.; Halali, M. Synergistic effect of Cyanex 272 and Cyanex 302 on
separation of cobalt and nickel by D2EHPA. Hydrometallurgy 2005, 77
(3−4), 227−238.
(107) Joo, S.-H.; Shin, D. j.; Oh, C.; Wang, J.-P.; Senanayake, G.;
Shin, S. M. Selective extraction and separation of nickel from cobalt,
manganese and lithium in pre-treated leach liquors of ternary cathode
1520
Perspective
material of spent lithium-ion batteries using synergism caused by
Versatic 10 acid and LIX 84-I. Hydrometallurgy 2016, 159, 65−74.
(108) Virolainen, S.; Fallah Fini, M.; Laitinen, A.; Sainio, T. Solvent
extraction fractionation of Li-ion battery leachate containing Li, Ni,
and Co. Sep. Purif. Technol. 2017, 179, 274−282.
(109) Chen, X.; Zhou, T.; Kong, J.; Fang, H.; Chen, Y. Separation
and recovery of metal values from leach liquor of waste lithium nickel
cobalt manganese oxide based cathodes. Sep. Purif. Technol. 2015, 141,
76−83.
(110) Yang, Y.; Huang, G.; Xie, M.; Xu, S.; He, Y. Synthesis and
performance of spherical LiNixCoyMn1‑x‑yO2 regenerated from nickel
and cobalt scraps. Hydrometallurgy 2016, 165, 358−369.
(111) Sa, Q.; Gratz, E.; He, M.; Lu, W.; Apelian, D.; Wang, Y.
Synthesis of high performance LiNi1/3Mn1/3Co1/3O2 from lithium ion
battery recovery stream. J. Power Sources 2015, 282, 140−145.
(112) Yang, Y.; Huang, G.; Xu, S.; He, Y.; Liu, X. Thermal treatment
process for the recovery of valuable metals from spent lithium-ion
batteries. Hydrometallurgy 2016, 165, 390−396.
(113) Yao, L.; Yao, H.; Xi, G.; Feng, Y. Recycling and synthesis of
LiNi1/3Co1/3Mn1/3O2from waste lithium ion batteries usingd,l-malic
acid. RSC Adv. 2016, 6 (22), 17947−17954.
(114) Zou, H.; Gratz, E.; Apelian, D.; Wang, Y. A novel method to
recycle mixed cathode materials for lithium ion batteries. Green Chem.
2013, 15 (5), 1183−1191.
(115) Yao, L.; Xi, Y.; Xi, G.; Feng, Y. Synthesis of cobalt ferrite with
enhanced magnetostriction properties by the sol−gel−hydrothermal
route using spent Li-ion battery. J. Alloys Compd. 2016, 680, 73−79.
(116) Yao, L.; Feng, Y.; Xi, G. A new method for the synthesis of
LiNi1/3Co1/3Mn1/3O2from waste lithium ion batteries. RSC Adv. 2015,
5 (55), 44107−44114.
(117) Sa, Q.; Gratz, E.; Heelan, J. A.; Ma, S.; Apelian, D.; Wang, Y.
Synthesis of Diverse LiNixMnyCozO2 Cathode Materials from Lithium
Ion Battery Recovery Stream. Journal of Sustainable Metallurgy. 2016, 2
(3), 248−256.
(118) Weng, Y.; Xu, S.; Huang, G.; Jiang, C. Synthesis and
performance of Li[(Ni1/3Co1/3Mn1/3)(1‑x)Mgx]O2 prepared from spent
lithium ion batteries. J. Hazard. Mater. 2013, 246−247, 163−172.
(119) Li, L.; Zhang, X.; Chen, R.; Zhao, T.; Lu, J.; Wu, F.; Amine, K.
Synthesis and electrochemical performance of cathode material
Li1.2Co0.13Ni0.13Mn0.54O2 from spent lithium-ion batteries. J. Power
Sources 2014, 249, 28−34.
(120) Marinos, D. An approach to beneficiation of spent lithium-ion
batteries for recovery of materials; University of Colorado: Boulder, CO,
2014.
(121) Liu, Y. Research on recycling and reusing of carbonate based
electrolyte for lithium ion batteries by super critical CO2; Harbin Instiute
of Technology, Harbin, China, 2017.
(122) Liu, Y.; Mu, D.; Li, R.; Ma, Q.; Zheng, R.; Dai, C. Purification
and Characterization of Reclaimed Electrolytes from Spent Lithium-
Ion Batteries. J. Phys. Chem. C 2017, 121 (8), 4181−4187.
(123) Guo, Y.; Li, F.; Zhu, H.; Li, G.; Huang, J.; He, W. Leaching
lithium from the anode electrode materials of spent lithium-ion
batteries by hydrochloric acid (HCl). Waste Manage. 2016, 51, 227−
233.
(124) Zhao, T.; Yao, Y.; Wang, M.; Chen, R.; Yu, Y.; Wu, F.; Zhang,
C. Preparation of MnO2-Modified Graphite Sorbents from Spent Li-
Ion Batteries for the Treatment of Water Contaminated by Lead,
Cadmium, and Silver. ACS Appl. Mater. Interfaces 2017, 9 (30),
25369−25376.
(125) Zhang, Y.; Guo, X.; Wu, F.; Yao, Y.; Yuan, Y.; Bi, X.; Luo, X.;
Shahbazian-Yassar, R.; Zhang, C.; Amine, K. Mesocarbon Microbead
Carbon-Supported Magnesium Hydroxide Nanoparticles: Turning
Spent Li-ion Battery Anode into a Highly Efficient Phosphate
Adsorbent for Wastewater Treatment. ACS Appl. Mater. Interfaces
2016, 8 (33), 21315−21325.
(126) Al-Thyabat, S.; Nakamura, T.; Shibata, E.; Iizuka, A.
Adaptation of minerals processing operations for lithium-ion (LiBs)
and nickel metal hydride (NiMH) batteries recycling: Critical review.
Miner. Eng. 2013, 45, 4−17.
DOI: 10.1021/acssuschemeng.7b03811
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521
ACS Sustainable Chemistry & Engineering Perspective

(127) Chagnes, A.; Swiatowska, J. Lithium Process Chemistry Resources,

Extraction, Batteries, and Recycling; Elsevier: MA, 2015.
(128) Valio, J. Critical review on lithium ion battery recycling
technologies; Aalto University, Helsinki, Finland, 2017.
(129) Knights, B. D. H.; Saloojee, F. Lithium batteries recycling;
Metallurgical Consultancy & Laboratories: South Africa, 2015; http://
www.sagreenfund.org.za/wordpress/.
(130) Yang, Y.; Xu, S.; He, Y. Lithium recycling and cathode material
regeneration from acid leach liquor of spent lithium-ion battery via
facile co-extraction and co-precipitation processes. Waste Manage.
2017, 64, 219−227.
(131) Sun, Z.; Xiao, Y.; Sietsma, J.; Agterhuis, H.; Yang, Y. Complex
electronic waste treatment - An effective process to selectively recover
copper with solutions containing different ammonium salts. Waste
Manage. 2016, 57, 140−148.
(132) Gao, W.; Zhang, X.; Zheng, X.; Lin, X.; Cao, H.; Zhang, Y.;
Sun, Z. Lithium carbonate recovery from cathode scrap of spent
Lithium-Ion Battery: s closed-loop Process. Environ. Sci. Technol. 2017,
51 (3), 1662−1669.
(133) Li, H.; Xing, S.; Liu, Y.; Li, F.; Guo, H.; Kuang, G. Recovery of
lithium, iron, and phosphorus from spent LiFePO4 batteries using
stoichiometric sulfuric acid leaching system. ACS Sustainable Chem.
Eng. 2017, 5 (9), 8017−8024.
(134) Dunn, J. B.; Gaines, L.; Sullivan, J.; Wang, M. Q. Impact of
recycling on cradle-to-gate energy consumption and greenhouse gas
emissions of automotive lithium-ion batteries. Environ. Sci. Technol.
2012, 46 (22), 12704−12710.
(135) Dunn, J. B.; Gaines, L.; Sullivan, J.; Wang, M. Q. Material and
energy flows in materials production, assembly, and end-of-life stages
of the automotive lithium-ion battery life cycle; United States, 2012;
https://www.osti.gov/scitech/biblio/1044525.
(136) Kushnir, D.; Sandén, B. A. Multi-level energy analysis of
emerging technologies: a case study in new materials for lithium ion
batteries. J. Cleaner Prod. 2011, 19 (13), 1405−1416.

1521 DOI: 10.1021/acssuschemeng.7b03811

ACS Sustainable Chem. Eng. 2018, 6, 1504−1521