pubs.acs.

org/journal/ascecg Research Article

Selective Recovery of Lithium from Spent Lithium-Ion Batteries by

Coupling Advanced Oxidation Processes and Chemical Leaching
Processes
Weiguang Lv,∥ Zhonghang Wang,∥ Xiaohong Zheng, Hongbin Cao, Mingming He, Yi Zhang, Haijun Yu,
and Zhi Sun*
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ABSTRACT: Traditional technologies for the recycling of spent lithium-ion batteries (LIBs)
mainly focus on reductive leaching, which often leads to total leaching rather than selective
leaching of metals. As a result, loss of valuable metal ions, particularly Li+, occurs in subsequent
extraction processes, causing low recycling efficiency of valuable metals. Inspired by the oxide-
delithiation process in materials science, here, advanced oxidation processes (AOPs) are first
introduced to selectively recover Li from spent LIBs during hydrometallurgical leaching
(oxidative leaching), and a high Li recovery rate is achieved with an extremely high slurry
density. In AOPs, the sulfate radical (SO•− •
4 ) and hydroxyl radical (HO ), which have high
oxidation potentials, are in situ generated by heat-activated persulfate to prevent the leaching of
Co2+ and Mn2+ and, simultaneously, promote the leaching of Li. Besides, chemical leaching
processes are coupled with AOPs to enhance the leaching of Li for the incomplete delithiation of
AOPs. Through the selective recovery, the extraction process of Li is drastically shortened. A
lithium-rich solution (18.2 g/L of Li+), which is available to directly prepare qualified lithium
products, can be obtained in only two steps. The reaction mechanisms between AOPs and spent
LIBs are also comprehensively investigated. In the end, the loss of Li is only 2.06% in the purification processes, leading to a high
recycling efficiency of Li. Li2CO3 with a purity of 99.0% was obtained. Furthermore, the introduction of AOPs for selective
extraction of metals will not only show its significant value in the waste recycling field but also in the mineral resource utilization.
KEYWORDS: recycling, selective recovery, advanced oxidation processes, persulfate, lithium loss, radical, oxidative leaching

1. INTRODUCTION difference, particle size, and magnetic, electrical, and soluble

With the rapid growth of energy demand for consumer
electronics, electric vehicles, and energy storage, lithium-ion
batteries (LIBs) have experienced a leapfrog development in
the technology and market share since first being introduced to
the market by Sony in the 1990s. In the meantime, the
generation and disposal of spent LIBs have become a global
concern in terms of environmental protection and resource
recycling. These spent LIBs can cause severe environmental
effects by means of exuding toxic and flammable fluorine-
containing organic electrolytes and heavy metals, such as
nickel, cobalt, and copper, if disposed improperly.1,2 Never-
theless, this “waste” stream is also a potential “urban mine” that
can provide a great amount of secondary resources for
remanufacture, refurbishment, and recycling.3,4 The increased
mining of natural ores for these metals is also leading to
shortages, creating a market for LIB recycling.5
Generally, the collected spent LIBs would be first
disassembled to remove casting, foil, and and so forth,
followed by mechanical/mechanochemical/thermal treatment
and dissolution in organic/supercritical solvents to separate
active materials from the scraps based on the density
properties.1,6 Then, various pyro-/hydro-/bio-/electrometal-
lurgical methods are adopted and combined to recover
valuable materials, mainly rare and precious metals, from
active materials, among which hydrometallurgical methods
have been adopted most widely because of their advantages of
simultaneous recovery of several valuable metals and lower
energy consumption in comparison with the pyrometallurgical
ones.7−9 During a hydrometallurgical process, almost all
valuable metals are first leached into acidic or ammonium-
based alkaline aqueous solutions through reductive leaching,
and then, separation and purification techniques, such as
solvent extraction, chemical precipitation, adsorption, ion
exchange, and electrodeposition, are applied for the recovery
of target metals.10−12 Valuable metals can be recovered using
Received: December 16, 2019
Revised: February 19, 2020
Published: March 16, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acssuschemeng.9b07515

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these long extraction processes, but great loss of metals is still a
problem for these processes, especially the loss of Li, which is
always extracted at the end of the current recycling strategies.
Lots of Li+ are lost in the process because of the entrainment
or wrapping during the separation of the abovementioned
valuable metals.13 Besides, recent investigations had identified
that only the Li+ concentration of the leachate was higher than
20 g/L, and the recovery rate of Li could reach 80% to produce
Li2CO3 with Na2CO3. However, the Li+ concentration of the
leachate from traditional technology was usually about 10 g/L,
even lower than this, for which the recovery rate of Li would be
lower than 50%.14,15 Cycle leaching needs to be conducted in
traditional technology to increase the concentration of Li+,
leading to more loss of Li+ in every cycle. Sometimes, the
leachate with low concentration of Li+ is directly discarded.
Thus, in order to achieve efficient and low-cost recovery of Li
from spent LIBs, it is necessary to develop a highly selective
leaching technology.
Selective leaching methods for the target metals are required
for simple separation and recovery processes of the valuable
metals, especially the efficient recovery of lithium.16−19
Recently, sulfate and nitrate roasting methods have been
widely researched to achieve selective leaching of Li but need
high roasting temperatures, 250 °C for the nitrate system and
800 °C for the sulfate system.20,21 In addition, the typical
pollutant NO (g) is released from the nitrate system. Oxidative
leaching methods are other choices for the selective leaching of
Li.22,23 Venkatraman et al.24 investigated the extraction rate of
Li from the layered LiNi1−y−zCoyMnzO2 with the oxidizer
NO2BF4 in an acetonitrile medium. They found that the
extraction rate of Li decreased with increasing cation disorder
and decreasing interslab space for Li. However, the delithiation
efficiencies were still less than 80% after reacting for 24 h
under the determined optimum conditions through this
technology. Ji et al.25 proposed a similar approach for
delithiation from spinel-type LiMn2O4 (LMO) based on the
hydrolysis of Na2S2O8. They found that the extraction ratio of
Li (XLi) was significantly positively related to the hydrolysis of
Na2S2O8. At 75 °C, XLi can rapidly reach 93% almost without
Mn loss, while the loss ratio of Mn could reach ca. 13% when
delithiation was carried out in Na2S2O8 solution that has been
hydrolyzed for 72 h at 75 °C. However, the delithiation
efficiency is usually unsatisfactory under the premise of
ensuring a high selectivity, especially for the selective recovery
of Li from complex materials, such as binary, ternary, or the
blend of different kinds of cathode materials. Although, as far
as we know, there has been no systematic study on the
evolution of composition and crystal and electronic structure
of delithiated materials during the delithiation process in
aqueous solutions, extensive work has been performed and
reported in organic aprotic media.22,26−32 In addition, the
ambiguity of the leaching process has led to a lack of effective
optimization for the actual delithiation process, especially for
the selective recovery of Li from spent LIBs.
To address this issue, selective leaching from spent LIBs in
aqueous solutions under a strong oxidizing environment was
investigated in this paper by coupling advanced oxidation
process (AOPs) and chemical leaching processes (CLPs)
(AOPs−CLPs). The effects of various factors, including the
amount of oxidant added, reaction temperature, solid-to-liquid
mass ratio, and solution acidity on the leaching rate and
selectivity were investigated systematically. On this basis, the
underlying mechanism of the process was proposed, verified,
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and discussed, with monitoring compositional, morphological,
and crystal evolution of residues during the selective leaching
process. It is expected that this work can help to further
improve the efficiency and selectivity of the recovery of Li from
the spent LIBs in the future.
2. EXPERIMENTAL SECTION
There are two different waste materials used in the studies, and both
of them were supplied by Ganzhou Highpower Technology Co., Ltd.
One of the waste materials (defined as material W1) is a mixture of
lithium nickel cobalt manganese oxide (NCM) with different ratios of
transition metals and lithium cobalt oxide, which mainly contains
5.2% Li, 21.13% Co, 12.71% Ni, and 10.79% Mn. The other one is
cathode scrap (defined as material W2), which has been separated
from aluminum foil through the pyrolysis of the binder. This scrap
with a dominant phase of LiNi0.5Co0.2Mn0.3O2 (NCM523) contains
6.34% Li, 10.77% Co, 26.75% Ni, and 15.34% Mn. Because the
composition of W1 is very complex, it is hard to research the reaction
mechanism. The cathode scrap is used to deeply investigate the
underlying mechanism of the process because of the simple
composition, even only a phase of LiNi0.5Co0.2Mn0.3 (NCM523).
All experiments in this work were carried out in a homemade round-
bottomed double-layer cylindrical glass reactor under atmospheric
pressure. Before each experiment, a predetermined amount of
deionized water (produced by water superpurification using Milli-Q,
Millipore) and waste particles were added to the reactor to produce a
uniform slurry under constant magnetic stirring. During heating, by
circulating the heating medium through the sandwich of the reactor,
temperature and pH of the slurry were monitored with a temperature
meter (0−200 °C, Yancheng Qianhe Experimental Instrument Co.,
Ltd.) and a pH probe (FiveEasy Plus, Metter Toledo). After adding
sodium persulfate (AR, Xilong Scientific) into the slurry, the reactor
was quickly sealed and the experiment started. All chemicals
(Na2S2O8, 98 wt % H2SO4, NaOH, and Na2CO3) were of analytical
grade from Aladdin Chemical Co. Ltd, China. The chemical
composition, structure, and morphology of the residues were analyzed
using an inductively coupled plasma-optical emission spectrometer
(PE Optima 6300DV, Perkin Elmer), an X-ray diffraction analyzer
(Phillips PW 223/30), and a scanning electron microscope (JEOL
SEM). In order to reduce the error from volume change, the internal
standard method was used and Na+ was chosen as the reference.
Because Na+ is only from sodium persulfate, the total amount of it
remains constant in the reaction. Although there is evaporation of
solution in the reaction process, the volume of the solution at a
specific reaction time can be ensured through the concentration of
Na+, CNa,t. Therefore, the leaching rate Xi of metal i (i = Li, Ni, Co,
and Mn) at a specific reaction time can also be better analyzed. The
leaching rate Xi and leaching selectivity XSi were calculated using the
following equations
ci, t · c Na,0· V0
Xi = × 100%
mi · c Na, t (1)
X im i / M i
XSi = × 100%
∑j X jmj /Mj (2)
where ci,t and cNa,t are the respective concentrations of i and Na in the +
leachate at a specific reaction time of t in g/L, cNa,0 is the initial
concentration of Na+ in the leachant in g/L, V0 is the initial volume of
the solvent in L, mi is the mass of i in the pristine material in g, Mi is
the molar mass of i in g/mol, and Xj, mj, and Mj are the leaching rate
of j in %, mass of j in the pristine material in g, and molar mass of j in
g/mol, respectively.
3. RESULTS AND DISCUSSION
3.1. Process Control for Selective Extraction of Li
from Cathode Materials. 3.1.1. Effect of the Amount of
Persulfate Added on the AOPs. Because the maintenance of a
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strong oxidizing environment is the key to achieving selective

leaching of Li from cathode materials, the effect of sodium
persulfate on the leaching of metals from W1 was researched at
first. Different amounts of persulfate were added into slurries
with a fixed slurry density of 400 g/L at 85 °C to investigate its
effect on Xi and XSLi, with results summarized in Figure 1.

Figure 2. Effect of reaction temperatures on the leaching process

(W1, [S2O82−]/[M] 0.30, slurry density 400 g/L, stirring speed 300
rpm, and reaction time 240 min).

3.1.3. Effect of the Slurry Density on the AOPs. Besides the

abovementioned two factors, the solid-to-liquid (STL) ratio is
also a key parameter for the leaching process. Under the
Figure 1. Effect of the amount of persulfate added on the leaching
premise of fixed equipment and the other reaction conditions,
process (W1, temperature 85 °C, slurry density 400 g/L, stirring a lower STL ratio will increase the contact possibility and
speed 300 rpm, and reaction time 120 min). contact time between cathode material particles and the
reaction medium, so the leaching process can be enhanced to
some extent. Figure 3 summarized the XM and XSLi over the
Obviously, more persulfate is beneficial for increasing the
leaching rate of Li (XLi), while it would cause deterioration in
leaching selectivity of Li (XSLi) at the same time, especially
when the molar ratio of persulfate to M [S2O82−]/[M] is larger
than 0.30, as reported by other researchers.25,33 This is because
the contents of H+ and sulfate radicals increase almost linearly
with the amount of persulfate added, considering that its
hydrolysis rate constant is fixed under a specific temperature.
More H+ is conducive to increase the leaching rate of Li via
either substitution of Li or destruction of the material.
However, during the destruction of the material, M2+ will be
leached into the solution simultaneously with Li+ and only
Co2+ and Mn2+ can be oxidized as solid-state oxides by
persulfate or sulfate radicals, resulting in the deterioration of
XSLi. Meanwhile, increasing the usage of sodium persulfate
means the increase of cost. Thus, a [S2O82−]/[M] of 0.30 was
selected as the optimum value and was maintained in the
following experiments.
3.1.2. Effect of Temperature on the AOPs. When the
amount of persulfate added is fixed, the rate of its hydrolysis is Figure 3. Effect of the solid-to-liquid ratio on the leaching process
(W1, temperature 85 °C, [S2O82−]/[M] 0.30, stirring speed 300 rpm,
mainly affected by temperature.25 Figure 2 demonstrates Xi and reaction time 240 min).
and XSLi variation over temperature in the range from 55 to 95
°C, with other conditions controlled as follows: [S2O82−]/[M],
0.30; slurry density, 400 g/L; and reaction time, 240 min. STL ratio. It can be seen that XM increases accordingly as
By increasing T from 55 to 85 °C, XLi and XNi both exhibit a decreasing STL from 600 to 200 g/L. Conversely, a higher
significant increase, while XCo and XMn show small changes, STL ratio causes significant deterioration to the XLi, especially
and this might be due to Co2+ and Mn2+ being more readily when it is higher than 400 g/L.
oxidized. Meanwhile, XSLi decreases with the increase of T. 3.1.4. Effect of Solution pH on the AOPs−CLPs.
Further increasing T to 95 °C, a slight increase in all XM is Furthermore, to enhance the leaching efficiency of Li of
observed, indicating that the destruction of the cathode AOPs, different amounts of sulfuric acid were added into the
material is further promoted at 95 °C, but it only has a slight slurry together with persulfate at t = 0, and the solution pH was
effect on the process. Thus, it can be concluded that a higher T measured at the end of leaching at 85 °C (defined as solution
favors the leaching kinetics, while it is not conducive to the endpoint pH). Figure 4 shows the effect of solution endpoint
leaching selectivity. pH on XM and XSLi at 85 °C and 240 min with an STL ratio of
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Figure 4. Effect of solution endpoint pH on the leaching process
(W1, temperature 85 °C, [S2O82−]/[M] 0.30, slurry density 400 g/L,
stirring speed 300 rpm, and reaction time 240 min).
400 g/L and [S2O82−]/[M] = 0.30. It was found that all XM
exhibited significant increase with decreasing solution pH
during the leaching process, and the value for XLi remained
stable after the solution endpoint pH of about 3.0. Further
lowering the solution pH only resulted in an increase in XTM
and a decrease in XSLi because the structure of the cathode
material was more susceptible to be destructed in more acidic
solutions. Thus, although adding acid into the system can
greatly enhance the chemical delithiation process, it will lead to
severe deterioration of reaction selectivity and even make the
selectively chemical delithiation unachievable.
3.2. Mechanisms for Selective Extraction of Li with
AOPs. Although persulfate oxidation has been widely used to
achieve the AOPs, it is still rare to be used in the waste
recycling field. The process mechanism remains ambiguous
with only some overall equations expressed as25,33
LiMO2 + 0.5xS2 O82 − → Li1 − xMO2 + xSO4 2 − + x Li+
(3)
where M represents transition metals, such as Ni, Co, and Mn
and x is the removal ratio of Li. For this, more mechanisms of
AOPs or AOPs−CLPs are researched, discussed, and proved in
the following sections. For seeking simplification, the NCM523
scrap (W2) was chosen as the raw material to understand the
leaching mechanisms.
3.2.1. Mechanism Analysis for AOPs. To better understand
the mechanism of leaching of valuable metals from spent LIBs
in AOPs, the parameters of the leaching process were
monitored and are shown in Figure 5. In early reports, it
was believed that M in the cathode material would not be
leached unless sulfuric acid was excessive when persulfate was
sufficient in the leachant. Thus, to ensure a high selectivity of
lithium extraction, [S2O82−]/[M] should be controlled at a
quite low level.33 However, the abovementioned conclusions
contradict the phenomenon of the initial sharp drop of
solution pH and the continuous leaching of transition metals,
especially Ni, along with the leaching process, as shown in
Figure 5.
In Figure 5, the moment when persulfate was added into the
slurry was defined as t = 0 min. Right after adding NCM523
particles into preheated deionized water at t = −15 min, the
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Figure 5. Variation of solution pH and leaching rates of various
metals during the leaching of W2 (NMC523) in Na2S2O8 aqueous
solution at 85 °C (solid-to-liquid ratio 400 g/L, [S2O82−]/[M] 0.33,
and stirring speed 300 rpm).
solution pH increased from 6.51 to 9.83 in a couple of seconds,
then gradually decreased, and remained at 9.46. This is caused
by the rapid exothermic dissolution of LiOH formed by the
reaction of excess Li2O on the surface of NCM523 with
moisture in the air.34 After persulfate was added, the solution
pH instantly dropped to 9.21 along with releasing lots of
oxygen bubbles and continuously dropped to 6.50 in the
following 5 min. In the end, the pH of the leachate remains at
4.5. The reactions 4 and 5 describe the reaction of the
hydrolysis of persulfate. With progressive hydrolysis, H+ is
continuously released into the medium accompanying the
release of O2. In the initial 5 min, only 5.32% of Li was leached
and M in the material cannot be leached at all, meaning that
H+ is essential for the leaching process. Li+ in the LiO2 plane in
NCM523 would be preferentially substituted by H+ to form
the metastable layered phase of Li1−xHyMO2 (0 ≤ y < x < 1),
as described in reaction 6.31,35−37 However, after a rapid
decline, the pH of the solution remains at 4.5 in the following
time with the Li and Ni continuous leaching. It means that the
rate of reaction between H+ and NCM is equivalent to the rate
of the hydrolysis of persulfate, when the pH of the solution
reaches at 4.5.
S2 O82 − + H 2O → 2SO4 2 − + 2H+ + 0.5O2 ↑ (4)
H+ + OH− → H 2O (5)
y H+ + LiMO2 → Li1 − xHy(0 ≤ y < x < 1)MO2 + x Li+ (6)
Figure 5 also shows that the leaching efficiencies of Co and
Mn are still nearly 0 in the process. Previous research studies
indicated that the sulfate free radical (SO•− •
4 ), even ( OH),
would be generated during the heat-activation of persulfate25
described as reactions 7 and 8.38 These free radicals could
readily accept the electrons that transferred from the
framework of the precursor LiMO2 to the surface, during the
lithium removal process.25 It can largely compensate for the
lithium vacancy formed due to the removal of Li+ and inhibit
the disproportionation of M and thereby help maintaining the
stability of the material structure. However, the destruction of
the structure is not completely limited. If the structure of
materials is still stable in the reaction process, it is hard to
explain the leaching of Ni in the process. Meanwhile, as we all
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Figure 6. Pourbaix diagrams for redox reactions of (A) Li, (B) Ni, (C) Co, and (D) Mn in persulfate solutions at 25 °C (black line) and 100 °C
(blue line) (ci = 1.0 × 10−3 mol/L, i = Li, Ni, Co, and Mn).
know, the leaching of Ni, Co, and Mn is synchronous in the
acid system with no other additive. Thus, leaching of metals
must exist in the AOPs or AOPs−CLPs. Of course, because of
the superior oxidizing ability of S2O82−, SO•− •
4 , or OH, the
2+ 2+
leached M , expect Ni , could all be oxidized to high-valence
oxides or ions in principle, and an increase in solution
alkalinity and temperature would thermodynamically favor
these reactions, as shown in Figure 6 and described as reaction
9. No Co2+ and Mn2+ leached in the solution because of the
combined effect of these two reaction processes. Thus, as
leaching proceeds, only XLi and XNi gradually increase over
time, while XCo and XMn always maintain at approximately
zero.
S2 O82 − → SO4•− + SO4•−
•− • −
SO4 + H 2O → HO + HSO4
SO4•− + M2 + + 2H 2O → SO4 2 − + MO•OH + 3H+
Along with leaching, the amounts of newly formed H+ and
SO•−4 gradually decrease because of the continuous con-
sumption of S2O82− and the fact that the hydrolysis rate
constant of S2O82− depends only on temperature but not its
concentration.25 Therefore, after leaching for 180 min, the pH
value stabilizes at 4.65, and similar phenomena have been
discovered by Joo et al when using persulfate to oxidize
Mn2+.39 Interestingly, the leaching process gradually deceler-
ates and eventually stagnates after 180 min, although the
acidity of the solution is suitable for the leaching-related
reactions mentioned above. It is caused by the coating of newly
formed oxides on the surface of residues, thus hindering the
leaching process. The identifications of the new phase are
listed in the next section. Of course, the lower reaction rate of
the leaching process in the weak acid environment is also the
problem to further limiting the leaching of Li+.
Besides, more experiments were carried out to explore the
mechanism of AOPs, especially the effects of S2O82−, SO•− 4 ,
and •OH in this system. Ethanol (EtOH) and tert-butanol (t-
BuOH) are used as quenchers to quench SO•− •
4 and OH.
pubs.acs.org/journal/ascecg Research Article
Previous research studies have reported that EtOH has no
selectivity for the high reaction rate with SO•−
4 (1.6−7.7 × 10
7
−1 −1 • −1 −1
M S ) and OH (1.2−2.8 × 10 M S ). The reaction
9
rate constant of t-BuOH with •OH (4.0−8.1 × 108 M−1 S−1) is
1000 times higher than that with SO•− 4 (4.0−9.1 × 10 M
5 −1
−1
S ). Because huge amounts of EtOH or t-BuOH need to be
used to quench SO•− •
4 and OH for the previous system, in this
section, the effect of SO4 and •OH was investigated in a small
•−
system, in which the molar concentration of EtOH or t-BuOH
was 50 times or only 0.5 times than that of S2O82−. Results
indicate that the leaching of Co2+ and Mn2+ is released by
quenchers, which are different with no quenchers (Figure 7A).
When the usage of quenchers such as EtOH or t-BuOH is
(7)
excessive, 50 times those of S2O82−, as shown in Figure 7B,C, a
large amount of Co2+ and Mn2+ is present in the leachate with
(8)
(9)
Figure 7. Leaching efficiency of (A) without EtOH and t-BuOH; (B)
with 1.6 M EtOH; (C) with 1.6 M t-BuOH; (D) with 0.02 M EtOH;
and (E) with 0.02 M t-BuOH (W2, solid-to-liquid ratio 10 g/L,
[S2O82−]/[M] 0.30, stirring speed 300 rpm, 85 °C, and reaction time
360 min).
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the decrease of leaching efficiency of Li compared to the
reaction with no quencher (Figure 7A). It indicates that
oxidative radicals are essential for the selective leaching. If most
of the radicals are captured by quenchers, only the H+ is
generated from the hydrolysis of persulfate to react with NCM
materials. The leaching efficiencies of Co and Mn in the EtOH
system are higher than those in t-BuOH. The reaction rate
constant of t-BuOH with SO•− 4 is minimal compared with
other reactions. Therefore, it can be inferred that the reaction
rate constants of Co2+ and Mn2+ with SO•− 4 are similar with the
constant of t-BuOH with •SO4− but lower than the constant of
EtOH with SO•− •−
4 . Furthermore, SO4 is the main free radical
to maintain the selectivity of the leaching process and is easier
to react with Co2+ and Mn2+ than t-BuOH. When the usage of
quenchers was insufficient, only parts of free radicals were
quenched, resulting in the slight decrease of leaching rates of Li
and increase of leaching rates of Co and Mn. The results in
Figure 7D,E indicate that the leaching of Mn can be hindered
with insufficient t-BuOH, but not with insufficient EtOH.
Therefore, it suggests that the reaction rate between Mn2+ and
SO•−4 is faster than that between Co2+ and SO•− 4 for the
insufficient t-BuOH and can mainly quench •OH compared
with insufficient EtOH.
3.2.2. Mechanisms Analysis for AOPs−CLPs. It is hard to
achieve a leaching rate of Li greater than 90% only with AOPs,
as the data in Figures 1−3 show. The reason may be that there
is inadequate H+ to react with waste in the system. The
previous research studies have indicated that when about 60%
Li is leached from materials, the remaining materials will be
hard to react with H+ at high pH without the additive; in other
words, the structure of materials is difficult to be further
damaged. Therefore, AOPs−CLPs were introduced into the
system to enhance the leaching rate of Li, as shown in Section
3.1.4. More in-depth analysis was conducted to show the
mechanism of AOPs−CLPs, as shown in Figure 8.
Figure 8. Variation of solution pH and leaching rates of various
metals during the leaching of W2 (NMC523) in Na2S2O8 and H2SO4
aqueous solution at 85 °C (solid-to-liquid ratio 400 g/L, [S2O82−]/
[M] 0.33, stirring speed 300 rpm, and solution endpoint pH = 2.98).
In Figure 8, the moment when persulfate was added into the
slurry was defined as t = 0 min. Right after adding NCM523
particles into preheated deionized water at t = −15 min, the
solution pH increased from 6.51 to 9.83 in a couple of seconds,
then gradually decreased, and remained at 9.46. H2SO4 was
added in the solution after 10 min, resulting in the pH drop
from 9.46 to 4.5 for the amounts of H+ introduced in the
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system. At t = 0 min, the pH of the solution was still dropping
to a lower value following the adding of persulfate. In the end,
the pH of the solution arrived at pH = 2.98. ICP results
indicated that part of Li, Ni, Co, and Mn has been leached
from the spent materials at t = 0 min because of the adding of
H2SO4. However, all of the metal ions were precipitated into
the slag phase again in the following reaction time, except for
Ni and Li ions, which were hard to be oxidized by SO4•− or
•
OH.
Figures 9 and S1 show the morphological and structure
evolution of delithiated materials obtained from persulfate-
Figure 9. Morphological variation during chemical delithiation in
Na2S2O8−H2SO4 aqueous solution.
containing dilute acidic solution at 85 °C. Obviously, the
pristine material started as compact regular balls with a smooth
surface, and the diffractogram mainly has 10 well-indexed
peaks at 18.65, 36.64, 37.85, 38.29, 44.37, 48.54, 58.55, 64.29,
64.87, and 68.16°, corresponding to (003), (101), (006),
(012), (104), (015), (107), (018), (110), and (113) of
Li(Ni0.5Co0.2Mn0.3)O2, respectively.40
With selective leaching proceeding for less than 120 min, a
shift of the plane (003) to lower 2θ values and a spacing
expansion of the (018)/(110) doublet are observed and shown
in Figure 10 A,B. They jointly indicate a lattice expansion
along the c-axis direction and a contraction along the a-axis
direction, which is induced by the increase in the electrostatic
repulsion of oxygen anions among adjacent layers caused by
the preferentially leaching of Li+ from the lattice.27,41 Besides
the peak shift, the peak intensity would also vary with the
leaching depth. As shown in Figure S2, I(003)/I(104) increases
from 1.50 to 3.37 and (I(006) + I(012))/I(104) decreases from 0.24
to 0.14 associated with a decrease in Li content from 1.00 to
0.35, indicating a significant improvement in crystallinity and a
decline in the cation mixing inside the material. Moreover, this
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ACS Sustainable Chem. Eng. 2020, 8, 5165−5174
ACS Sustainable Chemistry & Engineering
Figure 10. XRD patterns of residues over time in (A) 18−20° 2θ; (B)
63−68° 2θ; (C) 18.8−19.0° 2θ; and (D) 36.5−39.5° 2θ.
is due to the removal of Li+ existing in the interslab space and
the lattice expansion along the c-axis as discussed above.
Furthermore, as shown in Figure 9 (t = 30 min), clear
exfoliation at the surface of the particles is observed because of
the proton intercalation and the neutralization reactions
between protons and oxides of TMs inside the layered
structure. The leached Co2+ and Mn2+ cannot keep stable in
the presence of persulfate or sulfate radicals and would readily
be oxidized to the corresponding oxides MO2. By gliding of
MO2 sheets along the c-axis of the original O3-type phase, an
emerging P3-type phase with an oxygen stacking sequence of
AABBCC is formed and reflects as a tiny peak at 18.89° 2θ
next to the original (003) peak,26 as shown in Figure 10C.
With accumulation of the P3-type phase, the residue is
wrapped with a flaky substance (Figure 9, t = 60 and 120 min),
and the (006) peak gradually approaches and eventually
merges with the (101) peak, as shown in Figure 10D. In the
meantime, as circled by a purple dotted line in Figure 10A, the
intensity of the P3 phase gradually degrades and vanishes
finally at t = 120 min, suggesting that with the continuous
oxidation of Co2+ and Mn2+, they would be converted into
mixed oxide with a small amount of Ni and even Li,
considering that the (101) and (012) peaks after position
Figure 11. AOPs−CLP technology and traditional technology flowsheet for the overall stepwise treatment of the spent NCM523.
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shifting are quite similar to the (100) and (011) peaks of
NixCoyMn1−x−yO2.26
After leaching for 120 min, the hydrogen content in the
residue reaches 0.11 and increases rapidly to 0.23 at t = 240
min and 0.39 at t = 360 min through calculation and the
electrostatic repulsion mentioned previously is greatly
alleviated with the insertion of protons, and this would make
the lattice collapse along the c-axis. Also, with the continuous
insertion of protons and the gradual accumulation of MO2 on
the surface of the residue, cation mixing will be severely
promoted. All these contribute to the return of the (003) peak
to its initial position, the decrease of I(003)/I(104) from 3.37 to
2.39, and the increase of (I(006) + I(012))/I(104) from 0.14 to
0.38, as shown in Figure S2. Moreover, at t = 240 min, an
acicular substance is found intergrown with MO2 sheets on the
surface of particles, and tiny diffraction peaks show up at 12.6
and 25.5°, which are assigned as the (001) and (002) peaks of
a birnessite-type layered structure with the empirical formula
Li4Mn14O27·xH2O.41 Until 360 min, the particle is wrapped
with a Mn-containing flocculent substance, and the selective
leaching process of Li is almost stagnant.
3.3. Development of a Closed-Loop Process. AOPs−
CLP technology reported in this article and traditional
technology summarized from previous research studies are
shown in Figure S3. After the selective leaching process, a
lithium-rich solution with little Ni2+ and an M-rich (M = Ni,
Co, and Mn) oxide residue was obtained (a typical selective
leaching recovery rate comparison can be found in Figure S4).
Many purification processes, such as precipitation, solvent
extraction, or electrolysis can be used to remove Ni2+ from the
leachate as the Ni product. Here, a mixed solution with 10%
NaOH and 15% Na2CO3 was used to remove Ni from the
leachate. After that, only 1.39 ppm Ni2+ remained in the
solution with 2.06% Li being absorbed by precipitation. Then,
sodium carbonate solution (25 wt.%) was used to produce
Li2CO3 at 90 °C, leaving nearly 3.1 g/L Li (17.2% of initial
content) in the solution for the solubility of Li2CO3 and the
increase of solution volume. Li2CO3 with a purity of 99.0%
(Figure S5 shows the XRD and SEM images of Li2CO3) was
obtained after being washed with 90 °C deionized water three
times. The residual Li+ in the solution can be removed as
Li3PO4 from solution, which has been reported in our previous
research.15,42 The cold waste solutions from the recycling
process can be directly used to regenerate Na2S2O8 through
https://dx.doi.org/10.1021/acssuschemeng.9b07515
ACS Sustainable Chem. Eng. 2020, 8, 5165−5174
ACS Sustainable Chemistry & Engineering
electrolysis.43−45 After that, the solutions with regenerated
Na2S2O8 can be directly returned to the leaching process.
Using the experimental data from this article (shown in
Figure 8 and the abovementioned section) and previous
research studies, simple material flows are shown in Figure 11.
Because of the common ignorance in the precipitation process,
it is hard to find an accurate value to describe the loss of Li in
these processes. Therefore, the loss of lithium in the
precipitation process is maintained in the same ratio with the
quality of the precipitate in AOPs−CLP technology and
traditional technology. As for solvent extraction process, the
loss of Li has been reported.46,47 Then, compared with
traditional technology, the biggest difference of AOPs−CLP
technology is that lithium is selectively extracted from waste
first. Meanwhile, the Li+ concentration of the leachate
approaches nearly 18.2 g/L and is much higher than the
previous 3−4 g/L (even lower than this) reported in the
literature.48,49 Previous investigations have identified that the
Li+ concentration of the solution needs to be around 20 g/L
for achieving an extraction efficiency of Li2CO3 more than
80%.50 However, the material flow shows that the Li
concentration of the solution from traditional technology is
only 3−4 g/L, which means nearly 80% water need to be
evaporated in the evaporation process.48,51 Much energy will
be consumed in this process. Meanwhile, the solid-to-liquid
ratio of traditional technology is also limited for the solubility
of salts. To obtain a 4 g/L Li+ solution from the spent
NCM523 through traditional technology, the total salt content
of the solution will be higher than 280 g/L. It means that the
salt content of the solution will be nearly 1000 g/L, when the
Li+ concentration is concentrated to 20 g/L. As we all know,
the solubility of many sulfates is much lower than this value. In
other words, all of these sulfates are easy to be precipitated
from the solution in the process, when extract Li2CO3. It is
difficult to directly extract high-purity Li2CO3 from this
solution without other processes. Significantly, previous
research also indicated that 15−20% Li would be absorbed
by the hydroxide product or extractant.48,49 Therefore, lithium
is always ignored by factories for little, even no, benefits. As for
AOPs−CLPs, the leachate containing nearly 20 g/L Li+ can be
directly used to precipitate Li2CO3 after removing Ni with little
loss of Li. The merit of AOPs−CLPs is that a high extraction
efficiency of Li can be achieved through the short process. This
process tremendously enhances the real extraction efficiency of
Li with little loss of other valuable metals. In other words, the
total recovery efficiency is greatly enhanced through this
process compared with traditional technology. As we all know,
it means huge economic benefits. For example, the data shown
in Figure 11 indicated that about 4.25 kg Li per ton of
NCM523 was recovered as Li2CO3 compared with the
traditional technology. Meanwhile, about 7.6 m3 water per
ton of NCM523 need to be evaporated in the traditional
technology with no water in AOPs−CLP technology.
4. CONCLUSIONS
The AOPs−CLP technology was successfully used to achieve
the selective extraction of Li from spent LIBs in a fairly mild
reaction environment. About 91.23% Li can be extracted from
spent NCM523 scraps with only 17.56% Ni leached in the
process. The Li concentration of the leachate is around 18.2 g/
L, which can be directly used to produce the Li product after
extracting Ni. Li2CO3 with a purity of 99.0% was obtained in
the end in the short process. Besides, the mechanism for the
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pubs.acs.org/journal/ascecg Research Article
AOPs−CLPs was also investigated in detail. In persulfate-
containing dilute acidic aqueous solutions, adequate H+ in the
solution would preferentially substitute Li+ in the interslab
space of the LiNi0.5Co0.2Mn0.3O2 cathode material, while
destroying the stability of the layered structure. The leached
Co2+ and Mn2+ cannot keep stable under a strong oxidizing
environment and are readily oxidized to the corresponding
oxides MO2 by •SO4− and •OH leaving only Ni2+ and Li+ in
the solution. In the end, acicular Li4Mn14O27·xH2O was
observed with MO2 sheets on the surface of particles. Besides,
research studies also proved that the reaction rate between
SO•− 2+ •−
4 and Co was higher than that between SO4 and Mn
2+
in the AOPs. In summary, the AOPs propose a novel direction
for future applications in both hydrometallurgy and solid waste
field.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.9b07515.
Completed XRD patterns for the residues from the
leaching process, position shift and intensity changes of
some peaks in XRD patterns, process flowsheet for the
technologies, and XRD and SEM images for Li2CO3
synthesized from the leaching process (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Zhi Sun − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China; School of Chemical Engineering, University of Chinese
Academy of Sciences, Beijing 100190, China; orcid.org/
0000-0001-7183-0587; Phone: +86 10 82544844;
Email: sunzhi@ipe.ac.cn; Fax: +86 10 82544845
Authors
Weiguang Lv − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China; School of Chemical Engineering, University of Chinese
Academy of Sciences, Beijing 100190, China
Zhonghang Wang − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China
Xiaohong Zheng − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China
Hongbin Cao − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China; orcid.org/0000-0001-5968-9357
Mingming He − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
https://dx.doi.org/10.1021/acssuschemeng.9b07515
ACS Sustainable Chem. Eng. 2020, 8, 5165−5174
ACS Sustainable Chemistry & Engineering
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China
Yi Zhang − National Engineering Laboratory for
Hydrometallurgical Cleaner Production Technology, Institute of
Process Engineering, Innovation Academy for Green
Manufacture, Chinese Academy of Sciences, Beijing 100190,
China
Haijun Yu − Hunan University, Changsha, Hunan 410082,
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.9b07515
Author Contributions
∥ 2019, 52, 484.
W.L. and Z.W. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge the financial support for this
research from the National Key Research and Development
Program of China (2017YFB0403300/2017YFB0403305), the
National Natural Science Foundation of China under grant
nos. 51934006 and 51874269, and the 1000 Talents Program
of China (Z.S.).
■
REFERENCES
(1) Lv, W.; Wang, Z.; Cao, H.; Sun, Y.; Zhang, Y.; Sun, Z. A Critical
Review and Analysis on the Recycling of Spent Lithium-Ion Batteries.
ACS Sustainable Chem. Eng. 2018, 6, 1504−1521.
(2) Harper, G.; Sommerville, R.; Kendrick, E.; Driscoll, L.; Slater, P.;
Stolkin, R.; Walton, A.; Christensen, P.; Heidrich, O.; Lambert, S.;
Abbott, A.; Ryder, K.; Gaines, L.; Anderson, P. Recycling lithium-ion
batteries from electric vehicles. Nature 2019, 575, 75−86.
(3) Natarajan, S.; Aravindan, V. Burgeoning Prospects of Spent
Lithium-Ion Batteries in Multifarious Applications. Adv. Energy Mater.
2018, 8, 1802303.
(4) Zeng, X.; Xu, M.; Li, J. Examining the sustainability of China’s
nickel supply: 1950−2050. Resour., Conserv. Recycl. 2018, 139, 188−
193.
(5) Zhang, X.; Li, L.; Fan, E.; Xue, Q.; Bian, Y.; Wu, F.; Chen, R.
Toward sustainable and systematic recycling of spent rechargeable
batteries. Chem. Soc. Rev. 2018, 47, 7239−7302.
(6) Wang, M.; Tan, Q.; Liu, L.; Li, J. Efficient Separation of
Aluminum Foil and Cathode Materials from Spent Lithium-Ion
Batteries Using a Low-Temperature Molten Salt. ACS Sustainable
Chem. Eng. 2019, 7, 8287−8294.
(7) Gao, W.; Song, J.; Cao, H.; Lin, X.; Zhang, X.; Zheng, X.; Zhang,
Y.; Sun, Z. Selective recovery of valuable metals from spent lithium-
ion batteries − Process development and kinetics evaluation. J.
Cleaner Prod. 2018, 178, 833−845.
(8) Sattar, R.; Ilyas, S.; Bhatti, H. N.; Ghaffar, A. Resource recovery
of critically-rare metals by hydrometallurgical recycling of spent
lithium ion batteries. Sep. Purif. Technol. 2019, 209, 725−733.
(9) Zhang, J.; Hu, J.; Zhang, W.; Chen, Y.; Wang, C. Efficient and
economical recovery of lithium, cobalt, nickel, manganese from
cathode scrap of spent lithium-ion batteries. J. Cleaner Prod. 2018,
204, 437−446.
(10) Porvali, A.; Aaltonen, M.; Ojanen, S.; Velazquez-Martinez, O.;
Eronen, E.; Liu, F.; Wilson, B. P.; Serna-Guerrero, R.; Lundström, M.
Mechanical and hydrometallurgical processes in HCl media for the
recycling of valuable metals from Li-ion battery waste. Resour.,
Conserv. Recycl. 2019, 142, 257−266.
(11) Chen, X.; Kang, D.; Cao, L.; Li, J.; Zhou, T.; Ma, H. Separation
and recovery of valuable metals from spent lithium ion batteries:
Simultaneous recovery of Li and Co in a single step. Sep. Purif.
Technol. 2019, 210, 690−697.
5173
pubs.acs.org/journal/ascecg Research Article
(12) Fan, E.; Li, L.; Lin, J.; Wu, J.; Yang, J.; Wu, F.; Chen, R. Low-
Temperature Molten-Salt-Assisted Recovery of Valuable Metals from
Spent Lithium-Ion Batteries. ACS Sustainable Chem. Eng. 2019, 7,
16144−16150.
(13) Liu, C.; Lin, J.; Cao, H.; Zhang, Y.; Sun, Z. Recycling of spent
lithium-ion batteries in view of lithium recovery: A critical review. J.
Cleaner Prod. 2019, 228, 801−813.
(14) Zhu, S.-g.; He, W.-z.; Li, G.-m.; Zhou, X.; Zhang, X.-j.; Huang,
J.-w. Recovery of Co and Li from spent lithium-ion batteries by
combination method of acid leaching and chemical precipitation.
Trans. Nonferrous Met. Soc. China 2012, 22, 2274−2281.
(15) Zhao, C.; Zhang, Y.; Cao, H.; Zheng, X.; Van Gerven, T.; Hu,
Y.; Sun, Z. Lithium carbonate recovery from lithium-containing
solution by ultrasound assisted precipitation. Ultrason. Sonochem.
(16) 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, 1662−1669.
(17) Meng, Q.; Zhang, Y.; Dong, P. A combined process for cobalt
recovering and cathode material regeneration from spent LiCoO2
batteries: Process optimization and kinetics aspects. Waste Manage.
2018, 71, 372−380.
(18) Hu, J.; Zhang, J.; Li, H.; Chen, Y.; Wang, C. A promising
approach for the recovery of high value-added metals from spent
lithium-ion batteries. J. Power Sources 2017, 351, 192−199.
(19) 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, 11960−11966.
(20) Lin, J.; Liu, C.; Cao, H.; Yang, Y.; Chen, R.; Li, L.; Sun, Z.
Environmentally benign process on selective recovery of valuable
metals from spent lithium-ion batteries by using conventional
sulfation roasting. Green Chem. 2019, 21, 5904.
(21) Peng, C.; Liu, F.; Wang, Z.; Wilson, B. P.; Lundström, M.
Selective extraction of lithium (Li) and preparation of battery grade
lithium carbonate (Li2CO3) from spent Li-ion batteries in nitrate
system. J. Power Sources 2019, 415, 179−188.
(22) Tian, C.; Xu, Y.; Nordlund, D.; Lin, F.; Liu, J.; Sun, Z.; Liu, Y.;
Doeff, M. Charge Heterogeneity and Surface Chemistry in
Polycrystalline Cathode Materials. Joule 2018, 2, 464−477.
(23) Yang, Y.; Meng, X.; Cao, H.; Lin, X.; Liu, C.; Sun, Y.; Zhang,
Y.; Sun, Z. Selective recovery of lithium from spent lithium iron
phosphate batteries: a sustainable process. Green Chem. 2018, 20,
3121−3133.
(24) Venkatraman, S.; Choi, J.; Manthiram, A. Factors influencing
the chemical lithium extraction rate from layered LiNi1−y−zCoyMnzO2
cathodes. Electrochem. Commun. 2004, 6, 832−837.
(25) Ji, Z.-Y.; Zhao, M.-Y.; Zhao, Y.-Y.; Liu, J.; Peng, J.-L.; Yuan, J.-S.
Lithium extraction process on spinel-type LiMn2O4 and character-
ization based on the hydrolysis of sodium persulfate. Solid State Ionics
2017, 301, 116−124.
(26) Manthiram, A.; Choi, J. Chemical and structural instabilities of
lithium ion battery cathodes. J. Power Sources 2006, 159, 249−253.
(27) Basch, A.; de Campo, L.; Albering, J. H.; White, J. W. Chemical
delithiation and exfoliation of LixCoO2. J. Solid State Chem. 2014, 220,
102−110.
(28) Ishida, N.; Tamura, N.; Kitamura, N.; Idemoto, Y. Crystal and
electronic structure analysis and thermodynamic stabilities for
electrochemically or chemically delithiated
Li1.2−xMn0.54Ni0.13Co0.13O2. J. Power Sources 2016, 319, 255−261.
(29) Sekizawa, O.; Hasegawa, T.; Kitamura, N.; Idemoto, Y. Crystal
and electronic structure change determined by various method for
delithiation process of Lix(Ni,Mn)O2-based cathode material. J. Power
Sources 2011, 196, 6651−6656.
(30) Yoo, S.; Kang, B. Inhomogeneous delithiation behavior of
chemically delithiated Li0.49FePO4 particles of different sizes using a
simple centrifuge separation method. Electrochim. Acta 2015, 151,
270−275.
https://dx.doi.org/10.1021/acssuschemeng.9b07515
ACS Sustainable Chem. Eng. 2020, 8, 5165−5174
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

(31) Choi, J.; Alvarez, E.; Arunkumar, T. A.; Manthiram, A. Proton (51) Wu, C.; Li, B.; Yuan, C.; Ni, S.; Li, L. Recycling valuable metals
Insertion into Oxide Cathodes during Chemical Delithiation. from spent lithium-ion batteries by ammonium sulfite-reduction
Electrochem. Solid-State Lett. 2006, 9, A241−A244. ammonia leaching. Waste Manage. 2019, 93, 153−161.
(32) Takahashi, Y.; Kijima, N.; Dokko, K.; Nishizawa, M.; Uchida, I.;
Akimoto, J. Structure and electron density analysis of electrochemi-
cally and chemically delithiated LiCoO2 single crystals. J. Solid State
Chem. 2007, 180, 313−321.
(33) Higuchi, A.; Ankei, N.; Nishihama, S.; Yoshizuka, K. Selective
Recovery of Lithium from Cathode Materials of Spent Lithium Ion
Battery. JOM 2016, 68, 2624−2631.
(34) Torres, A. E.; Balbuena, P. B. Exploring the LiOH Formation
Reaction Mechanism in Lithium−Air Batteries. Chem. Mater. 2018,
30, 708−717.
(35) Zhecheva, E.; Stayanova, R. Li1‑x‑yHyCoO2: Metastable Layered
Phases Obtained by Acid Digestion of LiCoO2 (O3). J. Solid State
Chem. 1994, 109, 47−52.
(36) Zhecheva, S.; Stoyanova, R. New Phases Obtained by Acid
Delithiation of Layered LiMO2 (M=Co,Ni). Mater. Sci. Forum 1994,
152−153, 259−262.
(37) Venkatraman, S.; Manthiram, A. Investigation of the possible
incorporation of protons into oxide cathodes during chemical
delithiation. J. Solid State Chem. 2004, 177, 4244−4250.
(38) Zhang, M.; Chen, X.; Zhou, H.; Murugananthan, M.; Zhang, Y.
Degradation of p-nitrophenol by heat and metal ions co-activated
persulfate. Chem. Eng. J. 2015, 264, 39−47.
(39) Joo, S. H.; Kang, J.; Woong, K.; Shin, S. M. Production of
Chemical Manganese Dioxide from Lithium Ion Battery Ternary
Cathodic Material by Selective Oxidative Precipitation of Manganese.
Mater. Trans. 2013, 54, 844−849.
(40) Lv, W.; Wang, Z.; Cao, H.; Zheng, X.; Jin, W.; Zhang, Y.; Sun,
Z. A sustainable process for metal recycling from spent lithium-ion
batteries using ammonium chloride. Waste Manage. 2018, 79, 545−
553.
(41) Billy, E.; Joulié, M.; Laucournet, R.; Boulineau, A.; De Vito, E.;
Meyer, D. Dissolution Mechanisms of LiNi1/3Mn1/3Co1/3O2 Positive
Electrode Material from Lithium-Ion Batteries in Acid Solution. ACS
Appl. Mater. Interfaces 2018, 10, 16424−16435.
(42) Zhao, C.; He, M.; Cao, H.; Zheng, X.; Gao, W.; Sun, Y.; Zhao,
H.; Liu, D.; Zhang, Y.; Sun, Z. Investigation of solution chemistry to
enable efficient lithium recovery from low-concentration lithium-
containing wastewater. Front. Chem. Sci. Eng. 2019, 21.
(43) Zhu, J.; Hii, K. K.; Hellgardt, K. Toward a Green Generation of
Oxidant on Demand: Practical Electrosynthesis of Ammonium
Persulfate. ACS Sustainable Chem. Eng. 2016, 4, 2027−2036.
(44) Chen, L.; Lei, C.; Li, Z.; Yang, B.; Zhang, X.; Lei, L.
Electrochemical activation of sulfate by BDD anode in basic medium
for efficient removal of organic pollutants. Chemosphere 2018, 210,
516−523.
(45) Yang, S.-Q.; Cui, Y.-H.; Liu, Y.-Y.; Liu, Z.-Q.; Li, X.-Y.
Electrochemical generation of persulfate and its performance on 4-
bromophenol treatment. Sep. Purif. Technol. 2018, 207, 461−469.
(46) Chen, L.; Tang, X.; Zhang, Y.; Li, L.; Zeng, Z.; Zhang, Y.
Process for the recovery of cobalt oxalate from spent lithium-ion
batteries. Hydrometallurgy 2011, 108, 80−86.
(47) Torkaman, R.; Asadollahzadeh, M.; Torab-Mostaedi, M.;
Ghanadi Maragheh, M. Recovery of cobalt from spent lithium ion
batteries by using acidic and basic extractants in solvent extraction
process. Sep. Purif. Technol. 2017, 186, 318−325.
(48) 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.
(49) 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.
(50) Wang, W.; Chen, W.; Liu, H. Hydrometallurgical preparation of
lithium carbonate from lithium-rich electrolyte. Hydrometallurgy
2019, 185, 88−92.

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