Environmental Research 239 (2023) 117393

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Environmental Research
journal homepage: www.elsevier.com/locate/envres

A simple green method for in-situ selective extraction of Li from spent

LiFePO4 batteries by synergistic effect of deep-eutectic solvent and ozone
Shujie Tang, Ziyue Yang, Mei Zhang, Min Guo *
State Key Laboratory of Advanced Metallurgy, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing, 100083, PR
China

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

Keywords: Efficient and clean extraction lithium (Li) from spent LiFePO4 batteries (LIBs) still remains a challenge. In this
Spent LiFePO4 batteries paper, a green deep eutectic solvent (DES) based on ethylene glycol (EG) and choline chloride (CC), combined
FePO4 with ozone (O3) from air source, realized highly selective leaching Li from LiFePO4 in situ for the first time. The
LiCl
influence of experimental parameters on Li and Fe leaching efficiencies (ηLi, ηFe) were studied by orthogonal and
Reusability
Green recovery
single-factor tests, and ηLi ≥ 92.2% while ηFe ≤ 1.6% were obtained under the optimal conditions (6 h, 20 g/L,
8EG:1CC, 40 ◦ C). The impurity Fe in the filtrate was completely precipitated as amorphous FePO4⋅3H2O after
heating (150 ◦ C, 0.5 h), achieving a pure Li-solution. The leaching mechanism elucidated that the synergistic
effect (acidification, replacement and oxidation reaction) between the DES and O3 determined the phase tran­
sition of Li and Fe, promoting the efficient selective extraction of Li and in-situ separation of Fe (FePO4). The
average ηLi and ηFe were separately 85.4% and 2.0% after ten cycles of the 8EG:1CC, indicative of its’ excellent
reusability. Meanwhile, LiCl was recovered from the filtrate. This process avoided the use of strong acid/alkali
and discharge of waste water, providing fresh perspectives on the green recovery of spent LiFePO4 batteries.

1. Introduction hydrogen bond acceptor (quaternary ammonium salt, organic alcohol,

Currently, LiFePO4 batteries (LIBs) with low cost and more safety,
has become the first choice in electric vehicles field (Wang et al., 2022).
However, the actual recovery rate of the spent LIBs is less than 5%,
resulting in serious environmental pollution and resource waste (Wu
et al., 2022). Thus, recycling spent LIBs is imperative, especially the
cathode active materials (LiFePO4) containing precious metal Li (Chaves
et al., 2021). Compared with the high energy-consumed pyrometallur­
gical method, hydrometallurgical process using solvents of H2SO4,
acetic acid, etc., could realize selective extraction of Li by adding
additional oxidants (H2O2, Na2S2O8, NaClO, etc.) (LiFePO4(s) +
Oxidant + H+ = Li+ + FePO4(s) + Reduced product) (Kumar et al.,
2022; Li et al., 2020; Mahandra and Ghahreman, 2021; Liu et al., 2022;
Gong et al., 2022), but inevitably produce more refractory wastewater.
Achieving a high-purity Li-solution by selectively dissolving Li while
minimizing Fe leaching still remains challenge. Developing a green se­
lective recovery process, especially designing a green leaching solvent is
the key issue.
Deep eutectic solvents (DESs) as a kind of novel green solvents,
consist of hydrogen bond donor (carboxylic acid, alcohol, etc.) and
etc.), possessing the ability to dissolve metal oxides and avoid discharge
of refractory wastewater, thus having been applied in extracting metals
from various resources (Hansen et al., 2021; Yuan et al., 2022; Zhu et al.,
2023). In 2019, Tran et al. utilized DES (2 mol ethylene glycol and 1 mol
choline chloride, 2EG:1CC) firstly to realize efficient dissolution of
LiCoO2, and more than 90% of Li and Co were leached (220 ◦ C, 24 h) by
coordination and reduction ability of Cl− (Tran et al., 2019). Since then,
various types of DESs were formed by optimizing the reducibility,
acidity, coordination ability and viscosity of solvents, including
1CC:2urea, 1CC:1oxalic acid, etc., for extraction of the specific cathode
active materials (LiCoO2, LiNi1/3Co1/3Mn1.3O2, LiMn2O4, etc.) under
more mild conditions (Chang et al., 2022; Lu et al., 2021; Morina et al.,
2022; Tang et al., 2022a, 2022b; Wang et al., 2020; Yang et al., 2023).
Unfortunately, it is difficult to provide oxidation environment required
for selective leaching of LiFePO4 in the above DESs just because of their
reductive components (carboxylic acid, amide, alcohol, etc.), and
notably, no effort has been taken on recovery of LiFePO4 using any DES
up to now. Therefore, developing a green leaching system utilizing the
synergistic effect of DES and oxidant, is of great significance for the
in-situ selective extracting Li from LiFePO4.

* Corresponding author.
E-mail address: guomin@ustb.edu.cn (M. Guo).

https://doi.org/10.1016/j.envres.2023.117393
Received 5 June 2023; Received in revised form 30 August 2023; Accepted 11 October 2023
Available online 12 October 2023
0013-9351/© 2023 Elsevier Inc. All rights reserved.
S. Tang et al.
In contrast with the complex electrochemical-assisted DESs leaching
process for Au/Ag ore and Cu/Zn alloys etc. (Abbott et al., 2015),
selecting some low-cost oxidants, for an example, O3, may be able to
establish a simple and efficient process. The O3 produced by simple
ozone generator using air as resource, could avoid regional restriction
and reduce the process cost (Mubarok et al., 2018). The introduction of
strong oxidizing O3 (Eθ(O3/O2) = 2.076) into the DESs leaching system,
could remove the toxic organic by-product (aldehydes, dioxin, etc.) in
the leaching process, achieving the goal of green chemistry (Sun et al.,
2022). In this oxidative environment, how to choose the appropriate
DES compositions to match the oxidant is the key problem.
The design of DES system with a certain acidity is an important
prerequisite to accelerate the highly leaching, but, the choice of acid-
based DESs would cause the risk of Fe excessive dissolution (Yadav
et al., 2020; Yang et al., 2017). This contradiction may be solved by
selecting strong oxidant (O3) and DES component containing hydroxyl
(-OH) that could be partially oxidized to produce acid (-COOH). But,
there was no report on using the synergistic effect of oxidant and DES to
realize the selective leaching of LiFePO4. Thus, non-acid based DES
containing alcohol components would be an ideal choice. DESs (EG:CC)
with low toxicity and low viscosity (57 cp) containing –OH met the
above requirements and could be used as candidate leaching system
(Zhang et al., 2012).
In this study, clean and simple in situ selective extraction of Li from
spent LIBs cathode active materials (LiFePO4) was firstly realized by
synergy of leaching medium (DESs, EG:CC) and strong oxidant (O3).
Some physicochemical properties of the as-prepared DESs were char­
acterized to demonstrate their potential leaching ability. The effects of
different leaching factors on Li and Fe leaching efficiencies (ηLi, ηFe)
were explored by orthogonal experiments and single factor experiments
to obtain the optimal leaching conditions. Moreover, the cyclic stability
of the as-prepared DES was also tested. The mechanism of the synergistic
leaching process of LiFePO4 was elucidated. In addition, the trace im­
purities Fe in the filtrate were removed by heat treatment (150 ◦ C, 0.5
h), achieving a pure Li-containing filtrate, then LiCl was obtained
subsequently.
2. Experimental section
2.1. Reagents and materials
Choline chloride (C5H14ClNO, CC, analytical grade) and LiFePO4
(analytical grade) were purchased from Aladdin Reagent (Shanghai)
Limited Company. Ethylene glycol (EG, C2H6O2, analytical grade) was
purchased from Sinopharm Chemical Reagent Limited Company. Fig. S1
gives the atom model of EG and CC containing plenty of –OH that could
be transformed to –COOH by oxidation reaction, and the as-prepared
DESs would possess certain acidity for efficient selective Li from
LiFePO4 under oxidizing atmosphere (O3). LiFePO4 batteries
(LFP18650-150) were purchased from TaoBao (China) Software Limited
Company, discharged in saturated NaCl solution and disassembled
manually to obtain cathode electrode, and the active materials was
obtained by ultrasonic treatment of cathode electrode. According to the
characterization of LiFePO4 from pure reagent and spent LIBs in the
Supplementary materials (Fig. S2), both the two cathode active mate­
rials were LiFePO4 with orthorhombic phase (JCPDS: 81–1173)
composing of irregular particles.
In the whole leaching process, two ozone generators using pure O2
and air respectively, both were from Guang Zhou Quan Ju Ozone
Technology Limited Company, and their models and performance pa­
rameters were shown in Table S1. For each generator, the gas flow was
constant and the O3 productivity could be adjusted at 0 to maximum
value. The as-used O2 (≥99.9%) was purchased from Beijing Huan Yu
Jing Hui Jing Cheng Gas Technology Limited Company.
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Environmental Research 239 (2023) 117393
2.2. Experimental procedure
The whole experimental flowsheet (Fig. 1) consisted of preparation
process of DESs, leaching process and Li recovery process.
Preparation of DESs: EG and CC were mixed in a sealed glass
container at different mole ratios (MEG:CC, 2:1, 4:1, 6:1, 8:1), stirred by
magnetic force at 50 ◦ C until a clear and transparent solvent was ob­
tained. After that, the as-prepared DESs were stored in a dryer at room
temperature.
Leaching process of LiFePO4: Firstly, the DESs with different MEG:CC
(2:1, 4:1, 6:1, 8:1) and LiFePO4 powder were added into a three necked
flask with a certain solid-liquid ratio (RS/L, 10, 20, 30, 40, 50 g/L). After
the system was heated to the target temperature (T, 30, 40, 50, 60 ◦ C)
using water bath heating device with magnetic stirring (60 rpm), O3
with different O3 productivity (0, 2, 10 g/h) was introduced into the
system through a glass tube for a period of time (t, 1–8 h). Subsequently,
the filtrate was obtained by filtrating the slurry, and the residue was
washed three times with deionized water and absolute ethanol, dried at
90 ◦ C for 6 h. All leaching experiments were conducted three times to
ensure the accuracy of the results.
The orthogonal experiment was designed to explore the effects of
experimental factors (t, RS/L, MEG:CC and T) on ηLi and ηFe, as shown in
Table S2. Based on the orthogonal experiment results, t (1–8 h), RS/L (10,
20, 30, 40, 50 g/L), MEG:CC (2:1, 4:1, 6:1, 8:1) and T (30, 40, 50, 60 ◦ C)
were selected to obtain optimal experimental conditions by single-factor
experiment. Moreover, the untreated filtrate was reused for extraction
process to enrich Li solution under optimal conditions. In order to
reduce cost, the pure reagent LiFePO4 and air source ozone generator
(16 L/min of gas flow, 2 g/h of O3 productivity) was used in orthogonal,
single factor and reusability of DES experiment, and the air humidity
was about 10–60%.
In-situ recovery process of Li: The as-obtained filtrate was heated to
150 ◦ C by oil bath and held for 0.5 h. After that, the trace impurity Fe in
the filtrate was entirely precipitated as canary yellow solid. Pure Li-
containing solution was obtained by filtrating, and as-obtained precip­
itated was washed three times with deionized water and absolute
ethanol, dried at 90 ◦ C for 6 h. Then, the pure Li solution was placed in a
flask, treated (220 ◦ C, 2 h) with the self-made vacuum distillation device
(Fig. S3) for recycling EG. The residual Li-bearing residue was calcined
(600 ◦ C, 1 h) to remove organic phase, obtaining the solid product
(LiCl).
2.3. Characterization method
The phase structure of cathode active materials, residues and prod­
uct, etc., were characterized using X-ray diffractometer (XRD, Rigaku D/
max-2500, Japan) with 40 kV and 300 mA Cu Kα radiation at a scanning
rate of 10◦ /min.The scanning electron microscope (SEM, Zeiss Supra-55,
Germany) at an operating voltage of 10 kV, was used to observe the
micromorphology. The melting point of as-prepared DESs was deter­
mined by the differential scanning calorimeter (DSC, Netzsch 200 F3,
Germany), and all samples placed in aluminum hermetic crucibles were
cooled to − 150 ◦ C before heating up to room temperature at a heating
rate of 10 ◦ C/min. The Fourier transform infrared spectrometer (FTIR,
Nicolet iS10, America) with a range of 400–4000 cm− 1, was used to
analyze the functional groups of EG, CC, DESs, filtrate and residue, etc.
The NMR spectrometer (NMR, Bruker Advance III 400 MHz,
Switzerland) was used to obtain the solution 1H nuclear magnetic
resonance spectra of EG and DESs (different MEG:CC), and the external
standard (deuterium oxide, D2O) was placed in the capillary glass tube
(1.0 mm) to avoid the effect of D2O on the sample characteristic peaks of
NMR. The dynamic shear rheometer (DSR, Haake MARS60, America)
with a heating rate of 10 C/min was used to measure the viscosities
◦
changes of DESs in the range of 25–110 ◦ C. The phase composition of
LiFePO4 and as-removed impurity from filtrate, were analyzed through
thermogravimetry (TG, Netzsch STA 449 F5 Jupiter, Germany) at a
S. Tang et al.
Fig. 1. The flowsheet of recovering Li from spent LIBs cathode active material (LiFePO4).
heating rate of 10◦ /min, and the as-tested temperature range was
25–800 ◦ C. The absorbance spectra of the as-obtained filtrate under
optimal leaching conditions in the range of 200–500 nm, were collected
by the double beam UV–vis absorption recording spectrophotometer
(UV–Vis, TU-1901, China) at a scan rate of 2 nm/s. Significantly,
8EG:1CC that of ozone treatment (40 ◦ C, 6 h) was the reference solution.
Inductive coupled plasma - optical emission spectrometer (ICP-OES,
Varian, America) was used to determine the metal ions concentrations
(Li, Fe) in the filtrate, and all the samples were dissolved in 2% HNO3
solution before analysis. The leaching efficiencies (ηm) of metal ions
from LIBs cathode active materials were calculated according to Eq. (1).
Moreover, the leaching residue (FePO4) or product (LiCl) was dissolved
in a 1 M HNO3 solution at 90 ◦ C for 6 h. Then, Li and Fe contained in
FePO4 or LiCl were calculated through determining the metal ions
contents in the solutions.
C m Vf
ηm = × 100% (1)
Mc Wm
where, Cm is the metal ion (Li, Fe) concentration in the filtrate, g/L; Vf is
the volume of the filtrate, L; Mc is the mass of cathode active material, g;
Wm is the mass fraction of metal in cathode active material, wt.%.
3. Results and discussion
3.1. Physicochemical properties of the as-prepared DESs
The key property of DESs is that its melting point is lower than any of
its components and it is a liquid phase at room temperature, which is
generally determined by DSC curves of solvent (Zhang et al., 2012).
Since 2006, green DES based on EG and CC has been widely utilized due
to low toxicity of the components (Abbott et al., 2006). However, it was
not until 2010 that the eutectic point of EG:CC was verified to be
2EG:1CC, at which point the lowest melting point was − 66 ◦ C (Shahbaz
et al., 2010). This study only listed the experimental results, and did not
give the detailed test analysis process, which could not provide reference
for designing other novel DESs.
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Environmental Research 239 (2023) 117393
Fig. 2a presents the DSC curves of as-prepared DESs with different
MEG:CC. During the heating process of the solvents (MEG:CC = 4:1 to 8:1)
from − 120 ◦ C to 30 ◦ C, the endothermic peak from the second-order
phase transition, and the successive exothermic/endothermic peaks
from the first-order phase transition appeared, illustrating that the sol­
vents underwent glass transition (glass phase to molten phase), crys­
tallization (molten phase to crystalline phase) and melting (crystalline
phase to liquid phase) processes in turn, which agreed well with that in
1CC:2Urea system. The peak-max temperatures of melting processes
(Mp, oC) were considered to be the phase transition point of DESs (Yuan
et al., 2019). With the EG proportion increasing, the corresponding Mp
decreased from − 29.2 ◦ C (4EG:1CC), to − 24.5 ◦ C (6EG:1CC) and
− 22.9 ◦ C (8EG:1CC), lower than those of pure EG (− 12.9 ◦ C) and CC
(303 ◦ C) (Smith et al., 2014), which proved that the solvents were
typical DESs and remained stable as liquids at room temperature for a
long time (Inset in Fig. 2b). Based on the above data, the relevant binary
phase diagram of EG:CC systems was presented in Fig. 2b. The compo­
nents of the eutectic point was 4EG:1CC instead of 2EG:1CC reported in
the literature (Ibrahim et al., 2019), and the Mp of this system was about
− 29.2 ◦ C mainly due to hydrogen bonds formation between EG and CC.
Moreover, unlike the previous phenomena, the DSC curve of 2EG:1CC
showed a weak exothermic peak at about 0.72 ◦ C, which meant the
solvent was unstable and would crystallize at room temperature. This
was also confirmed by the appearance of floccule in 2EG:1CC (Inset in
Fig. 2b) standing still for 1 week at room temperature (from − 10 to
10 ◦ C).
Generally, hydrogen bonds formed between EG and CC lead to a
decrease in the melting point of as-prepared DES, which could be
elucidated by the shift or disappearance of the corresponding functional
groups characteristic peaks in FTIR spectra, as shown in Fig. 2c. The O–H
(~3300 cm− 1) used for acidification reaction with O3 still existed in
DESs with different MEG:CC, suggesting that as-formed solvent still had
the ability to efficiently and selectively recover LiFePO4. Moreover,
some characteristic peaks attributed to CC disappeared, such as the
tensile vibration peak of O–H (3219 cm− 1) and the characteristic peak of
hydroxyl or amino group (N–H stretching and C–N+ anti-symmetric
S. Tang et al. Environmental Research 239 (2023) 117393

Fig. 2. (a) DSC curves, (b) binary phase diagram of DESs with different MEG:CC; (c) FTIR spectra and 1H NMR spectra of pure EG, CC and corresponding DESs. Inset in
Fig. 2(b): digital photos of DESs with different MEG:CC at room temperature for a period of time.

stretching) (1100-850 cm− 1), etc., indicating strong interaction 3.2. Selection of oxidant
occurred between EG and CC (Delgado-Mellado et al., 2018). Taking EG,
CC and 4EG:1CC for examples, the stretching vibration characteristic During the leaching process of LiFePO4, the strong oxidizing envi­
peaks of O–H (EG) showed a blue shift (from 3296.3 to 3300.1 cm− 1) ronment ensures the structural stability of LiFePO4 and avoids the for­
and the characteristic peak of Cl− (CC) disappeared (629.7 cm− 1) after mation of soluble Fe3(PO4)2, which is also the key to selective Li
formation of DES, proving the formation of hydrogen bond between Cl− leaching (Kumar et al., 2022). More importantly, some components (e.
(CC) with strong electronegativity and O–H (EG) (Jafari et al., 2022; g., alcohol) of the DESs could be oxidized to produce a small number of
Shafie et al., 2019). In addition, both the C–O tensile vibrational peaks protons (Eq. (2)), ensuring the rapid leaching of LiFePO4.
(from 1082.9, 1032.2 cm− 1 to 1083.3, 1033.7 cm− 1) and the ammonium Table 1 listed the effects of different oxidizing atmospheres from
salt feature peaks (from 952.2 to 953.6 cm− 1) showed slight blue shift different ozone generators (Table S1) on ηLi and ηFe under the same
(Gajardo-Parra et al., 2019). Similar changes in the absorption bands leaching conditions. Results indicated that O3 (Eθ(O3/O2) = 2.076) had a
were also seen in 6EG:1CC and 8EG:1CC, which confirmed the formation significant effect on ηLi, while O2 (Eθ(O2/H2O) = 1.229) had almost no
of hydrogen bonds between EG and CC. effect, which may be because the oxidation capacity of O2 was not
1
H NMR test can give more direct evidence for the existence of enough to oxidize the components of DESs and produced enough pro­
hydrogen bonds between EG and CC, as shown in Fig. 2d. The chemical tons to achieve efficient selective leaching of LiFePO4 as depicted in Eq.
shift (δ) value of –OH in DESs with different MEG:CC all decreased (3). In addition, ηFe maintained at a low level (<1.7%), which meant that
compared to pure EG (5.30 ppm). This was ascribed to that the hydrogen the ozone atmosphere ensured the structural stability of LiFePO4, thus
bonds formation between Cl− (CC) and –OH (EG) reduced the electron avoiding excessive Fe dissolution, and achieving the efficient selective
cloud densities around the hydrogen atom (-OH) and weakened the leaching of Li.
shielding effect of the electron cloud. With MEG:CC decreasing from 8:1 to
3(RCH2 OH) + 2O3 = 3(RCOOH) + 3H2 O (2)
4:1, the δ moving distance of –OH peak increased from 5.02 to 4.87 ppm,
indicating the hydrogen bond strength enhancement between CC and
2LiFePO4 (s) + O3 + 2H+ = 2Li+ + 2FePO4 (s) + H2 O + O2 (3)
EG. In the meantime, the –CH2 (EG) peak at 3.64 ppm also showed the
similar δ change trend due to the high electron absorption capacity of
Cl− , eg., from 3.64 ppm in pure EG to 3.50 ppm in 4 EG: 1CC, further Table 1
confirming the generation of high-intensity hydrogen bonds between EG The leaching results using different oxidizing atmosphere (Leaching conditions:
and CC. 6 h, 20 g/L, 8EG:1CC, 40 ◦ C).
Low viscosity solvents have excellent mass transport and filtration Oxidizing Atmosphere ηLi ηFe H2O content of filtrate
properties, which are important for industrial applications of DESs. The (%) (%) (wt.%)
Oxidant O3 productivity (g/
viscosities of the four DESs 2EG:1CC, 4EG:1CC, 6EG:1CC and 8EG:1CC h)
at 25 ◦ C were only 45.4, 24.4, 19.9 and 18.1 cp, respectively (Fig. S4),
O2 0 0 0 0.38
significantly lower than other types of DESs (amide or organic acid Air 0 0 0.1 6.33
DESs) (Smith et al., 2014), which demonstrated that the low-viscosity O2 source 10 49.9 0.3 1.40
EG:CC systems were suitable as the leaching mediums and beneficial O3
for the leaching and separation process of the cathode active materials. Air source 2 91.9 1.7 5.64
O3

4
S. Tang et al.
Furthermore, the leaching efficiency of air source ozone atmosphere
(ηLi = 91.9%, ηFe = 1.7%) was higher than that of oxygen source O3
atmosphere (ηLi = 49.9%, ηFe = 0.3%) though the latter possessed higher
O3 productivity and concentration (2 L/min, 10 g O3/h, about 83.3 mg
O3/L). As can be seen from Table 1, the water contents of the leaching
solutions obtained from the oxygen source and air source were 1.40 wt%
and 5.64 wt%, respectively, which were caused by oxidation of the
hydroxyl component of DESs (Eq. (2)) and the water in air source. The
increased water contents enhanced the proton activity and reduced the
system viscosity. So, the air source O3 atmosphere (16 L/min, 2 g O3/h,
about 2.1 mg/L) was selected as suitable oxidant from the point of view
of process cost and metal leaching performance.
3.3. Selective leaching of Li and in-situ recovering Fe from LiFePO4
3.3.1. Effects of leaching parameters on the extraction of Li and Fe from
LiFePO4
Using air source O3 atmosphere as oxidant, an orthogonal experi­
ment was designed to explore the effect sequence of leaching time, RS/L,
MEG:CC and leaching temperature on the ηLi and ηFe, as shown in
Table S2. Results indicated that leaching time had the greatest influence,
followed by RS/L, MEG:CC and leaching temperature. Moreover, ηFe was
maintained at a low level (<0.6%) all the time due to the strong
oxidation potential of the leaching system. The optimal parameters of
each factor were identified and used as the initial conditions (6 h, 20 g/
L, 6EG:1CC, 50 ◦ C) to explore the effects of different factors on the ηLi
and ηFe.
Fig. 3a illustrates the influence of leaching time on ηLi and ηFe. It can
be seen that ηLi increased rapidly from 15.1% to 89.7% as the leaching
time increasing from 1 h to 6 h, then slightly increased to 90.1% at 8 h.
Meanwhile, ηFe only showed a gradual upward trend from 0.3% to 1.3%,
which may be ascribed to the slight distortion of LiFePO4 structure after
Li+ deintercalation. Therefore, 6 h was selected as the optimal leaching
time. In addition, the influence of RS/L on ηLi and ηFe was shown in
Fig. 3b. The ηLi showed a trend of increasing first and then decreasing
with the RS/L from 10 to 50 g/L, reaching the maximum 89.7% at 20 g/L.
When the RS/L was less than 20 g/L (e.g., 10 g/L), the ηLi was slightly
reduced (84.0%), which may be due to the low RS/L resulted in the
decrease of slurry density, then caused the strong splash of liquid and
Fig. 3. Effects of experimental factors of (a) time, (b) RS/L, (c) MEG:CC, and (d) temperature on ηLi and ηFe from LiFePO4.
5
Environmental Research 239 (2023) 117393
affected the leaching process. However, when the RS/L was greater than
20 g/L (e.g., 20–50 g/L), ηLi decreased from 89.7% to 52.8%. The con­
stant ozone concentration and flow rate added in the DES system were
not enough to ensure the sufficient leaching reaction of LiFePO4. In the
meantime, as for the ηFe, with RS/L increasing from 10 g/L to 50 g/L, ηFe
decreased from 10.7% to 0.1%, which was probably due to the incom­
plete leaching reaction of LiFePO4. Thus, 20 g/L was the optimal RS/L.
The MEG:CC and temperature had minor effects on ηLi and ηFe shown
in Fig. 3c–d, which was consistent with the results of orthogonal
experiment. With the MEG:CC increasing from 2:1 to 8:1, ηLi increased
from 89.7% to 93.5%, while ηFe always remained at a low level (1.4%–
1.8%). Therefore, the 8EG:1CC was appropriate. In addition, the ηLi
reached maximum value (94.7%) at 40 ◦ C and decreased slightly to
91.4% at 30 ◦ C, mainly because of the lower temperature reducing the
viscosity of DES (Fig. S4) and reaction rate of leaching process (Eqs. (2)
and (3)). Even at 60 ◦ C, ηLi also decreased to 90.1%, which may be due to
the higher temperature resulting in evaporation of water in the DES
system to decrease the reaction rate. While, as for ηFe, when the tem­
perature was lower than 50 ◦ C, the ηFe kept stable around 1.4%–1.7%
but 3.3% at 60 ◦ C. The relatively high temperature might strengthen the
oxidation of O3, thus destroying the structure of LiFePO4 and causing the
excessive dissolution of Fe. Therefore, 40 ◦ C was chosen as the optimal
leaching temperature.
Based on the above analysis, the optimal leaching conditions were
determined under an air source ozone atmosphere as follows: 6 h, 20 g/
L, 8EG:1CC, 40 ◦ C, at which, the ηLi reached 94.7%, and ηFe was only
1.6%. The process realized the in situ selective leaching of Li from
LiFePO4, and the residue was in the form of FePO4 (Fig. S5a).
Moreover, 92.2% of Li and 1.5% of Fe was leached from spent LIBs
cathode active materials (LiFePO4) under optimal conditions, and the
content of Li and Fe in residue were 0.26 wt% and 37.89 wt%, respec­
tively. As shown in Fig. 4a, the XRD diffraction peaks of residue agreed
well with the standard diffraction peaks of (Mn, Fe)PO4 with ortho­
rhombic phase (JCPDS: 37–0478), and there was no diffraction peaks of
LiFePO4. The results inferred that the residue should be FePO4 with
lattice distortion, realizing efficient selective leaching Li. The micro
morphology of the corresponding residue is consistent with that of
LiFePO4. They both consisted of irregular particles, as illustrated in
Fig. 4b and Fig. S2d. Fig. 4c gives the XPS spectra of Fe 2p in LiFePO4
S. Tang et al.
Fig. 4. (a) XRD pattern and (b) SEM image of residue, (c) XPS spectra of Fe 2p in spent LIBs cathode active material and corresponding residue, (d) UV–vis absorption
spectrum of filtrate. Inset in (a, c): Digital photo of residue and filtrate from spent LIBS under optimal conditions.
and corresponding residue. It can be found that the main peaks of Fe
2p1/2 and Fe 2p3/2 change from 725.3 eV and 711.0 eV to 726.2 eV and
712.3 eV, respectively, before and after leaching of LiFePO4, which in­
dicates that all Fe2+ ions in LiFePO4 were oxidized to Fe3+. Three ab­
sorption peaks appeared at 264, 326 and 363 nm in the UV–vis
absorption spectrum of the filtrate (Fig. 4d), which were generated by
charge transitions in complex FeCl−4 and FeCl+ 2 as well as FeCl3 (aq),
formed by Fe(III) in high concentrations of ligand (Cl− ), respectively
(Liu et al., 2006). The above result for the XRD pattern and UV–vis
spectrum of the residue and the filtrate, were in agreement with the
results for pure reagent LiFePO4 (Fig. S5), which declared that the
leaching system based on EG:CC and O3 had excellent applicability for
the recovery of spent LiFePO4 batteries.
Although ηFe was only 1.5–1.6% under the optimal conditions, the
removal of impurity Fe was necessary for obtaining a high-purity Li-
containing solution. In the 8EG:1CC system, only heating the filtrate to
150 ◦ C and holding for 0.5 h to precipitate canary yellow solids, could
achieve impurity Fe removal and avoid the use of strong alkali to adjust
the pH value of filtrate in previous studies (Kumar et al., 2022). Results
showed that the concentration of Fe in filtrate decreased from 104 ppm
to 3.6 ppm with color changing from yellow to colorless (Fig. S6) after
separating the solids, confirming that the pure Li-containing solution
was obtained. In order to explore the impurity removal mechanism, the
as-separated canary yellow solid was intensively characterized as shown
in Fig. S7, and this amorphous material was finally determined to be
FePO4⋅3H2O after analysis in the Supplementary materials. The stability
constant of FePO4⋅3H2O at high temperature greater than that of FeCl3−x
x
(x = 1, 2, 3) in 8EG:1CC may be the key reason for impurity Fe removal
according to Eq. S1.
3.3.2. Selective oxidative leaching mechanism by synergistic interaction of
DES and O3
LiFePO4 possesses stable olivine structure with FeO6 octahedra and
PO4 tetrahedra. In the process of selective leaching of LiFePO4 using
6
Environmental Research 239 (2023) 117393
ozone atmosphere in DESs medium, in order to achieve selective
leaching of Li and ensure the existence of Fe in the form of solid FePO4,
the leaching system must meet the following conditions: (1) the as-
prepared DESs should have a suitable concentration of H+, which not
only ensures that Li + can be replaced from the layered structure of
LiFePO4, but also prevents excessive dissolution of Fe2+ in the FeO6
octahedron. (2) At the same time of Li+ is replaced, the Fe(II) in LiFePO4
should be immediately oxidized to Fe(III), forming a FePO4 precipitate.
This requires the leaching system to have a suitable acidity and oxida­
tion potential (Chen et al., 2022). Fig. 5 presents the reaction process of
selective leaching Li from LiFePO4 by EG:CC combined with O3,
including the hydroxyl group (-R–CH2–OH) being oxidized by ozone to
carboxylic group (-R-COOH) (Synergetic acidification reaction), the
substitution reaction of Li+ in LiFe(II)PO4 by leaching of free H+ ions
(Replacement reaction), and the oxidation process of intermediate
product H–Fe(II)PO4 being oxidized by ozone to Fe(III)PO4 (Oxidation
reaction).
In the first stage (synergetic acidification reaction), the partial
-R–CH2–OH from EG and CC was oxidized to form minor -R-COOH and
H2O by O3 (Eθ(O3/O2) = 2.076), as depicted in Eq. (2). The increased
water content of DES (8EG:1CC) to the filtrate (oxygen source O3 at­
mosphere) from 0.14% to 1.40%, confirmed the effective and feasibility
of the reaction (Eq. (2)). Moreover, FTIR spectrum of the filtrate showed
(Fig. S8) that a tensile vibration characteristic peak attributed to C––O
appeared at 1636.3 cm− 1, further confirming the -R-COOH formation.
In the second stage (replacement reaction), Li+ ions (76 pm) in Li–Fe
(II)PO4 was replaced by free H+ ions (38 pm), entering into the solvent,
which was also the reason why acid system could accelerate Li leaching
(Jin et al., 2022). At the same time, the intermediate product H–Fe(II)
PO4 was produced according to Eq. (4). However, due to the small H+
ion radius (38 pm) in the displacement into H–Fe(II)PO4, the interme­
diate was very unstable and may result in excessive Fe dissolution.
In the third stage (oxidation reaction), H–Fe(II)PO4 (Eθ(Fe3+/Fe2+)
= 0.771) was easily oxidized by ozone (Eθ(O3/O2) = 2.076) to produce
S. Tang et al.
Fig. 5. Schematic diagram of the leaching mechanism of Li from LiFePO4 in DES with O3.
Fe(III)PO4 with stable structure (Eq. (5)). This was confirmed by the
presence of partially dissolved Fe (III) in the filtrate (Fig. 4d).
In a word, in the leaching process of LiFePO4, the free H+ ions
generated by the synergistic effect of ozone and hydroxyl group (DESs)
selectively displaced Li+ in Li–Fe(II)PO4, while the formed H–Fe(II)PO4
was oxidized to Fe(III)PO4 with stable structure under ozone atmo­
sphere. Finally, the selective leaching of Li and the efficient separation of
Fe were realized.
LiFe(II)PO4 + H+ = Li+ + HFe(II)PO4 (4)
2HFe(II)PO4 + O3 = 2Fe(III)PO4 + O2 + H2 O (5)
3.3.3. Reusability of the as-prepared DES
Thanks to the high concentration of components, DES should have
excellent recycling performance, which is also one of its important ad­
vantages as a new green solvent (Morina et al., 2022). Fig. 6 illustrate
the ηLi and ηFe at ten cycles under the optimum leaching conditions (6 h,
20 g/L, 8EG:1CC, 40 ◦ C). The ηLi fluctuated at 72.5–96.1% with an
average value of 85.4%, meanwhile the ηFe varied among 0.6–5.1% with
an average value of 2.0%, indicating good reusability of 8EG:1CC. The
above fluctuations in leaching values may be mainly attributed to
changes in H2O content in the DES system due to the changes in air
humidity. The H2O content of the 1st cycle and the 10th cycles were
5.64 wt% and 4.53 wt%, while the corresponding ηLi were 96.1% and
82.3%, respectively, which also confirmed that the water content in the
leaching system had an important influence on the ηLi. Furthermore,
after 10 cycles, the concentration of Li and Fe were 7.5 g/L and 1.4 g/L,
Fig. 6. ηLi and ηFe at ten cycles under the optimum conditions (6 h, 20 g/L,
8EG:1CC, 40 ◦ C).
7
Environmental Research 239 (2023) 117393
respectively.
3.4. Recycle of EG and recovery of Li from the filtrate
During the distillation process of the pure Li solution, approximately
95% of the EG was recovered and all of Li remained in the residue. As
shown in Fig. 7a, the characteristic peaks of the functional groups (O–H
and C–O) of the as-recycled EG were basically consistent with those of
the pure reagent EG, indicating that it could be reused for the synthesis
of new DESs. The characteristic peak of the C– – O, which originally
belonged to the filtrate, was changed from 1636.3 cm− 1 to 1652.7 cm− 1
(as-recycled EG), which was due to the fact that the C– – O functional
group was no longer subject to hydrogen bonding interactions of CC. The
residue was calcined at 600 ◦ C for 1 h to obtain LiCl (JCPDS:74–1972)
with cubic phase (Fig. 7b). Due to the hygroscopic nature of LiCl, some
characteristic peaks attributed to LiCl(H2O) (JCPDS:73–1273) with
tetragonal phase also appeared in the XRD pattern (Fig. 7b). The con­
tents of Li and Fe in the product (LiCl) were 12.26 wt% and 0.03 wt%,
which was consistent with the XRD test (Fig. 7b). The whole treatment
process is simple and clean, avoiding the use of strong-alkali/precipitant
and the generation of secondary wastewater, which has important
practical significance.
3.5. Comparative analysis of recovery processes for LiFePO4
The comparison of selective leaching and recovery of Li from
LiFePO4 using traditional and the proposed methods was summarized in
Table 2. In conventional processes, a weak acidity and a strong oxidizing
environment are necessary for the selective leaching of Li (Jing et al.,
2019). The separation of impurity Fe and the recovery of Li from the
filtrate consumed large amounts of strong alkali (NaOH) and precipi­
tating agents (Na3PO4 and Na2CO3), which led to discharging alkaline
wastewater. Moreover, no effort was taken on the recovery of leaching
solvent.
Fortunately, in selective leaching Li based on DES, the solvent (DES,
EG) could be recovered, and the subsequent steps of removing impurity
Fe and recovering Li substances only required distillation and heating
operations. Consequently, the recovery process in this study consumed
fewer reagents and did not discharge wastewater. And the detailed
calculation analysis of reagent and energy consumption costs between
this study (DES + O3) and typical traditional processes (H2SO4 and
H2O2) (Li et al., 2017) in the supplementary materials (Table S3 and
Table S4), further proved that the method proposed in this study was
more economical and environmentally friendly.
4. Conclusion
In this paper, the green DESs (EG:CC) realized the efficient and se­
lective in-situ leaching Li from spent LIBs cathode active materials
S. Tang et al. Environmental Research 239 (2023) 117393

Fig. 7. (a) FTIR spectrum of as-recycled EG, filtrate and pure reagent EG, (b) XRD pattern of as-obtained product.

original draft. Ziyue Yang: Data curation, Investigation. Mei Zhang:

Table 2
Writing – review & editing. Min Guo: Methodology, Resources, Data
Comparison of selective leaching and recovery of Li from LiFePO4 by traditional
curation, Supervision, Funding acquisition.
and the proposed methods.
Selective leaching of Li Remove Fe Recovery of Li Ref

Leaching system Precipitant Precipitant and Declaration of competing interest

product

H2SO4, H2O2, 60 ◦ C, 2 h, NaOH Na3PO4, 65 ◦ C, 2 h, Li et al. The authors declare that they have no known competing financial
ηLi = 96.85%, ηFe = Li3PO4 (2017) interests or personal relationships that could have appeared to influence
0.027% the work reported in this paper.
H2SO4, Na2S2O8, 60 ◦ C, NaOH, Na2CO3, 100 ◦ C, Li et al.
1.5 h, Fe2(SO4)3 Li2CO3 (2020)
ηLi = 97.53%, ηFe = Data availability
1.39%
NaHSO4, H2O2, 65 ◦ C, – Na2CO3, 95 ◦ C, 10 h, (Gong Data will be made available on request.
15 min, Li2CO3 et al.,
ηLi = 99.84%, ηFe = 2022)
0.048% Acknowledgements
Citric acid, H2O2, 2 h, NaOH, 70 ◦ C Na2CO3, 95 ◦ C, Li et al.
ηLi = 99.35%, ηFe = Li2CO3 (2019)
This work was financially supported by the National Natural Science
3.86%
Acetic acid, H2O2, 50 ◦ C, NaOH Na2CO3, 95 C,◦
Yang
Foundation of China (No. U1810205).
0.5 h, Li2CO3 et al.
ηLi = 95.05%, ηFe<1% (2018) Appendix A. Supplementary data
8EG:1CC, O3, 40 ◦ C, 6 h, Distillation, Distillation, 220 ◦ C, 1 This
ηLi>92.2%, ηFe<1.6%, 150 ◦ C, 0.5 h h, Calcination, 600 ◦ C, study
1 h, Supplementary data to this article can be found online at https://doi.
LiCl org/10.1016/j.envres.2023.117393.

(LiFePO4) for the first time under the O3 atmosphere. Results revealed
that O3 atmosphere containing H2O could greatly promote the leaching
of Li, and more than 92.2% of Li and less than 1.6% of Fe were leached
under the optimal leaching conditions (6 h, 20 g/L, 8EG:1CC, 40 ◦ C).
The leaching mechanism confirmed that the synergetic acidification
reaction between –OH (DES) and O3 played an important role in the
replacement reaction of Li+, and the strong oxidizing O3 atmosphere led
to the formation of structurally stable FePO4 (Oxidation reaction),
avoiding the dissolution of Fe. The 8EG:1CC system possessed excellent
cycle extraction ability, and the average value of ηLi and ηFe reached
85.4% and 2.0% respectively in ten cycles. Heating filtrate at 150 ◦ C for
0.5 h, realized the in-situ removal of trace Fe in the form of FePO4⋅3H2O.
Moreover, the as-obtained pure Li-containing solution was treated by
vacuum distillation unit to recover 95% EG and LiCl. The entire recovery
process was performed without the use of strong acid/alkali and
discharge of secondary wastewater, providing a green and simple new
method for the extraction of Li and separated Fe from spent LiFePO4
LIBs.
Credit authorship contribution statement
Shujie Tang: Data curation, Formal analysis, Visualization, Writing –
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