Chemical Engineering Journal 436 (2022) 133200

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Ionization potential-based design of deep eutectic solvent for recycling of

spent lithium ion batteries
Yunhui Hua a, b, Yongqi Sun b, Feng Yan a, Shubin Wang a, Zhenghe Xu c, Baojun Zhao d, *,
Zuotai Zhang a, *
a
School of Environmental Science and Engineering, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China
b
School of Chemical Engineering, The University of Queensland, St Lucia 4072, Brisbane, Australia
c
Department of Materials Science and Engineering, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China
d
College of Materials, Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China

A R T I C L E I N F O A B S T R A C T

Keywords: Deep eutectic solvent (DES) is becoming an important alternative for green and high efficient recycling of spent
Ionization potential lithium ion batteries (LIBs). In this study, we proposed a simple and universal approach by applying ionization
Deep eutectic solvent potential (IP) calculation assisted with cyclic voltammetry test to assist selection of organic acid as efficient
Recycling spent lithium ion batteries
reductant in the DES for battery recycling. The reducibility of organic acid was found to have a close relationship
with the IP, with organic acids of lower IP being a more preferred reductant. Based on this approach, the hydrous
choline chloride-L-ascorbic acid DES was identified and verified to be efficient for metals leaching from LiNi1/
3Co1/3Mn1/3O2 cathode in multiple cycles, exhibiting leaching efficiencies over 96% for Li, Mn, Co and Ni under
a mild leaching condition (50℃, 1 h). The IP calculation is effective for screening reductive acids, and is also
feasible for predicting reaction mechanism. Metals were effectively recovered through sequential precipitation.
The deep eutectic solvent designed from IP calculation is versatile for treating various kinds of spent battery
cathodes and recyclable for multiple uses, decreasing the production of secondary chemical waste and pollution.

1. Introduction terrestrial, among which merely 7 Mt of Co is available for production.

The global tendency towards emission reduction and pollution
mitigation is leading to a rapid growth of electric vehicles (EV) in the
past a few years. In 2020, although the world economy was negatively
impacted by COVID-19, the annual global sale of EVs still boosted and
reached 3.1 M, representing a 39% increase compared with 2019 [1]. As
a carbon–neutral society is becoming the future development goal, it is
predicted that substituting internal combustion vehicles in subsequent
years requires a continuous growth in annual EV sale which is estimated
to reach around 12 M by 2025 [2,3]. In this case, the use of lithium-ion
batteries (LIBs), which is the dominant power source for both EVs and
portable electronic devices, will grow significantly [4–6]. However,
such growing utilization will unavoidably generate massive amounts of
spent LIB waste. In 2019, the global LIB recycling market was approxi­
mately US$1.5 billion and is estimated to reach US$18.1 billion by 2030
[7]. LIBs contain several valuable metals such as cobalt (Co), nickel (Ni)
and lithium (Li) that would be depleted if not recycled. Although there
are 145 Mt of global natural reserves of Co, only 25 Mt of them is
The recycle of these valuable metals is therefore extremely critical
[8–10]. Apart from resource sustainability concern, the environmental
concern of spent LIBs, such as the toxicity of Co and Ni, also calls for the
need for recycling.
In recycling of spent LIBs, effective recovery of valuable metal ele­
ments such as Co, Ni, and Li from battery cathodes is a key issue [11,12].
At present, carbothermal reduction-based pyrometallurgy or reductive
leaching-based hydrometallurgy are two main approaches for recovery
of valuable metals in spent LIBs. Although some of these processes have
already been scaled up, [13–15] the commercial applications remain
rather limited due to their inherent drawbacks. The traditional pyro­
metallurgy treatment incurs for example high energy consumption, CO2
emission and waste gas pollution with difficulties in Li recovery. For the
hydrometallurgy, chemical solutions for battery recycling are often not
reusable after the process but become wastewater that need to be further
treated. The generation of secondary pollution is contrary to the envi­
ronmentally friendly objective of recycling, while the cost for further
treatment is considerable. Moreover, huge consumptions of chemicals

* Corresponding authors.
E-mail addresses: baojun16302@163.com (B. Zhao), zhangzt@sustech.edu.cn (Z. Zhang).

https://doi.org/10.1016/j.cej.2021.133200
Received 7 June 2021; Received in revised form 19 October 2021; Accepted 22 October 2021
Available online 27 October 2021
1385-8947/© 2021 Published by Elsevier B.V.
Y. Hua et al. Chemical Engineering Journal 436 (2022) 133200

and long processing time are also prohibitive for commercial use of these organic acids with distinct IP were then selected to CV tests for verifi­
existing methods. Therefore, alternative recycling methods that can cation. Following the IP calculation and CV study, several organic acids
achieve better metal recovery with minimal generation of secondary were selected to synthesize DES which were used for metal leaching
wastes and multiple uses of processing medium are needed [11,16–18]. from spent LiNi1/3Co1/3Mn1/3O2 (NCM111) cathodes. L-ascorbic acid
In recent years, battery recycling using deep eutectic solvent (DES) with ChCl showed the best leaching performance, which proves that IP
has been investigated and is drawing increasingly more attentions calculation assisted by CV tests is a powerful tool for design of hydrous
[19–21]. Based on interactions between hydrogen bond acceptors (HBA) organic acid DES for recycling of spent LIBs.
and hydrogen bond donors (HBD), DES features such characteristics as
low melting points, non-volatile, non-toxic, thermal stable and wide 2. Experimental
operating temperature range [22–25]. DES has excellent performance in
dissolving metal oxides and salts with much larger capacities than many 2.1. Theoretical calculation of ionization potential
aqueous solutions, acting as ideal green solvent for metal extraction
[26–29]. DES is normally used with choline chloride (ChCl), ethylene Considering IP as the energy difference after and before an atom or
glycol (EG) or urea for metal recovery from spent LIBs. Apart from metal molecule ionizes, the value of vertical IP (VIP) and adiabatic IP (AIP)
leaching ability, it has also been reported that DES is effective in sepa­ were calculated using Eq. (1) and Eq. (2):
rating different metal elements under controlled conditions [20].
However, the obstacles of rigorous operating condition such as high VIP = EV (N − 1) − E(N) (1)
temperature and long reaction time in existing processes must be
AIP = EA (N − 1) − E(N) (2)
addressed for wide applications of such methods.
The selection of DES is based on characteristics of cathodes. The
where EV(N-1) is the vertical potential when a molecule loses an elec­
widely used LiCoO2 (LCO) and LiNixCoyMnzO2 (NCM) cathodes for
tron, while EA(N-1) is the adiabatic potential when a molecule loses an
example have a layered structure of lithium, oxygen and transition
electron. The system charge is + 1 for both EV(N-1) and EA(N-1). E(N) is
metals [30,31]. The transition metals in spent batteries are normally in
the potential of the initial neutral molecule with no charge, and N is the
mixed valences and those in high valences are usually not soluble in
number of electrons in the molecule.
water [32,33]. Therefore, these high-valence transition metals need to
In this study, the ChemDraw software was first applied to simulating
be first reduced. Moreover, to enhance the release of metal ions,
molecular structures of organic acids. Each simulated organic acid
hydrogen ions are needed to take away the oxygen and destroy the
molecule was automatically adjusted to minimal energy state by the
structure. EG and urea applied in previous studies are normally neutral
corresponding MM2 Minimize function in the software. The corre­
compounds. Therefore, it was not until high temperatures were reached
sponding organic acid structure files were transferred into the Gaussian
before they behaved their leaching ability. To achieve the goal for high
software for energy calculation. For the calculation of initial potential E
efficiency leaching under mild conditions, DES mixed with ChCl and
(N) and vertical potential EV(N-1), the Energy job type was selected. For
reductive acids is a feasible option for metal extraction. Composed of
the calculation of adiabatic potential, the Optimization to Minimum job
ChCl and organic acids such as citric acid or p‑toluenesulfonic acid, DES
type was selected. As for calculation method, the Ground State – DFT
has been shown to be effective for metal leaching below 100℃, but the
–B3LYP was used. For E(N) calculation of initial neutral species, the (R)
process mechanisms remain unclear [34,35]. Additionally, a theoretical
B3LYP level with Singlet spin was selected. The charge of the neutral
guidance to measure reducibility is also required to efficiently pick out
system was set as 0. For EV(N-1) and EA(N-1) calculation of the ionized
suitable reductive acid. It is therefore necessary to develop a benchmark
system, the (U)B3LYP level of Doublet spin was applied while the charge
to evaluate the reducibility of alternative acids and design a high-
of the ionized system was set as + 1. Basis Set was determined to be6-
efficient process for metal leaching using DES.
311G++ (d, p) for both neutral and ionized species [36,37]. Finally, the
In this study, different from previous work which screened DES
VIP and AIP were calculated using Eq.1 and 2 given above.
simply by experiments, we propose a novel and universal method
through applying the calculation of ionization potential (IP) assisted
with cyclic voltammetry (CV) test to determine reductive acids for DES 2.2. Cyclic voltammetry study
synthesis. IP for a series of inorganic and organic acids was first calcu­
lated using Discrete Fourier Transformation (DFT) principle. The The CV study was conducted using an electrochemical workstation

Scheme 1. Flow diagram of metal recovery process by ChCl-L-ascorbic acid DES.

2
Y. Hua et al.
produce by Wuhan Corrtest. The DES in this study was a hydrous organic
acid-based system which had similar environment as aqueous solution.
In previous studies about hydrous DES, it was reported that water would
influence the mass transfer, diffusion, electro-conductivity and some
other physical properties. The more or less of water did not have impact
on the redox ability of other DES components [38–39]. In this study, it
was found that organic acids had same redox behaviors and sequences in
hydrous DES and aqueous solution. To improve the stability and elec­
trical conductivity for CV test, the electrolyte solution was prepared by
mixing potassium chloride (KCl) with the selected organic acids at molar
ratio of 10:1 and then dissolved in the deionized water. The concen­
tration of each organic acid was set at 0.1 M. The glassy carbon electrode
of 3 mm diameter was used as working electrode, while a platinum wire
of 0.5 mm in diameter and 35 mm in length was used as the auxiliary
electrode. The calomel electrode (reference potential 0.28 V) was used
as reference electrode throughout this study. The Corrtest software
supplied to the work station was used in CV tests. The initial potential
was set at − 0.5 V and the potential scan ranged from − 0.5 V to 2.3 V at
the scan rate of 50 mV/s.
2.3. Synthesis of DES
The DES was prepared by mixing ChCl (applied as HBA) with an
organic acid (applied as HBD) at 2:1 in molar ratio. Such ratio provided
suitable melting point and fluidity for all selected organic acids in this
study (optical photographs of ChCl-L-ascorbic acid DES in different
molar ratios in Fig. S1). At the same time, concentrations of organic
acids were high enough. Since water content was an impact factor, a
small amount of deionized water was added to the DES in some groups.
The mixture then went through ultrasonic heating under 60℃ for
several hours until homogeneous liquid was formed. Similar approaches
to synthesize hydrous organic acid-based DES have also been reported in
previous studies [34,35].
2.4. Processes for leaching and recovery of metals
The flow process for leaching and recovery of metals from spent
cathode materials was given in Scheme 1. Cathode scraps from spent
LIBs were first crushed and sieved. The black powder of − 200 mesh was
mixed with DES in the glass flask at a given solid to liquid ratio (S/L) to
allow the leaching of metals in water bath. After leaching, the mixture
was diluted with deionized water and filtered with 0.22 μm pore size
filter to remove unreacted residues. A suitable amount of oxalic acid
solution, which was 1.5 times molar of NCM111, was then added into
the filtrate as precipitant. After collection of transition metal pre­
cipitates by filtration, the filtrate was heated at 60℃ under vacuum to
evaporate water. To assist removal of water, a desired amount of ethanol
was added into the filtrate. Subsequently, absolute ethanol was added to
generate lithium oxalate precipitates. After filtration to collect the solid
product, the filtrate liquor was again heated under vacuum to evaporate
ethanol. The remaining DES after the initial leaching still contained
unreacted reductant which was feasible for the next cycle.
2.5. Metal leaching efficiency analysis
Metals leached from raw material were analyzed by Inductively
Coupled Plasma Mass Spectrometry (ICP-MS) using the Agilent Tech­
nologies 7700X ICP-MS equipment, and the leaching efficiency was
calculated using Eq. (3),
cV
x= (3)
m
where × is the leaching efficiency, expressed as the fraction of extracted
metal from the initial raw cathode material, c is the concentration of
different metal ions in the leaching solution, V is the solution volume
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Chemical Engineering Journal 436 (2022) 133200
and m is the initial mass of element in the powder. To determine the
composition of the spent NCM111 cathode powder, the powder was
digested by aqua regia (composing of hydrochloric acid and nitric acid)
using the digestion apparatus, then diluted by deionized water. The
concentration of metals in the liquid was determined also by ICP-MS.
The leaching efficiencies at different leaching time were fitted to
various leaching kinetics equations, including mass transfer in the liquid
boundary layer (Eq. (4)), chemical reaction on the surface (Eq. (5)) and
diffusion in the solid surface layer (Eq. (6)).
x = k1 t (4)
(5)
1
1 − (1 − x)3 = k2 t
(6)
2
1 − 3(1 − x)3 + 2(1 − x) = k3 t
where × refers to leaching efficiency in the reaction time t, k1, k2 and
k3 are the slope of the fitting line, considered as the reaction rate con­
stant, and t represents reaction time. The activation energy of leaching
was calculated based on Arrhenius equation described by Eq. (7) or Eq.
(8).
(7)
Ea
k = Ae− RT
( )
Ea 1
lnk = − + lnA (8)
R T
where k represents the reaction rate constant (min− 1), A is the pre-
exponential factor, T represents temperature of reaction (K), Ea is the
activation energy of the reaction (J/mol), R is universal gas constant
(8.314 J/mol⋅K)
2.6. Characterization of solution and recovered product
The Fourier Transform Infrared (FT-IR) spectroscopy measurement
was conducted by NICOLET-IS50-FTIR. The ChCl powder, ascorbic acid
powder, the best leaching effect hydrous DES, and the recovered
leachate were taken for analysis. Each of them was mixed with potas­
sium bromide (KBr). The mixture was grounded to ensure complete
homogenization. The mixture was then pressed into small tablets for
FTIR analysis over a wave number range from 500 to 4000 cm− 1. The
absorbance was obtained through measured transmittance with auto­
matic baseline correct, scale normalization and automatic smoothing.
Peaks of FT-IR absorbance spectra were characterized from the
database.
The morphology and element distribution of raw material, pre­
cipitates and calcined products were analyzed by Scanning Electron
Microscope (SEM) accompanied by Energy Dispersive X-Ray Spectros­
copy (EDX) using a Zeiss Merlin SEM. The scanning voltage of SEM and
EDX mapping was set at 15 kV.
The raw material and products sampled during the process were
loaded on the silicon wafer after grinding, and then characterized by X-
Ray Diffraction (XRD) using the Rigaku Smartlab XRD operating at
45 kV and 200 mA. The scanning angle 2θ ranged from 10 to 80◦ at the
scanning rate of 5◦ per minute.
To determine the types and valences of elements, samples collected
during the process were analyzed by X-Ray Photoelectron Spectroscopy
(XPS) using PHI 5000 Versaprobe III XPS. The carbon binding energy
was set at 284.8 eV for standard calibration. The MultiPak software was
applied to identify types and valences of key elements in the sample. For
semi-quantitative analysis, the XPS original spectra were auto-smoothed
and manually fitted with Gauss-Lorentz method.
Y. Hua et al.
3. Results and discussion
3.1. Deep eutectic solvent design: IP calculation and CV test
The redox reaction is essentially an electron transferring process. IP
is an indicator to assess the reducibility, which is the minimum energy
required to remove an electron from an atom, ion or molecule. The value
of IP could provide information on the possibility and complexity for a
matter to lose electron while it is being oxidized. As sketched in Fig. 1a,
if an atom, ion or molecule has a relatively low IP, it will have a weaker
constraint for its outer shell electrons, and can donate them more easily
when there is an oxidizing agent or potential, working as an ideal
reductant [40,41]. The prediction of redox reactions from IP could be
validated by oxidation and reduction characteristics of CV tests. Once
validated, IP calculation could provide the most possible potentials
where the ionization occurs, supporting the analysis of molecular re­
action mechanism.
3.1.1. Prediction of leachability based on IP calculations
In this study, we first calculated IP values of different acids based on
DFT principle to evaluate their reducibility. The IP is generally divided
into Vertical Ionization Potential (VIP) and Adiabatic Ionization Po­
tential (AIP). The VIP is the minimum energy when a molecule loses an
electron without structure changes, while AIP represents the atomic
relaxation energy and therefore is referred to as the energy difference
between the neutral and oxidized forms of molecule when both struc­
tures are optimized to lowest energy states (sketched Fig. S2). As a
direct indicator of ability to lose an electron, the VIP is more related to
the oxidation potential. The VIP is the negative energy value of the
energy for the highest occupied molecular orbital (HOMO) in the DFT
calculations, which has been reported to have a linear relationship with
oxidation potential [42–44]. Therefore, the oxidation potential is pre­
dicted by VIP (simplified as IP in the following) in this study.
Both inorganic and organic acids have been proved to be effective for
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Chemical Engineering Journal 436 (2022) 133200
Fig. 1. IP calculation-based DES design and the re­
sults of corresponding CV tests. AA, CA, PTA and LAA
are four organic acids of acetic acid, citric acid, p-
toluenesulfonic acid and L-ascorbic acid, respec­
tively. a) Schematic diagram of materials selection
based on ionization potential (IP) and the calculated
IP values of the four organic acids and four inorganic
acids including HCl, HNO3, H2SO4, H3PO4; b) CV
curve of organic acids between − 0.5 to 2.3 V and
their first oxidation potential; c) Validation of the
DES design method: leaching efficiencies of metals
(Li, Co, Ni and Mn) from spent NCM111 cathode
materials by various DES synthesized using these
organic acids. Leaching experiments conducted
under 50℃, 1 h, S/L = 0.1 g/2.5 g, and each DES
composed of ChCl : organic acid : water = 2:1:6
(molar ratio).
metal leaching in previous researches, sometimes with the assistance of
reducing agent [45,46]. Fig. S3 shows the IP of a series of inorganic and
organic acids calculated. The exact IP values of inorganic acids and
organic acids investigated in this study are given in Table S1 and
Table S2, respectively. Organic acids tended to have lower IP than
inorganic acids due to the presence of reductive functional groups such
as –OH, –NH2 in organic acids, providing an additional reducibility.
Further discussed in detail here were four organic acids with obviously
different IPs, including citric acid (CA), p-toluenesulfonic acid (PTA),
the common acetic acid (AA) and the typical reductive L-ascorbic acid
(LAA) [47–52]. Apart from reducibility reflected in IP, other properties
of organic acids such as acidity could also affect the metal extractions. In
previous studies, these organic acids have been proved to be freely
soluble in aqueous solution with high acidity for metal extraction.
Additionally, they could also co-exist with metal ions in the aqueous
environment. The reducibility of these organic acids, therefore, was the
key point in metal leaching behavior. Also considered were four inor­
ganic acids, including the common hydrogen chloride, sulfuric acid,
nitric acid and phosphoric acid as representatives [53–57]. Fig. 1a
shows significantly higher IP for inorganic acids which provide only
acidity for the leaching reactions. In this case, additional reductants such
as Na2SO3 or H2O2 are needed for metal reduction reactions. Further­
more, most of the inorganic acids could stably existed only in aqueous
solutions, and therefore are not suitable for DES. For organic acids, they
could provide both the acidity and the reducibility, suitable for DES
synthesis. Based on the results of calculations as shown in Fig. 1a, AA has
the highest IP, followed by CA and PTA with LAA being of the lowest IP.
Therefore, the reducibility of these organic acids follows the sequence of
LAA > PTA > CA > AA. The IP calculation provided an initial theoretical
indication of suitable and representative acids for the following tests.
Based on this prediction of IP calculation with the consideration of
needing the donor of hydrogen bonds in the DES synthesis, organic acid
LAA is anticipated to have the strongest leaching ability of metals from
cathode materials.
Y. Hua et al. Chemical Engineering Journal 436 (2022) 133200

3.1.2. Predicting reducibility of the acids by CV test

IP theoretically predicted the redox potential for a matter by evalu­
ating the difficulty of giving out its electrons, while CV test is a useful
experimental technique to prove reactions of electron transfer [58–60].
CV is a universal technique to measure redox behaviors. Previously, it
has been applied in comparing EG and urea in the DES [20]. In general a
matter with lower IP is considered to have a lower oxidation potential.
As a result, the transfer of electrons could be achieved at lower external
electric potentials, which is reflected by a more negative oxidation peak
position in CV curves. Based on this principle, several organic acids were
tested by the CV method. As shown in Fig. 1b, LAA exhibits multiple
oxidation peaks at 0.37 V, 1.70 V and 2.15 V, while PTA features only
one oxidation peak at 1.67 V which is close to the second oxidation peak
of LAA. The oxidation peak of CA is located at 2.14 V which almost the
same as the third oxidation peak of LAA. In contrast, AA did not show an
oxidation peak over the potential scanning range.
Oxidation potential and HOMO energy have been found to have a
linear relationship. In this study, IP and the negative value of HOMO
energy were shown to be in good relationship with the oxidation po­
tential, as expressed in Eq. (9). Based on this equation, the oxidation
potential of AA was predicted to be 4.15 V, as shown in Fig. S4. Among
the different organic acids, LAA has the lowest first oxidation peak po­
tential, indicating LAA being the first to be oxidized under the same
condition. The peak density, on the other hand, revealed the reactivity of
the matter including the effects of electron transferring numbers, con­
centrations, diffusions and other factors. A higher peak density indicated
a better reactivity. Selected organic acids in this study played a role as
reductants, their oxidation reactions involving electrons were given in
Fig. S5 [50,61,62]. The results revealed that LAA had the highest peak
current density, which could be caused by its low electric potential. LAA
was the most active one with the largest actual electron transferring
amount. The most negative peak potential and the highest peak density
of LAA revealed that it had the best oxidizing reactivity among all Fig. 2. Reaction mechanism based on IP calculation and FT-IR test. a) Proposed
ionizing active sites (atoms) of LAA: oxygen atoms linked with C = C radical
selected organic acids. PTA also showed a more negative oxidation po­
(blue and green electron cloud); b) FT-IR spectra of ChCl, LAA, hydrous DES
tential than CA. Therefore, the reducibility of various acids from CV tests
before leaching reaction, and the recovered DES after leaching of NCM111; c)
followed the as sequence of LAA > PTA > CA > AA, as predicted from IP oxidizing reaction mechanism of LAA, releasing two hydrogen ions and two
calculations. electrons to become dehydroascorbic acid. (For interpretation of the references
Pox = 0.023*IP − 19.76 (9) to colour in this figure legend, the reader is referred to the web version of
this article.)

3.1.3. Validation of design DES by leaching test

To further validate the prediction of reactivity from IP calculations, a method is suitable for acidic DES design in spent battery recycling. High-
series of DES were synthesized using the foregoing organic acids mixed efficiency leaching can be achieved under mild environment, which
with ChCl and water, which were used to leach the NCM111 cathode increases its environmental friendliness and practicality.
materials. Leaching results are shown in Fig. 1c. As noted, CA-based DES
exhibited a better performance than AA in leaching metals, but the ef­
3.2. Analysis of reaction mechanism
ficiency for both was less than 40%. PTA showed a much better per­
formance than CA but was still much less effective than LAA which
Because of its best leaching performance, ChCl-LAA DES was selected
showed a leaching efficiency over 90% for all metals. The leaching ef­
as leaching agent for further investigation. The ionizing atoms were
ficiency of Li+ using DES prepared by AA, CA or PTA was found to be
proposed based on the results of IP calculations by comparing the
higher than that of transition metals, which is attributed to lower sta­
charges of atoms in the molecule. The most probable ionization atoms of
bility in layered structure, smaller ionic radius and fewer charge of
the LAA from IP calculations were labeled in Fig. 2a. The two –OH
lithium ions. Among all DES tested, LAA-based DES showed the best
radicals linked with C = C were predicted as more reactive sites. The
performance for metal reductive extraction, which agreed with the re­
structure C = C-OH is reactive in many occasions due to strong attractive
sults from IP calculation and CV test. According to results in this study,
force of the oxygen atom on the C = C electron cloud. Such character­
the reducibility is more dominant than acidity for metal leaching effi­
istics leads to a reversible structure transformation of C = C-OH into
ciencies directly by organic acids because LAA (pKa = 4.17) has weaker
C–C = O with hydrogen atoms linked to the oxygen being released as
acidity than CA (pKa = 3.13) and PTA (pKa = 1.7). It was because that
hydrogen ions. The Fourier Transform Infrared spectra (FT-IR) of the
although different in acidity, the selected organic acids in this study
DES in different reaction stages were shown in Fig. 2b for verification.
were all capable of metal leaching with enough hydrogen ions. There­
The broad strong band at around 3437 cm− 1 is referred to –OH
fore, the influence from releasing hydrogen ions was not as distinct as
stretching vibration of inter-molecule hydrogen bonds. The presence of
reducibility for those selected organic acids. Consequently, the reduc­
–OH was also shown by the band at around 1083 cm− 1, regarded as
ibility of organic acids became the critical point in metal leaching
hydroxyl linked with carbon. The small band at 2959 cm− 1 is associated
behavior. The results convincingly demonstrate that an integration of IP
with the stretching vibration of C = C, while the band at 1691 cm− 1 is
calculation with CV test is able to provide guidance for selection of
linked to C = C bending vibrations. Small bands around 1744 cm− 1
reductive acid in both theoretical and experimental aspects. This
correspond to O–C = O stretching vibrations in the molecule [20,63].

5
Y. Hua et al.
The spectra of synthesized DES were a combination of ChCl and LAA
without visible variations. This spectral feature indicates the absence of
chemical reaction during the DES synthesis, suggesting simple inter­
molecular hydrogen bond in DES. After the leaching, the band at around
1636 cm− 1 became more evident. Such band manifests the existence of
C = O [52,64]. The variation in spectral feature before and after reaction
suggests the generation of C = O. During the leaching reaction, one of
the –OH lost an electron to become –OH+. The intermediate ionic group
–OH+ has a strong attractive force on the electron cloud of C = C. As
displayed in Fig. 2c, the C = C in the LAA molecule was broken and one
of the carbon atoms formed a C = O radical. The other –OH became
highly reactive and tended to form another C = O radical with the linked
oxygen atom. The generation of O = C–C = O pushed another –OH to
ionize, resulting in a second hydrogen ion and electron. As a result, the
LAA released two hydrogen atoms to become L-dehydroascorbic acid.
Such reaction is known as the oxidation of LAA [50,52].
3.3. Optimization of leaching condition
To determine the applicability of leaching agent, the leaching tests
were conducted using ChCl-LAA DES. The effect of different leaching
conditions such as water contents, leaching temperature and time, and
solid to liquid ratio (S/L) on leaching efficiency was investigated. Metals
leached out from the cathode materials were quantified by ICP-MS.
Despite many different chemical properties, Co and Li showed
similar trends of leaching, which was due to the layered structure of
NCM and LCO (see Fig. S6). In such case, metals were extracted into the
solution almost simultaneously as soon as the oxygen was taken away.
Fig. 3a and 3b show a notable increase in leaching efficiency with
increasing the content of water, with around 90% of Co and Li being
leached out at room temperature and water: DES molar ratio above 4.
The water was proven to be vital for leaching reactions by reducing the
viscosity of solvent to accelerate the transport of reactants and products
of leaching. The presence of water molecules also improved the
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Chemical Engineering Journal 436 (2022) 133200
Fig. 3. Efficiency of Co and Li leaching from
NCM111 by ChCl-LAA DES under various
conditions. ChCl, LAA and water were mixed
at certain molar ratios. Error bars represent
standard deviation (three replicates or
more): a) Effect of different temperatures
and water contents on leaching efficiency of
Co (leaching time 1 h, S/L = 0.1 g/2.5 g) ; b)
Effect of temperature and water content on
leaching efficiency of Li with water content
showing a more significant impact than
temperature (leaching time 1 h, S/L = 0.1 g/
2.5 g); c) Effect of leaching time on leaching
efficiency of Co and Li, showing a higher
leaching efficiency at a shorter leaching time
(temperature 50℃, ChCl : LAA :
H2O = 2:1:6, S/L = 0.1 g/2.5 g); d) Com­
parison of leaching efficiency of Co and Li by
ChCl-LAA DES from different spent lithium
ion battery cathode materials (temperature
50℃, time 1 h, ChCl : LAA : H2O = 2:1:6, S/
L = 0.1 g/2.5 g).
generation of hydrogen ions which could destroy the layered structure of
cathode material and release metal ions by taking away the oxygen.
However, the water amount should not be too much in order to preserve
the DES characteristics. In the DES environment, the organic acid could
be maintained in high concentration in the liquid phase by the eutectic
effect from ChCl. The temperature also showed an important impact on
leaching efficiency of both Co and Li. Higher temperature is anticipated
to enhance the rate and collision frequency of different molecules,
resulting in increasing reaction rate and hence higher leaching efficiency
for a given leaching time. Similar trends were found for the leaching of
Mn and Ni, as shown in Fig. S7.
Fig. 3c shows a close to 90% of leaching efficiency for both Co and Li
within 15 min, indicating a fast initial leaching reaction rate. Similar
trend was shown in Fig. S8 for Mn and Ni. The reaction reached the
highest leaching efficiency at around 60 min. The leaching kinetics was
further investigated and discussed in Supplementary Note 1, with the
fitting parameters of different kinetic models being given in Figs. S9-
S11. The fitting results show the chemical reaction and liquid mass
transfer process being more influential at lower temperatures, while
solid surface diffusion being more prevailing at higher temperatures.
Activation energies of leaching reactions were calculated using Arrhe­
nius equation to be 28.12 kJ/mol for Li, 34.49 kJ/mol for Mn, 27.37 kJ/
mol for Co and 24.91 kJ/mol for Ni as shown in Fig. S12. These acti­
vation energy values were lower than corresponding activation energies
obtained in previous DES and LAA aqueous solutions [50]. Effect of solid
to liquid ratio in Fig. S13 showed a maximum leaching efficiency at S/
L = 1/25 was suitable. In summary, a suitable DES composition was
identified to be ChCl : LAA : H2O = 2:1:6, with an optimal leaching time
of 1 h at 50℃ and S/L = 1/25 to achieve over 98% of Co, Ni and Mn
leaching with over 96% of Li leaching.
To verify the feasibility of ChCl-LAA DES in battery recycling, the
spent cathode material was extended to LiNi0.5Co0.2Mn0.3O2 (NCM532),
LiNi0.6Co0.2Mn0.2O2 (NCM622) and LCO. The leaching efficiency of Co
and Li under the optimal condition mentioned earlier is shown in
Y. Hua et al. Chemical Engineering Journal 436 (2022) 133200

Table 1 efficiency over 75% was obtained for LCO and other NCM. It is evident
Leaching efficiency of metals by DES and related hydrometallurgical processes. that the leaching efficiency affected by properties of raw materials such
Extracting Reagent Samples Conditions Efficiency (%) as chemical composition and particle sizes. Nevertheless ChCl-LAA DES
was proven to be effective for multiple kinds of spent LIBs.
ChCl : LAA : H2O NCM 30℃, 1 h, 0.1 g/2.5 g 88.4Li, 89.7 Mn, 88.9
DES Co, 85.4 Ni Table 1 summarizes leaching efficiencies of metals by different DES
50℃, 1 h, 0.1 g/2.5 g 96.2Li, 99.3 Mn, 98.1 or organic acids and shows clear advantages of organic acid–water
Co, 98.9 Ni containing DES including the ChCl-LAA DES studied here over ChCl-EG
ChCl : EG DES [19] LCO 160℃, 24 h, 0.1 g/5g 28.4Li, 23.8 Co DES or ChCl-Urea DES. Metals were leached out by hydrous organic acid
180℃, 24 h, 0.1 g/5g 89.8Li, 50.3 Co
220℃, 24 h, 0.1 g/5g 94.1 Co
DES at much lower temperatures and less leaching time, which was
ChCl : EG DES[20] NCM 90℃, 24 h, 0.5 g/25 g Removal of Cu much more environmental friendly. The reaction temperatures in hy­
160℃, 20 h, 0.5 g/25 g Selective 90 Co, 10 Ni drous DES were also lower than LAA and CA aqueous solutions, which
ChCl : Urea DES LCO 160℃, 12 h, 0.1 g/5g 61.2Li, 64.2 Co was attributed to higher concentrations of reductant in DES. Moreover,
[21]
Fig. S14 compared leaching efficiencies between DES and aqueous so­
180℃, 12 h, 0.1 g/5g 94.7Li, 97.9 Co
ChCl : CA : H2O LCO 40℃, 1 h, 20 g/L 93Li, 98 Co lutions. It could be found that after a cycle, the recovered DES was still
DES [34] able to reach a higher leaching efficiency than LAA aqueous solution.
ChCl : PTA : H2O LCO 90℃, 15 min, 0.05 g 94 Co The reason was that in the DES environment, the unreacted LAA was
DES [35] LCO / g HBD able to be preserved in liquid phase throughout the whole process. Ac­
LAA[50] LCO 70℃, 20 min, 25 g/L 94.8 Co, 98.5Li
LAA [51] NCM 75℃, 1.5 h, pulp 96.3Li, 95.6 Mn, 94.8
cording to the 1H NMR spectra in Fig. S15, no obvious changes of DES
density 6% Co, 95.6 Ni were observed before leaching and after recovery. The result further
CA + H2O2 [65] NCM 90℃, 1 h, 20 g/L 99.1Li, 95.2 Mn, 99.8 confirmed the sustainability of recovered DES.
Co, 98.7 Ni

Fig. 3d. Compared with NCM111, a slightly lower metal leaching

Fig. 4. Analysis of spent NCM111 cathode material before leaching (a), transition metal oxalate recovered (b) and product calcined at 1000℃ (c): 1) SEM image; 2)
EDX mapping image of Co in spent NCM111 cathode material, showing a uniform distribution; 3) XRD pattern; and 4) XPS spectra of Co 2p3/2.

7
Y. Hua et al.
3.4. Metal recovery
To demonstrate the recovery of metals from spent lithium batteries
by ChCl-LAA DES, transition metals and Li were precipitated and
recovered by oxalate acid (H2C2O4) from water and ethanol phases,
respectively. The X-ray diffraction (XRD) pattern and SEM image of
Li2C2O4 are shown in Fig. S16. The XRD pattern of the product matches
well with standard Li2C2O4, indicating an effective recovery of Li2C2O4
from ethanol.
As for transition metals, Co was included here while Mn and Ni were
given in supplementary information. Detailed discussions were given in
Supplementary Note 2. Fig. 4a1-4a3 confirmed the crystal structure of
NCM111 and uniform distribution of Co in spent lithium-ion cathode
materials before leaching [66]. Fig. 4b1 and 4b2 show uniform distri­
bution of Co in the round-shaped precipitates. Mn and Ni showed the
similar uniform distribution as shown in Figs. S17 and S18. The XRD
pattern in Fig. 4b3 revealed the existence of (Co, Ni, Mn)C2O4⋅2H2O,
demonstrating the effective recovery of metals. The XPS spectra of Co in
Fig. 4a4 and 4b4 confirmed the reduction reaction of Co during the
metal leaching process (from Co3+ 779.8 eV to Co2+ 777.6 eV), indi­
cating the need of Co reduction for its extraction from spent NCM
cathode [67–68]. The calcination was performed aiming to further
confirm the existence of transition metals and the possibility for material
regeneration. Fig. 4c1-4c3 show that the calcination merely decom­
posed the oxalate while metals remained as oxides. Mn was found to
combine with Co to form Co2MnO4 while Ni existed as separate phase of
NiO. Such result was also supported by the results of EDX mapping
shown in Fig. S19. After calcination, Co was shown in Fig. 4c4 to be
oxidized to Co(III) which was the valence in the new cathode material.
Combined with the information of XPS result in Figs. S20-S23, varying
valences of transition metals after calcination indicate the regeneration
of new cathode material with proper treatment of recovered products.
The theoretical calculation of IP has been introduced to predict
reducibility of acid in this study. The results of CV test verified the
feasibility of IP calculation in organic acid system. Based on IP predic­
tion and CV test, the selected hydrous ChCl-LAA DES proved to have
excellent extracting performance for various kinds of spent LIBs under
mild conditions. Since IP and electrochemical activity are self-
characteristics of the reductant, such method is expected to be appli­
cable to treatment of other electronic wastes involving redox reactions.
Traditional hydrometallurgy for recycling of spent LIBs faces challenges
of water pollution and not able to fully use the leaching agent. DES has
been shown to be a kind of green and multi-cycle feasible leaching agent.
Therefore, the DES is anticipated to be an effective agent for the treat­
ment of other electronic heavy metal wastes with high efficiency and
environmental friendliness.
4. Conclusion
IP has been used for assessing the redox potential in various appli­
cations, yet it has not been considered in recycling of spent LIBs. In this
study, we demonstrate application of IP for theoretically predicting the
reducibility of acids and the molecular reaction mechanism as applied to
recycling of lithium-ion batteries. The CV test was applied into organic
acid system for verification of IP prediction. The experimental results
were also in good agreement with the IP prediction and CV test that
lower IP with negative oxidation electrical potential represents a
stronger reducibility, indicating that IP calculation and CV test are both
applicable in hydrous organic acid DES design for recycling spent LIBs.
The ChCl-LAA DES selected based on the prediction from the
calculated IP proved to be effective for metal leaching from spent battery
cathode for both NCM and LCO types. By adjusting reaction parameters,
leaching efficiency of Co and other metals could reach over 96% under
mild leaching conditions. Valuable metals were recovered by adding
precipitant, and in-situ regeneration of new cathode material was shown
to be possible. DES can provide even better leaching efficiency and
8
Chemical Engineering Journal 436 (2022) 133200
higher productivity than traditional acid aqueous solutions. DES is also
more sustainable for multiple cycles to fully consume the reductant. As a
result, chemical waste and water pollution can be reduced. DES based on
theoretical IP prediction and CV test not only provides an alternative
pathway for recycling of spent LIB with high productivity and minimal
negative environmental impact, but such method is also anticipated to
provide possibility for green treatment of various electronic heavy metal
wastes.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We gratefully acknowledge supports from the National Natural Sci­
ence Foundation of China [22008104, 51772141]. This work was also
supported financially by Shenzhen Science and Technology Innovation
Committee [JCYJ20200109141642225, JCYJ20200109141437586,
KQJSCX20180322151507786]. Additional support was Basic and
Applied Basic Research Foundation of Guangdong Province
(2021A1515010148), Guangdong Province Universities and Colleges
Pearl River Scholar Funded Scheme 2018.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2021.133200.
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