Desalination 546 (2023) 116188

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Desalination
journal homepage: www.elsevier.com/locate/desal

Highly selective and efficient lithium extraction from brines by

constructing a novel multiple-crack-porous LiFePO4/FePO4 electrode
Wenhua Xu a, Dongfu Liu b, Xuheng Liu b, Dezhi Wang a, Lihua He b, c, *, Zhongwei Zhao b, c, *
a
School of Materials Science and Engineering, Central South University, Changsha 410083, China
b
School of Metallurgy and Environment, Central South University, Changsha 410083, China
c
Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Changsha 410083, China

H I G H L I G H T S

• Prepared multiple-crack-porous microstructures electrode with high hydrophilicity

• The current density of the multiple-crack-porous electrode can reach 20–30 A⋅m− 2.
• An industrial-scale EDIs remains 27 mg⋅g− 1 adsorption capacity over 1000 cycles.

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

Keywords: The rapid development of new energy vehicles stimulates the demand for lithium, and lithium extraction from
LiFePO4 brine has attracted much attention. Unfortunately, brines have high impurity content, high viscosity, and high
Porous electrode mineralization, while conventional electrodes are highly hydrophobic, which makes brine mass transfer difficult.
Brine
Herein, a novel electrochemical deintercalation/intercalation system (EDIs) with high hydrophilicity and
lithium extraction
Electrochemical intercalation/De-intercalation
permeability is constructed. The new system first introduces hydroxyl-rich PEG into PVDF by blending to modify
the electrode hydrophilicity. Moreover, NaCl and carbon fibers are used as porogenic and structural reinforcing
agents to increase channels for brine mass transfer and strengthen the electrode, respectively. The formed
multiple-crack-porous microstructures electrode exhibits excellent hydrophilicity, the contact angle of the
electrode decreases from 124◦ to 82.3◦ . Compared with the unmodified electrode, the lithium extraction speed
increases nearly three times, and the current efficiency increases from 62 % to 92 %. Moreover, an industrial-
scale EDIs is designed, and the capacity of the LiFePO4 is maintained at about 27 mg (Li) g− 1 (LiFePO4) with
the coulombic efficiency of 98.5 % over 1000 cycles at a high current density of 30 A m− 2. The proposed pseudo-
3D structured electrode with hydrophilic properties has broad application potential for lithium extraction from
salt laker brine.

1. Introduction
Since the rapid development of electric vehicles, electronic devices
and electrochemical energy storage, the demand for lithium has
increased significantly over the past few decades. Up to now, the global
consumption of lithium was estimated to be about 57,700 tons of lithium
content in 2019, which was increased by 18 % from 49,100 tons of
lithium content in 2018, and the proportion of Li-ion batteries increased
from 56 % to 65 % [1,2].
The booming international lithium market has also brought new
opportunities and challenges to the extraction metallurgy of lithium.
And lithium extraction from the salt-lake brines, which accounts for 70
% of the global lithium reserves, receives increasing attention [3].
Today, global lithium salt production has gradually undergone a stra­
tegic shift in lithium extraction from ore to salt-lake brines owing to its
low costs, environmental friendliness and abundant reserves [4,5].
Nevertheless, brine is a complex solution system, besides the low con­
centration of Li+, it contains a much higher concentration of cognate
alkali metal cations Na+, K+ and resemble alkaline earth Mg2+, which
makes it difficult to extract lithium directly. Especially for lithium
extraction from the high Mg/Li ratio brines has been a decades-long
technical challenge [6,7].

* Corresponding authors at: School of Metallurgy and Environment, Central South University, Changsha 410083, China.
E-mail addresses: helihua@csu.edu.cn (L. He), zhaozw@csu.edu.cn (Z. Zhao).

https://doi.org/10.1016/j.desal.2022.116188
Received 13 July 2022; Received in revised form 22 September 2022; Accepted 16 October 2022
Available online 29 October 2022
0011-9164/© 2022 Published by Elsevier B.V.
W. Xu et al.
To release the huge potential of lithium resources in brines, various
methods like solar evaporation, absorption, solvent extraction, electro­
dialysis, and membrane separation methods have been developed [6,8].
Generally, lithium can be effectively extracted via the solar evaporation
method from the brines with the Mg/Li ratio lower than 6, but about 50
% lithium in the initial natural brine will remain in the evaporative
crystalline salts during the evaporation process, especially for the
treatment of high Mg/Li ratio brines [9]. Electrodialysis and membrane
separation methods are environment-friendly [10,11], but the brines
need to be diluted with a large quantity of water, and what's worse, it
should be desalted Na+ and K+ via sola evaporation due to the ignorable
separation efficiency between the monovalent cations Li+ and Na+ & K+.
While as for the solvent extraction method, the emulsification phe­
nomenon happens occasionally because of the high viscosity of the
brines. Although centrifugal extraction technology can remit it to some
extent, the dissolution of organic extractant into brines will bring po­
tential pollution and harm to the environment. Ion-sieve absorption has
been considered as one of the promising approaches for lithium
extraction from brines since its high selectivity, low cost, and non­
toxicity. However, it suffers from serious capacity fading and great
challenges for the preparation of a high capacity and mechanical
strength absorbent. Moreover, large volumes of chemicals are needed
for regenerating the active materials.
To address the challenge of lithium extraction from brines, we pro­
posed an Electrochemical De-Intercalation/Intercalation system (EDIs)
based on the principle of Rocking-chair Lithium-ion batteries for lithium
extraction by using LiFePO4/FePO4 or LiMn2O4/Li1-xMn2O4 (0 < x < 1)
electrode couple as lithium acquirer [12–17]. More Recently, various
new electrochemical lithium extraction systems like λ-MnO2/NiHCF
[18], λ-MnO2/AC [19], λ-MnO2/ppy [20,21], LFP/I [ [22]], NMMO/AC
[23], LFP/NaFP [24] have been developed based on the similar concept.
Although all these methods exhibited good selectivity, low energy
consumption, they almost suffer from the same problem, i.e. low current
density (3–5A⋅m− 2) [25].
As for an electrochemical process, a higher current density often
means higher unit capacity, lower production costs, and less investment.
As mentioned above, an increase of impurity ions concentration results
in higher mineralization and viscosity of the brine. In particular, the
viscosity tends to be higher for salt-lake brines with high Mg/Li ratios
[26,27]. Meanwhile, the high mineralization and viscosity of the brine
also pose a great challenge for lithium extraction selectively. Since
serious cathodic polarization will happen at a high current density, and
impurity ions like Na+ will intercalate into the structure of cathode
materials, accompanied by the decrease of lithium selectivity. What's
worse, excess intercalation of Na+ will cause the crystal structure
destruction of the materials, corresponding with the cyclic performance
degradation of the materials [28–30]. Moreover, the strong hydropho­
bicity of conventional electrodes is another challenge for lithium
extraction selectively. The carbon black and PVDF used in conventional
electrodes are both strongly hydrophobic substances, which will hinder
the wetting of brine to the electrode. In summary, reducing the current
density becomes a trade-off measure for lithium extraction efficiently.
Therefore, improving the mass transfer in the lithium extraction process
can effectively increase the current density.
In this study, we showed a PEG (a polymer containing a large number
of hydroxyl groups) modified porous LiFePO4/FePO4 electrode for
lithium extraction from high Mg/Li and Na/Li brines. The PEG-modified
porous LiFePO4 electrode can effectively wet the electrode surface with
brine (the contact angle is 82.3◦ , which is lower than 90◦ ). In the same
way, pore-microcrack-forming and carbon fiber reinforcing combined
method can provide multi-channels for brine mass transfer, and
dramatically reduce concentration polarization and cathodic over­
potential. Based on the above measures, the modified electrode can
reduce the intercalated sodium side reaction. Meanwhile, the prepared
pseudo-3D structure electrode can provide abundant mass transfer
channels and more reactive sites, and the lithium extraction speed is
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Desalination 546 (2023) 116188
increased nearly 3 times. Moreover, the capacity of the LiFePO4 can be
maintained at about 27 mg (Li) g− 1 (LiFePO4) for 1000 cycles with great
lithium selectivity and high current density. And a designed industrial-
scale EIDs lithium extraction system by using porous-LiFePO4/FePO4
as electrodes exhibited good working stability and outstanding cycle life
at a high current density of 30 A m− 2.
2. Experiment
2.1. Electrode synthesis
PVDF-LiFePO4 electrode and the de-lithiation FePO4electrode pre­
pared as our previous work [15], but the current collector changed to
brushed titanium mesh.
Preparation of PEG-modified porous LiFePO4 electrode: Firstly,
added PVDF and PEG to the N-methyl-2-pyrrolidone (NMP) solution in
proportion, and stirred vigorously under vacuum at 50 ◦ C until PVDF
was completely dissolved (about 8 h). Added the LiFeO4/C and acety­
lene black to the mixed adhesive solution. After stirring for 6 h, the
finished slurry (solid content controlled at 40–45 %) was obtained by
adding pore-forming agent NaCl and short-cut carbon fiber (2–3 mm)
and continuing to stir for 1 h. Second, coated the slurry on the titanium
net by scraping method and placed the wet electrode in a 2 × 2 × 2 m3
oven for blast drying (dried at 70 ◦ C for 5 h and then at 100 ◦ C for 8 h).
Finally, the dried-electrode was immersed in water until the pore-
forming agent NaCl dissolved and removed, and the finished PEG-
modified (PEG-1000) porous LiFePO4 electrode was obtained. The
addition ratio (mass ratio) of each substance was, LiFePO4:acetylene
black:PVDF:carbon fiber:PEG:NaCl = 7:2:1:0.07:0.14:3.5. The PEG-
modified porous FePO4 electrode was obtained by the electrochemical
de-lithiation method [15].
2.2. Lithium extraction
The prepared LiFePO4 and FePO4 electrodes were used as cathode
and anode, respectively, IONAC MA-3475 was used as the anion-
selective membrane. For the laboratory experiments, the size of both
electrodes was 17 × 20 cm2 with the LiFePO4 coated surface density of
85 mg cm− 2. The cathode chamber and the anode chamber were filled
with 1.3 L brine and 1.3 L 10 g L− 1 KCl (supporting electrolyte). In the
process of lithium extraction, the anode or cathode of the electrode was
connected to the positive terminal of the multimeter, and the negative
terminal of the multimeter was connected to the saturated calomel
electrode (SCE) to determine the anodic and cathodic potentials during
the reaction, respectively.
For the extraction of lithium via industrial-scale EDIs devices, the
size of the electrodes was 80 × 100 cm2 with the LiFePO4 coated surface
density of 200–300 mg cm− 2 (double sides). The EDIs device comprised
15 pieces of PEG-modified porous LiFePO4 and 15 pieces of PEG-
modified porous FePO4 electrodes, and the volume of the brine and
anolyte was 500 L and 1000 L respectively. The separation process was
carried out under a constant current density of 20–30 A m− 2 until the
cell voltage reached the cutoff value of 0.25–0.3 V. At the end of each
cycle, the positive and negative terminals of the power supply are
switched and the position of the brine and anode solution adjusted to
continue the electrolysis for the next cycle. The whole process worked
automated by our developed Real Time Expert Intelligent Control Sys­
tem (RTEICS).
2.3. Material characterization
Cyclic voltammetry and chronopotentiometry were carried out with
Versa-STAT4 (Princeton Applied Research, America) at the scanning
rate of 0.02 mV s− 1 and current density of 0.2 mA cm− 2, respectively.
The concentration of ions was determined by ICP-AES (IRIS intrepid
XSP, Thermo Electron Corporation), and the Na/Fe and Li/Fe of the
W. Xu et al.
materials were measured by dissolving the electrode materials in aqua
regia, and subsequently measure the content of sodium, lithium and iron
in aqua regia and calculate the corresponding ratio. The crystallographic
structure of the samples was measured by X-ray diffraction (XRD:
Siemens D-500, Cu Kα radiation, λ = 1.8A◦ ) under the scan rate 2(◦ )
min− 1 and step 0.02 . The STEM images and EELS/EDS spectra were
◦
performed in a CEOS probe corrected FEI Themis TEM at an electron
accelerating voltage of 300 kV with a probe convergence angle of 17.8
mrad, a spatial resolution of 0.08 nm, and probe current of ~30 pA for
STEM imaging and ~100 pA for EELS/EDS acquisition. The 3D Ultra-
deep field microscopic images were performed via Digital
MicroscopeVHX-7000 (KEYENCE, America). Contact angle measure­
ments were carried out by dropping a deionized water droplet on the
surface of the electrodes (Drop shape analysis system, Phoenix 300,
Korea).
3. Results and discussion
The schematic diagram of the EDIs for lithium extraction is shown in
Fig. 1. In the electrochemical system of “LiFePO4 (anode)|supporting
electrolyte|anion-selective membrane|brine|FePO4 (cathode)”, LiFePO4
and de-lithiated FePO4 are used as anode and cathode, respectively.
Under the action of external electric field, Fe (II) in the anode LiFePO4
will be oxidized (the anode is gradually transformed into FePO4), and
Li+ in LiFePO4 will be de-intercalated and enriched in the anolyte
(LiFePO4-e = Li++FePO4). At the same time, Fe (III) in the cathode
FePO4 will be reduced and Li+ ions will be intercalated into FePO4 to
form LiFePO4 (Li++e + FePO4 = LiFePO4). Since FePO4 is obtained by
de-lithiating of LiFePO4, the Li vacancy allows the presence of positive
monovalent with the similar radius to Li+(90 pm). Therefore, the diva­
lent Mg2+ (86 pm) in the brine are difficult to intercalate due to charge
mismatch and strong coulomb effect, and Na+(116 pm) and K+ (152 pm)
are also because the ionic radius is much larger than that of Li+, thus
achieving the purpose of selective lithium extraction from salt-lake
brines. Meanwhile, the anion-exchange membrane can prohibit the
passing of Li+ from the anode chamber to the cathode chamber, and Li+
can be enriched in the supporting electrolyte. At the end of a cycle,
exchanging the cathode electrode and anode electrode, and then restart
the electrolytic process, lithium can be extracted continually from the
brine and concentrated in the supporting electrolyte.
For the EDIs or other electrochemical lithium extraction technolo­
gies, the core is the selectivity of lithium and lithium extraction effi­
ciency. Although LiFePO4 has a one-dimensional Li+ transport channel
for the selectivity extracting of lithium, this inherent advantage also
faces serious challenges for treating brines. In general, the cathodic
polarization is relatively mild at a lower current density. Similarly, when
LiFePO4/FePO4 is used for lithium extraction, it also shows good
selectivity at low current densities. Although the lithium concentration
Fig. 1. Schematic diagram of the EDIs for lithium extraction.
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Desalination 546 (2023) 116188
decreases leading to a gradual increase of cathode overpotential, Li+-
intercalation potential remains above 0.05 V (vs. SCE) even when
dealing with a solution of Li 0.35 g L− 1 (Fig. S1A). Compared to the high
current density situation, the Li+-intercalation cathode potential de­
creases to 0.0 V (vs. SCE) at 10 A m− 2 and − 0.2 V (vs. SCE) for 20 A m− 2
in a Li 7 g L− 1 solution (Fig. S1B). Compared with the Cyclic voltam­
metry test (Fig. S2) in the salt-lake brine (brine compositions listed in
Table S1), it can be found that the potential threshold for Na+-interca­
lation has been reached at 20 A m− 2. Unfortunately, the Na+-interca­
lation not only affects the selectivity to lithium, but also has a potential
threat to the LiFePO4 cyclic performance.
The causes of cathodic polarization at high current densities are
manifold. In general, the choice of the electrode materials for lithium
extraction from the salt-lake brines mostly comes from lithium-ion
batteries, and the preparation of the electrode is almost no exception.
The conventional way is to dissolve the adhesive PVDF in a NMP solu­
tion, then add the cathode materials (such as LiFePO4 or LiMn2O4) and
conductive agent (like acetylene black, Carbon black) in proportion, mix
thoroughly and coat on a current collector, and then vacuum dry. It is
worth noting that the electrolytes used for the Lithium-ion battery are
almost organic systems, such as LiPF6/EC/DMC electrolytes. To reduce
the interfacial impedance between electrode materials and electrolytes,
and improve the electrochemical performance of the electrode mate­
rials, a good wettability between the electrode materials and the organic
electrolyte is required. Fortunately, PVDF itself is lipophilic, so it pro­
vides good electrochemical compatibility to the battery system. How­
ever, completely different from the organic working environment of
lithium batteries, lithium extraction from salt lakes is an aqueous solu­
tion environment, and the electrodes used for lithium extraction from
the salt-lake brines should have good hydrophilicity rather than hy­
drophobicity. In addition, to increase the lithium adsorption capacity
per unit area, a more conventional operation is to increase the amount of
active material coating per unit area to increase the reaction area.
However, a higher coating density means a thicker electrode, which
seriously hinders the mass transfer of high viscosity brine inside the
electrode, thus reducing the adsorption capacity and current density.
Therefore, the current coating density of electrodes is almost maintained
at 10–30 mg cm− 2, or even lower.
Hence, to improve the competitiveness of EDI lithium extraction
systems, it is necessary to reduce the cathode overpotential at high
current densities. In this work, we approached this challenge with an
“hydrophilic-porous electrode preparation” strategy. Fig. 2 shows the
schematic of the process for the preparation of hydrophilic-porous
electrodes. PEG was introduced into PVDF by blending to modify the
hydrophilicity of the electrode, and NaCl solid and short-cut carbon fiber
was added as pore-forming and structural reinforcing materials to
strengthen the liquid mass transfer inside the electrode and the struc­
tural strength of the electrode plate. In addition, a “low-temperature
pretreatment & high-temperature drying” process was adopted to form
evenly distributed cracks on the surface of the electrode and the inside,
which can provide a secondary mass transfer path for the solution
outside the NaCl pore-making.
Fig. 3A showed the SEM image of the conventional PVDF-LiFePO4
electrode (coating density 85 mg cm− 2 after drying) without adding
porogenic agent, PEG, and short carbon fiber. Although crisscrossed
irregular cracks distribute on the surface of the electrode, the depth of
these cracks is relatively shallow, and the electrode is in a dense state
(Fig. 3B). Worse still, the surface NMP evaporates too fast during the
drying process, resulting in the PVDF dissolved in the NMP gradually
diffusing from the inside of the electrode to the outside of the electrode
with the NMP, thus forming a PVDF cladding layer on the surface of the
electrode. Due to the existence of this PVDF cladding layer, the electrode
plate was hydrophobic (contact angle 124◦ ), which makes the wetta­
bility of the electrode material poor. As for the PEG-modified porous
LiFePO4, the electrode hydrophilicity significantly improved by intro­
ducing PEG to blend with PVDF during the slurry preparation. The
W. Xu et al. Desalination 546 (2023) 116188

Fig. 2. Schematic of the preparation of PEG-b-PVDF-modified porous LiFePO4.

Fig. 3. Surface morphology of different electrodes. (A and B) SEM images of the PVDF-LiFePO4 electrode. Insets: Contact angle images of the electrode, (C, D and F)
3D Ultra-deep field microscopic images of the PEG-modified porous LiFePO4 electrode, (E) SEM images of the PEG-modified porous LiFePO4 electrode.

contact angle of the PEG-modified porous LiFePO4 electrode decreased
from 124◦ of the conventional PVDF-LiFePO4 electrode to 82.3◦
(Fig. 3C), indicating the hydrophilicity of the electrode was significantly
enhanced by the modification via PEG blending. It is worth noting that
in addition to the effect of PEG, the improvement of the hydrophilicity of
the electrode was also closely related to the change of the electrode
surface morphology. Furthermore, crisscrossed microcracks of different
sizes formed on the surface of the porous PEG-b-PVDF-LiFePO4 electrode
(Fig. 3C). Micro-area surface SEM (Fig. 3E) of the PEG-modified porous
LiFePO4 showed that the surface consists of agglomerates of LiFePO4
particles and crisscrossed carbon fibers, accompanied by various irreg­
ular fine pores, which is completely different from the conventional
PVDF-LiFePO4 electrode. These multiple-crack-porous microstructures
substantially increased the roughness of the electrode surface, and this
microscale composite structure is crucial for obtaining wetting behavior
according to the Cassie model derived from Young's equation [31–33].
In addition, the Ultra-deep field microscopic images of the porous
LiFePO4 electrode showed that the cracks were spanned by carbon fi­
bers, and these carbon fibers played a good role of “reinforcing skeleton
and wire”. The existence of carbon fibers not only connected the
“islands” generated by the cracks, strengthened the structural strength
of the electrode and avoided the shedding of the electrode material, also
it can transfer electrons, making the voltage and current in the electrode
plate more uniform division, which is conducive to the performance of
the electrode material in different parts (Fig. 3D). Moreover, the depth
of the large cracks on the electrode surface was comparable to the
coating thickness of the electrode material (Fig. 3F), and undoubtedly
the formation and existence of these cracks provided a good path for the

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W. Xu et al. Desalination 546 (2023) 116188

mass transfer of the solution from the outside to the inside of the
electrode.
It can be expected that this PEG-modified porous LiFePO4 electrode
has good hydrophilicity and permeability as well as good structural
properties. The porous structure can improve the solution mass transfer
and increase the material reaction area, and the Li+-intercalation cath­
ode overpotential will be gratifyingly reduced.
To verify the electrochemical performance of PEG-modified porous
LiFePO4 electrode, an electrochemical lithium extraction system of
“PEG-modified porous-LiFePO4|KCl 10g L− 1|anion-selective mem­
brane|brine|PEG-modified porous-FePO4” was established. For com­
parison, another electrochemical system with PVDF-LiFePO4/FePO4
electrode pair was also assembled in the same way. The brine used for
lithium extraction experiments takes from Dangxiongcuo Salt Lake in
Tibet of China, and Table S1 lists its composition. The comparison
experiment first started with constant current electrolysis of 10 A m− 2
and switched to constant voltage electrolysis when the cell voltage
reached 0.3 V. The same experiment was done for the PEG-modified
porous electrodes, except that the current density was increased to 15
A m− 2.
Fig. 4A shows the variation of cathode/anode potential, Li/Fe and
Na/Fe molar ratio of the cathode FePO4 with electrolysis time using the
PVDF-LiFePO4/FePO4 electrode pair. During the whole lithium extrac­
tion process, the anode potential of the anode LiFePO4 electrode main­
tained at about 0.15 V (vs SCE), and the cathode potential decreased
sharply during the lithium extraction process and remained around
− 0.15 V (vs SCE) after 10 h. In addition, the Li/Fe mole ratio of the
cathode electrode material gradually increases in the first 10 h, while a
significant increase in the Na/Fe after 10 h. Hence, the whole process
can be divided into two stages, namely the first 10 h for the Li+-inter­
calation section and the later Na+-intercalation afterward, which
confirmed by the variation of lithium concentration in the brine
(Fig. 4B) and the XRD pattern of the cathode electrode materials
(Fig. 4C). According to the mole ratio of Li/Fe and Na/Fe, the effective
ion intercalating efficiency is only 62 %.
The cathodic potential (Fig. 4A) no longer decreased after reaching
− 0.15 V (vs SCE) is mainly attributed to the high Na+ concentration of
brine (about 100 g L− 1). Even though Na+ ions have embedded into the
structure of FePO4 constantly, the diffusion of a small amount of highly
concentrated Na+ is sufficient to compensate for the capture of Na ions,
which maintained the cathodic potential for Na+-intercalation at a sta­
ble plateau. However, a large amount of Na+ intercalation not only
causes a decrease in capacity but also shortens the material's cycle life.
Fig. S3 showed the cycling performance of the PVDF-LiFePO4/FePO4

Fig. 4. Lithium extraction performance with different electrodes. (A) Cathode/anode potential of PVDF-LiFePO4/FePO4 electrode pair, Li/Fe and Na/Fe molar ratio
of the cathode FePO4, (B) Li concentration of the catholyte and lithium recovery using the PVDF-LiFePO4/FePO4 electrode pair for Li extraction, (C) XRD patterns of
the initial LiFePO4 (anode), initial FePO4 cathode (obtained by delithiation from LiFePO4 and LixFePO4 cathode under different Li+-intercalation time, (D) Cathode/
anode potential of PEG-modified porous LiFePO4/FePO4, Li/Fe and Na/Fe molar ratio of the cathode FePO4, (E) Cell voltage of the lithium extraction process with
PVDF- and PEG-modified porous electrode pair, (F) XRD images of the PVDF-modified porous FePO4 cathode under different Li+-intercalation time.

5
W. Xu et al.
electrode, and the capacity decreases from the initial 27 mg g− 1 (about
103 mAh g− 1) to 20 mg g− 1 after 50 cycles, with a capacity retention of
only 74 %. Moreover, the average effective current density (current
density only for lithium intercalation) for lithium extraction of the
whole process was about 3.4 A m− 2, and even in the Li+-intercalation
stage, it was only about 6.7 A m− 2 (Fig. S4).
In contrast, the use of PEG-modified porous LiFePO4/FePO4 elec­
trode pair for lithium extraction had a better plateau at a cathodic po­
tential around 0.0 V (vs SCE) even when operating at a higher current
density of 15 A m− 2 (Fig. 4D). Under this cathode potential, Na+ is
difficult to intercalate into the FePO4 structure, which fully ensures the
selectivity of cathode FePO4 for lithium. In addition, both the Na/Fe
ratio (Fig. 4D) and the XRD pattern of cathode FePO4 (Fig. 4F) indicate
that the intercalation of Na+ can be negligible during the whole elec­
trolysis process, which provides a good guarantee for the cycling per­
formance of porous LiFePO4/FePO4 lithium extraction system (the
cycling performance will be described in detail subsequently). We can
also see that when the lithiation of FePO4 reached the level of
Li0.69FePO4, the cathode potential also reached − 0.15 V (vs SCE) fast at
this time, and then the energization mainly causes the embedding of
Na+. According to the mole ratio of Li/Fe and Na/Fe, the effective ion
intercalating efficiency is higher to 92 %.
By comparing the cell voltage of PVDF-LiFePO4/FePO4 and PEG-
modified porous LiFePO4/FePO4 electrode pairs during the lithium
extraction process (Fig. 4E), it can find that there was a lower voltage
plateau (around 0.15 V) for the PEG-modified porous electrode, which
indicates that the porous electrode had a good solution mass transfer
effect inside the electrode, and the lithium extraction reaction was
mainly controlled by the chemical reactions.
Fig. 5 showed the Scanning transmission electron microscopy
(STEM) and the corresponding Fe, P and Na EDS elemental mapping,
and Li EELS elemental mapping of the PVDF- FePO4 and porous FePO4
after lithium extraction. It was clear from the mapping that main ele­
ments existed uniformly in the particle. Na EDS elemental mapping
showed that the content of Na in the PVDF-FePO4 was significantly
higher than that in the porous one. It again confirms that the hydrophilic
and porous modification of the electrode enhances the mass transfer
diffusion on the surface and inside the electrode, which can effectively
inhibit the intercalation of Na+, which not only improves the selectivity
of FePO4 for lithium but also enables high current density operation.
Based on the above experiments, we designed and assembled an
industrial-scale EDIs device (Fig. 6 and Fig. S5) for lithium extraction
from the same Dangxiongcuo salt-lake brine. The new device used PEG-
Fig. 5. STEM and the corresponding O, P and Fe EDS elemental mapping, and Li EELS elemental mapping of the (A) PVDF-FePO4 and (B) PEG-modified porous
FePO4 after lithium extraction from the Dangxiongcuo Salt Lake in Tibet of China.
6
Desalination 546 (2023) 116188
modified porous LiFePO4 as the anode and PEG-modified porous FePO4
as the cathode after de-lithiation, and the coating surface density of the
active materials LiFePO4 was 2 kg m− 2 (double sides). Considering the
change of cathode potential shown in Fig. 4D, we used 20 A m− 2 current
density for electrolysis in the lithium extraction process, and to achieve a
rapid enrichment of lithium concentration in the anolyte, the volume
ratio of anolyte and brine during the operation was chose as 1:2.
Fig. 7 shows the variation of lithium concentration in the brine and
anolyte during the first two cycles of lithium extraction. The lithium
extraction from the high sodium carbonate type brine using the PEG-
modified porous LiFePO4/FePO4 electrode is effective. During electrol­
ysis, the lithium concentration of the lithium-rich solution (anolyte)
gradually increased and reached 2.38 g L− 1 after two cycles (further
enrichment can be expected by continuing the cycle). In the same way,
the residual lithium concentration of the brine reduced to <0.15 g L− 1 at
the end of each cycle, and the lithium recovery rate maintained at >80
%. Additionally, the EDIs method not only has good extraction and
enrichment performance for lithium, but also has an excellent retention
rate for other impurity ions, and the retention rate of the main impurity
ions, Na, K, B, CO2− 2−
3 and SO4 were as high as 97 % ~ 98 % (Table S2).
Higher lithium concentration and lower impurity ions in lithium-rich
solutions reduce the intensity and difficulty of subsequent purification
and concentration.
In general, the lithium extraction process is environmental-friendly
without the addition of any chemical reagents and the generation of
toxic and harmful substances. Since only lithium is selectively extracted
from brine, there is almost no effect on the acid-base property and
components of the brine. Therefore, salt-lake brines after lithium
extraction can be directly returned or recovered other valuable
elements.
Generally, the current density is directly related to the efficiency of
the unit device, and the cycle performance of the LiFePO4/FePO4 elec­
trode determines the reliability of the technology. For this reason, we
plan to further verify the cycle performance of EDI. To facilitate the
operation and avoid frequent replacement of brine and anolyte, we
injected the brine of Dangxiongzuo Salt Lake both into the cathode and
anode chambers, and other conditions were consistent with those in
Fig. 7.
As can be seen from Fig. 8A, the entire system exhibited excellent
cycling performance after 600 h of continuous operation, and the
Coulombic efficiency was about 98 % over 120 cycles. The same can be
seen from the charge/discharge curves of the individual processes,
where a relatively stable voltage plateau appeared around ±0.15 V for
W. Xu et al.
Fig. 7. Lithium extraction performance from Dangxiongcuo salt-lake brine
of China.
the cell voltage during lithium extraction (Fig. 8B), which was consistent
with the results of our small experiment in Fig. 4E. And the capacity was
basically maintained at 27.5 mg (Li) g− 1 when the electrode reached to a
steady state (Fig. 8C).
Undoubtedly, the above results showed that the EDIs system with
porous electrodes has excellent adaptability to carbonate-type high‑so­
dium brines, corresponding with an excellent cycling performance and
stable long-time operation conditions.
In addition to high concentrations of Na+, salt lake brines are often
accompanied by high concentrations of Mg2+. Especially in recent years,
with the exploitation of high-quality brine resources, the magne­
sium‑lithium ratio of brine is increasing year by year, which brings
increasing difficulties to the extraction of lithium. Therefore, how to
economically extract lithium from the brines with a high Mg/Li ratio is
still a pressing technical problem. In China, most of the salt lakes located
in the Qinghai-Tibet Plateau, and most of these salt lakes are of the
magnesium sulfate subtype (brine with high magnesium/lithium ratio),
and their lithium extraction still faces great challenges [6,7].
For this reason, we investigated the stability and adaptability of the
EDIs by selecting the Chinese West Taijinar brine (Li 1.84 g L− 1, Mg/Li
= 62.2, Table S3 lists its composition) as the study object. Considering
the relatively high lithium concentration of the brine, the coating sur­
face density of the porous electrode and the electrolytic current density
increased to 3 kg m− 2 (double sides) and 30 A m− 2 respectively.
It can be seen from Fig. 9A that as the electrolysis process progresses,
the lithium concentration in the electrolyte increases roughly linearly.
After two cycles, the lithium concentration in the lithium-rich solution
reached 5.4 g L− 1 (about 10 times higher than that of the industrial
7
Desalination 546 (2023) 116188
Fig. 6. Industrial-scale EDIs device.
Prepared LiFePO4, FePO4 and IONAC MA-3475 were used as
the cathode, anode and anion-selective membrane respec­
tively. In addition to the EDIs, the system is equipped with a
Real-time expert intelligent control system (RTEICs), a Power
supply system (PSs) and a Solution switching/conversion
control system (SSCCs). Moreover, the EDI device was designed
with corresponding inlet and outlet pipes for brine, anode so­
lution and wash water, and only one solution can pass through
the same pipe at the same time. To distribute the solution
evenly on the electrode surface, the solution is fed with “bot­
tom inlet and top outlet”. The detailed see also Fig. S5.
aluminum salt adsorption method), and the Mg/Li ratio decreased from
Mg/Li = 62 in the initial brine to Mg/Li = 0.5 in the obtained anolyte,
which showed good lithium selective extraction performance. At the end
of each cycle, the lithium concentration in the residual brine reduced to
about 0.2 g L− 1, and the lithium recovery rate per cycle remains above
85 %. As shown in Fig. 9B, the charging curve has a stable voltage
plateau around 0.1 V, which is 0.05 V lower than the carbonate-type
brine voltage plateau shown in Fig. 8. The lower voltage plateau is
mainly attributed to the higher lithium concentration in the West Tai­
jinar brine, and thus the cathode overpotential was lower. Furthermore,
the adsorption capacity decreased from the initial 30 mg g− 1 to 27 mg
g− 1 in the first 100 cycles and then remained essentially constant when
the electrode reached a steady state. The industrial-scale EDIs showed an
excellent cycling performance, and the Coulombic efficiency contained
98.5 % over the 1000 cycles. In addition, the retention rate of adsorption
specific capacity is up to 86.1 % (decreased from the initial 31.7 mg⋅g− 1
to 27.3 mg⋅g− 1). Similarly, even when treating the brine with a high Mg/
Li ratio, the retention of impurity ions Na, K, Mg, B, and SO2− 4 by the
EDIs can also reach about 98 % (Table S3).
Fig. 10 shows the comparison of the main technical parameters
(lithium concentration, adsorption capacity, and current density) of
different electrochemical lithium extraction systems. Despite the dif­
ference in lithium concentration of brine treated by different systems, a
comprehensive comparison showed that this work had a great perfor­
mance in both adsorption capacity and current density.
Data on lithium extraction from different electrochemical systems
were selected from the literatures [15,18–20,22,23] and [34–42], and
the rightmost two data of LFP/FP belong this work. Note that for the
non-LFP/FP and LMO/MO systems, the current density was preferen­
tially selected for the lithium intercalating process because the lithium
intercalating and de-intercalating are performed in two separate steps in
these literatures, thus the effective current density of the actual full
process (including the whole lithium embedding and detachment) were
lower [43]. The rest of the literatures that does not directly give the
current density was calculated according to the data of coating density,
adsorption capacity, electrode area, coulomb number, etc.
In particular, the core index of current density, which determines the
yield per unit area, was particularly impressive, about 5–6 times higher
than other similar technologies (this work was 20–30 A m− 2, the
traditional technologies are about 3–5 A m− 2). This not only means that
the adsorption capacity per unit electrode area and per unit time is 5–6
times higher than the existing technology, and the amount of lithium
released from the anode is also 5–6 times higher, which can realize rapid
lithium enrichment. In addition, the number of lithium extraction de­
vices can be reduced to 1/6–1/5 of the traditional one, which can
significantly reduce the investment cost of equipment, and it is
W. Xu et al. Desalination 546 (2023) 116188

Fig. 8. Electrochemical Performance of EDIs in Chinese Dangxiongcuo salt-lake brine. (A) Voltage Profiles of EDIs with PEG-modified porous LiFePO4/FePO4
electrode at 20 A m− 2, (B) The detailed voltage profiles from the 255 h to 285 h in (A), (C) Adsorption capacity and cycle performance of the EDIs.

Fig. 9. Lithium extraction from high Mg/Li ratio Chinese West Taijinar brine via EDIs. (A) Lithium concentration of anolyte and brine, and lithium recovery of the
extraction process, (B) Voltage Profiles of EDIs with PEG-modified porous LiFePO4/ FePO4 electrode at 30 A m− 2, Insert: Adsorption capacity and cycle performance
of the EDIs.

extremely important for the construction and production of the actual
production lines.
4. Conclusion
In summary, a PEG-modified and carbon fiber reinforced crack-
porous microstructures LiFePO4 electrode with high hydrophilicity
and permeability was prepared, and lithium was efficiently and
economically extracted from the salt laker brine at a high current density
via EDIs method. In addition, we designed and assembled an industrial-
scale EDIs device with the PEG-modified porous LiFePO4/FePO4 as the
electrodes for lithium extraction, and the working current density
increased from the traditional 3–5A m− 2 to 20–30 A m− 2, corresponding
with a significant increase in the capacity per unit area. Furthermore,
the EDIs shows good adaptability both for high Na and high Mg brines,
and it has an excellent cycling performance with a stable adsorption
capacity above 25 mg (Li) g− 1 (LiFePO4) and Coulombic efficiency of
98.5 % over the 1000 cycles. It is worth mentioning that the EDI tech­
nology has no strict requirements for the viscosity and mineralization of
brines, In addition, the obtained lithium-rich solution has high lithium
concentration and low impurity content, which greatly reduces both the
subsequent purification and concentration workload. We believe this
work will provide a new opportunity for lithium extraction from the salt-
lake brines with more efficient, environmental-friendly and low-cost.
CRediT authorship contribution statement
Wenhua Xu: Methodology, Investigation, Data analysis, Writing
original draft. Dongfu Liu: Validation, Investigation, Resources.
Xuheng Liu: Validation, Investigation, Resources. Dezhi Wang: Vali­
dation, Investigation, Resources. Lihua He: Writing-review and editing,
Supervision, Formal analysis. Zhongwei Zhao: Conceptualization,

8
W. Xu et al.
Fig. 10. Comparison of the main technical parameters of different electrochemical lithium extraction systems.
Supervision, Writing-review & editing, Funding.
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.
Data availability
The authors do not have permission to share data.
Acknowledgements
This work was supported by the Young Scientist Project of National
Key Research and Development Program (2022YFC2906200) and the
Major Program of National Natural Science Foundation of China
(51934010). We thank Yunze Luo for his help in electrochemical testing.
We thank Fanjie Xia and Jinsong Wu for their technical assistance and
gratefully acknowledge work of S/TEM performed at the Nanostructure
Research Center (NRC), Wuhan University of Technology.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.desal.2022.116188.
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