Renewable and Sustainable Energy Reviews 154 (2022) 111813

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Renewable and Sustainable Energy Reviews

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Electrochemical technologies for lithium recovery from liquid resources:

A review
Jiajia Wang a, Xiyan Yue a, c, Peifen Wang a, e, Tao Yu a, Xiao Du d, Xiaogang Hao d,
Abuliti Abudula a, Guoqing Guan a, b, *
a
Graduate School of Science and Technology, Hirosaki University, 1-Bunkyocho, Hirosaki, 036-8560, Japan
b
Energy Conversion Engineering Laboratory, Institute of Regional Innovation (IRI), Hirosaki University, 2-1-3, Matsubara, Aomori, 030-0813, Japan
c
Henan Key Laboratory of Materials on Deep-Earth Engineering, School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, China
d
Department of Chemical Engineering, Taiyuan University of Technology, Taiyuan, Shanxi, 030024, PR China
e
Department of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China

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

Keywords: With the rapid increase of various electronic products with lithium-ion batteries in our daily life, it is difficult to
Lithium recovery provide enough supplement to satisfy the growing demand of the market only through exploiting limited lithium
Electrochemical technologies resources on land. Consequently, lithium recovery from salt-lake brines, geothermal brines, wastewater from the
Liquid lithium resources
treatment of wasted batteries, or even sea water has attracted great interest all around the world due to the
Electrically switched ion exchange (ESIX)
Electrodialysis
abundant reserves and low price. Nowadays, various conventional technologies such as solar evaporation-
precipitation way have been widely applied to extract lithium from the aqueous solution. Unfortunately, they
are always time-consuming, uncontrollable with the secondary pollution generation. Recently, various electro­
chemical technologies have been received considerable attention for lithium recovery owing to their time-saving,
little environmental impact as well as high efficiency. Herein, progresses for lithium recovery using the elec­
trochemical technologies were outlined and discussed based on the previous studies reported in the literatures.
The principles, advantages and challenges of electrochemical technologies were critically reviewed. Even though
these methods are technically feasible, they are still limited by the poor technical maturity for the large-scale
lithium recovery. Thence, more efforts should be made in the future development of electrochemical technol­
ogies for improving lithium selectivity as well as material stability, and simultaneously reducing some energy
consumption and investing and operating costs. It could provide guidance on the development and design of
more attractive electrochemical methods for lithium recovery from liquid resources, which will contribute to
achieving the sustainable and renewable society.

1. Introduction relatively high electrochemical standard voltage of 3.045 V, and high

heat capacity in comparison to any of other metallic elements [1–4].
Lithium, as the 25th richest element in the crust of the earth and the Thus, it has been extensively used in large-capacity rechargeable bat­
lightest metal in nature, is recognized as the energy-critical element with teries, especially the Li-ion batteries [5]. With the increasing application
high energy density owing to its very low density of 0.534 g cm− 3, of lithium-ion batteries in electric vehicles, laptops, camcorders,

Abbreviations: g, Gram; mg, Milligram; kg, Kilogram; V, Volt; cm− 3, Cubic centimeter; ppm, Parts per million; wt, Weight; h, Hour; L, Liter; mmol, Millimoles; min,
Minute; ◦ C, Degrees celcius; Li, Lithium; ESIX, Electrochemically switched ion exchange; PPy, Poly-pyrrole; PSS, Polystyrenesulfonate; UPED, Unipolar pulse
electrodeposition; rGO, Reduced graphene oxide; HKUST-1, Cu-based Metal Organic Frameworks material possessing open coordinative site and stable microporous
structure, where Cu–Cu = 2.628(2) Å, Cu–OCO = 1.952(3) Å, and Cu–OH2 = 2.165(8) Å; DFT, Density functional theory; ED, Electrodialysis; R, Resistance; IEC, Ion
exchange capacity; Tmax, Operating maximum temperature; BS, Burst strength; BMED, Bipolar membrane-based electrodialysis; PP13-TFSI, N-methyl-N-propylpi­
peridium bis (trifluoromethanesulfonyl) imide; TMPA-TFSI, N, N, N-trimethyl-N-propylammonium-bis(trifluoromethanesulfonyl) imide; LMO, LiMn2O4; Cl, Chlorine;
LNCM, LiNi1/3Co1/3Mn1/3O2; NCM, Li1− x[Ni1/3Co1/3Mn1/3]O2.
* Corresponding author. Energy Conversion Engineering Laboratory, Institute of Regional Innovation (IRI), Hirosaki University, 2-1-3, Matsubara, Aomori, 030-
0813, Japan.
E-mail address: guan@hirosaki-u.ac.jp (G. Guan).

https://doi.org/10.1016/j.rser.2021.111813
Received 23 June 2020; Received in revised form 5 February 2021; Accepted 24 October 2021
Available online 29 October 2021
1364-0321/© 2021 Elsevier Ltd. All rights reserved.
J. Wang et al.
mobile/smart phones as well as other electronic devices, the demand of
lithium resources is also becoming more and more urgent [6–14]. Be­
sides, other demands for lithium in the fields such as glasses and
ceramic, grease, metallurgical industry, as well as chemical­
s/pharmaceuticals are also significantly increasing in recent years [15].
It is predicted that over 50,000 tons of lithium will be required after
2020 [16] and the production of lithium will reach triple or more from
now, accompanying by a sharp rise in its price [17], which leads to the
large gap between the market supplies and demands without driving
lithium recovery from those probable resources [2,18–20]. Obviously,
the lithium natural resource on land are not enough to satisfy the market
demands [21]. Hence, it is necessary to obtain Li from various aqueous
resources including the salt-lake brines, the geothermal brines, waste­
water generated from the wasted batteries treatment and even sea
water. It is reported that there are more than 80% of lithium resource on
the earth, equal to about 2.69 × 1010 kg, in the salt-lake brine [22,23],
which could be applied to produce approximately 60% of lithium
compounds [24,25], and bridge the huge gap between the supply and
demand as a result of the rich reserve as well as low-price [26,27].
Geothermal water also contains abundant lithium resources, which is
worth exploiting in the future. Meanwhile, a large reserve of lithium,
about 2.5 × 1014 kg, exists in sea water, which is equal to 10,000 times
of that on land but the concentration is very low [1,23]. In addition, it is
also possible to recover the lithium from solids including minerals ores,
the wasted Li-ion batteries and other Li-containing goods. At present,
lithium recovery from minerals, e.g., spodumene, requires various pro­
cess such as acid/alkaline treatment and chlorination. Generally, owing
to the high lithium content in the minerals, the recovering rate of
lithium recovery is much higher and the lithium extraction is also more
efficient than those from brines and waste batteries. However, the
lithium recovery from minerals utilizes lots of chemical reagents, which
can not only cause the environmental pollution, but also accompany
with high energy consumption and high cost. Moreover, over-mining of
lithium containing minerals may also result in environmental damage
and serious pollution. Besides, it is also full of challenge for the lithium
recovery from some minerals like the gangue with high hardness and
strong acid resistance [28]. While, the methods for the recovery of
lithium from the waste lithium-ion batteries include pyrometallurgical,
hydrometallurgical, and bio-hydrometallurgical processes. Especially,
the pyrometallurgy is currently regarded as the industrial standard for
the recycling of lithium, which can be also used to recover other metals
including cobalt and nickel in the batteries. The main issues in the
application of these traditional lithium recovery methods are the
harmful gas emissions, high energy consumption in the high tempera­
ture operation, and the loss of lithium and aluminum in the slag. While,
the bio-hydrometallurgy is considered as an environmental friendliness
and cost-effective process, however, from a kinetical point of view, it is
not favorable. Hydrometallurgy is also an efficient,
environmentally-friendly method for the recovery of metals from the
waste lithium-ion batteries [29,30]. However, although the recovering
of lithium is generally the last step of this process, lithium recovery ef­
ficiency is not so satisfactory. Thus, it is still necessary to develop novel
techniques to strengthen the lithium selective extraction process in
order to effective extraction of lithium resource from the waste
lithium-ion batteries industrially. On the other hand, commercial-scale
lithium production from the aqueous resources such as brines is car­
ried out by a soda evaporation process. Nowadays, the lithium produced
from the brine through the conventional solar evaporation and precip­
itation process accounts for the largest share of the world lithium car­
bonate production [31]. However, it still cannot satisfy the demands of
lithium industries due to the limited productivity and high cost.
Therefore, developing efficient and environmentally friendly lithium
recovery technologies for the production of lithium from various liquid
solution is greatly significant for a renewable and sustainable society.
Conventional lithium recovery technologies include the solar evap­
oration and precipitate, solvent extracting, adsorption, as well as ions
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
exchange, which have been intensively developed and applied for
lithium recovery recently. Among them, the solar evaporation and
precipitation technology with a simple operation process and low-cost,
provides about 80% of lithium in the market. However, this technol­
ogy is not suitable for the lithium recovery from the salt-lake brines due
to the existence of large amounts of interfering ions such as high Mg2+.
Fig. 1 compares the conventional solar evaporation process for the
lithium recovery process and the membrane-based lithium recovery
process [41]. To obtain high-quality lithium from the batteries, the
lithium-containing brines should be concentrated into few thousand
ppm of lithium with the removal of various impurities. Based on the
capital cost, the usage of chemical and footprint and process intensifi­
cation, it is obvious that the solar evaporation process is time-consuming
(up to 24 months), tedious and greatly influenced by the meteorological
patterns and other operation conditions [16,32,33]. Especially, it always
requires a large operating site and a great quantity of chemical as well as
water to purify Li, which sometimes makes some resources wasted and
simultaneously leads to some environmental problems [32]. In contrast,
the member-based method is an environmentally friendly technology for
the lithium recovery although it needs a relatively long operating time.
While, the solvent extraction way presents excellent performance in
extracting lithium from the brines with a high ratio of Mg2+/Li+, how­
ever, it requires abundant organic solvents with high energy consump­
tion as well as high cost [34]. Also, the adsorption way is an effective
approach for the selective extracting of lithium from the salt-lake brines
with the high Mg2+/Li+ ratio. Unfortunately, the adsorption process is
always limited by low adsorption capability of the materials while the
desorption will result in the secondary pollution by using some chem­
icals [3]. In addition, the ion exchange way needs materials with high
selectivity but the regeneration of the materials also result in the sec­
ondary pollution and the process is complex and energy-consumption
[19,35,36]. Thusly, more efficient, more time-saving as well as
energy-saving, and more environmentally friendly technique for lithium
recovery is highly desirable. Recently, as the emerging alternative
lithium recovery technology, various electrochemical methods have
been proposed and attracted significant attention [2,37–40].
In this article, the progress on the researches and developments, the
challenges and potential opportunities of electrochemical technologies
for the recovery of lithium from liquid sources was critically reviewed.
Especially, the principles and applications of typical electrochemical
technologies were summarized and discussed. From now, the more
efficient electrochemical technology should be developed for the re­
covery of lithium from those liquid resources, eventually contributing to
the constructing of a clean and sustainable as well as renewable society.
2. Various electrochemical technologies for lithium recovery
Many researchers have put their great efforts into the lithium re­
covery from the wasted Li-ion battery [42–44], but only a few focused
on the lithium recovery from the aqueous lithium resource including
salt-lake brines, geothermal brine, as well as even sea water [2,4]. In
general, the lithium-ion concentration in the above liquid lithium re­
sources is very low and co-existing with other species with relatively
high concentrations [5,45–47]. Fig. 2 shows compositions of the main
Li-including brine resources all over the world, where the relatively high
concentrations of cations including Na+, Mg2+, K+ and Ca2+ always exist
in addition to Li+. One can see that the concentrations of lithium in
brines range from 100 to 1000 mg L− 1, and different brines contain
different ratios of other cations/Li+ [48,49]. Taking China as an
example, more than 80% Li resource exists in the brine, in which the
ratio of Mg-to-Li with a highest value even reaches 1837:1 [47,50]. In
the sea water, the Li concentration is only 0.17 mg/L even though a total
amount of lithium is very large in it as stated above [21,37,51]. Addi­
tionally, in some geothermal brines, the lithium concentrations are
considerably higher (10–20 ppm), which is also worth exploiting in the
future [37,52]. In short, there are a great quantity of Li resources
J. Wang et al.
Fig. 1. Schematic diagram of (a) the conventional process using solar evaporation and (b) the membrane-based lithium recovery process [41].
Fig. 2. Compositions of the main lithium-containing brine resources around the World. Data from Refs. [27,49].
existing in the aqueous phase with low concentrations. Thusly, it is
necessary to develop novel technologies which can effectively recover
the dilute lithium from the liquid lithium resources coexisting with other
elements.
Kanoh et al. firstly proposed one electrochemical method for
recovering of lithium ion from the liquid solution in 1993 [53]. They
researched the lithium-ion electrochemical insertion performance of
Pt/λ-MnO2 electrode in various solutions including the sea water and
geothermal water, and studied the kinetic properties of the electro­
chemical insertion/extraction of Li+ ions using the Pt/λ-MnO2 electrode
via the cyclic voltammetry and the potential-step chronoamperometry.
It is found that Li+ could be efficaciously recovered from the liquid so­
lution through utilizing Pt/λ-MnO2 electrode [53,54]. Thereafter,
various electrochemical methods have been reported for the lithium
recovery. Meanwhile, with the rapid application of Li-ion batteries, the
recovering of lithium from the wasted batteries has been attracting more
and more attention. Recently, some novel electrochemical methods such
as electrochemically switched ion exchange (ESIX) and electrodialysis
have been proposed and explored to recover lithium from the liquid
lithium resources. It is worth noting that such electrochemical ap­
proaches also can be applied in the recovery of lithium and other metals
from the wasted lithium-ion batteries, however, only a few articles have
been reported on it. Thus, in the following sections, the insights of these
electrochemical methods used for lithium recovery from the liquid
sources are mainly classified and discussed in detail.
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
2.1. ESIX process
ESIX process, firstly proposed in Pacific Northwest National Labo­
ratory [55], is an environmental benign and efficient technique. It
combines the electrochemistry with the ion exchange to provide a sep­
aration method with high selectivity and reversible property and has
attracted great attention for extracting the target ion from the aqueous
solution [56–60].
In the ESIX process, one electroactive ion exchange film (ESIX film)
coated electrode is necessary. As illustrated in Fig. 3, by adjusting the
electrochemical potential of the ESIX film, rapidly absorbing and
releasing those target ions will be easily controlled by maintaining the
charge neutrality. For the separation of the cations, as the cathode po­
tential, which is just enough for inducing the electrochemical reduction
of the electroactive species represented by X, is applied to the ESIX film,
the cation will be forced to enter the ESIX film from the solution, as
expressed in Eq. (1). Conversely, re-oxidation of X− will force the cations
out of ESIX films and get into solutions, as expressed in Eq. (2).
e− + X + M+ →X− M+ (1)
X− M+ → X + ​ M+ + ​ e− (2)
In general, various cations coexist in the liquid solutions. In this case,
the ESIX film should show high selectivity for the target cation. For
example, if the selectivity of X− for the target M1+ is much higher than
J. Wang et al.
Fig. 3. Schematic illustration of the ESIX process [59].
that of another M2+, the ESIX film can be "activated" firstly through the
reduction under the M2+ existence, and a conventional ion exchange
process will occur. That is, as shown in Eq. (3), in the spent solution, the
ESIX film will uptake M1+ through the ion exchange of M2+ so that M2+
is displaced into the spent solution. The selectivity of X− to the target
cation is important in the conventional ion exchange process whenever
the spent solution contains what kinds of other cations. Furthermore, in
this case, the competition of binding on the site is taken place, and
simultaneously the loading would be pushed by the thermodynamics.
Thence, ESIX films must prefer to bind the target cations so as to suc­
cessfully recover it [61].
M+ − +→ + − +
2 X + ​ M 1 ← M1 X + ​ M 2 (3)
Meanwhile, in this ESIX process, for the ion transport, the robust
Fig. 4. (a) Schematic diagram for the preparations of λ-MnO2/PPy/PSS hybrid film on the electrode by using the UPED method; (b) Mechanism of the ESIX process
using the as-prepared λ-MnO2/PPy/PSS core-shell nanorods film [62].
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
driving force is electricity. However, the applied potential on the ESIX
film coated electrode must not lead to water electrolysis, which is more
important to use the electrical energy more efficiently, eliminating the
safety issue related to the hydrogen evolution. More importantly, the
release of the target ion is electrochemically carried out without the
addition of any other chemicals, which effectively avoid any secondary
pollutants. In addition, this process is independent of the target ion
concentration in the aqueous solution, and theoretically the target ions
can be completely recovered by this technique. Thusly, it is an effective
way to recover any target ions even with an ultra-low concentration.
In the ESIX process, one of the key issues is to find a special ESIX
material with high selectivity to the target ion. So far, various ESIX films
have been designed to recover different target ions. For the utilization of
the ESIX method to recover lithium from aqueous solutions, it is
J. Wang et al.
essential to synthesize a special electroactive ion exchange film with the
high selectivity to lithium ions so that it can effectively inhibit some
interference from other cations including Mg2+, Na+ ions in the solu­
tions. Du et al. [62] fabricated a λ-MnO2/PPy/PSS (PPy is poly-pyrrole
and PSS is polystyrenesulfonate) nanorod hybrid ESIX film (see Fig. 4
(a)) by using a simple unipolar pulse electrodeposition (UPED) tech­
nique, which was applied to selectively recover the low concentration
Li+ in the aqueous solution. Herein, PPy has good electrochemical ac­
tivity in neutral solution, and PSS-doped PPy, as a conductive cross
linker reagent, has cation exchange property while λ-MnO2 has high
selectivity to Li + ions. After they were composited together, a novel
ESIX film for Li+ separation was obtained. When the λ-MnO2/PPy/PSS
hybrid film was used in the ESIX process to recover lithium ion, the
capacity of Li+ ion exchange achieved 35.2 mg g− 1 with a corresponding
adsorbing equilibrium time below 2 h. Moreover, after five-cycle testing,
its capacity of ion exchange still retained 98.9% when compared with
the initial value, indicating its excellent stability. It is found that this
ESIX film had low ion transfer resistance and distinctive lithium-ion
imprinted vacancy. Fig. 4(b) schematically illustrate the ESIX mecha­
nism of the λ-MnO2/PPy/PSS film. It can be seen that the reversible
insertion and release of Li+ was controlled through adjusting the
reduction or oxidation potential of this hybrid film. In addition, the
PSS-doped PPy also offered vacant sites to adsorb/desorb Li+ ions owing
to its inherent electrochemically switching cation exchange property.
Liu et al. [63] fabricated another LiMn2O4/λ-MnO2 ESIX film with
high Li + adsorption capacity for the recovery of Li + using the ESIX
technology, and discovered that the adsorption rate had an increase
when the operating potential was increased. However, under a high
potential, the crystal structure of LiMn2O4 was damaged. As a result, the
optimum applied potential was found to be 0.75 V, by which the cor­
responding Li+ adsorption capacity was 3.5 mmol g− 1 (equal to 24.2 mg
g− 1). In addition, they also found that the operating temperature and
initial lithium-ion concentration in the solutions also affected the
adsorption rate as well as the adsorption capacity. As the initial con­
centration of Li+ was diluted to 5 mmol L− 1, its adsorption capacity was
still as high as 1.0 mmol g− 1 (equal to 6.9 mg g− 1), indicating that the
ESIX process could be applied for the recovery of dilute Li+ in the
aqueous solution. Liu et al. [64] further studied the performance of
Fig. 5. Schematic illustration of adsorption/desorption on the H1.6Mn1.6O4/rGO composite film [65].
5
Renewable and Sustainable Energy Reviews 154 (2022) 111813
LiMn2O4/λ-MnO2 in this ESIX process for Li + recovery with the coex­
istence of multiple cations including K+, Mg2+, Na + as well as Ca2+, and
found that its selectivity coefficients of Li + to Ca2+, Mg2+, Na+, K+ were
29.04, 120.08, 38.78, 35.63, separately. After 50 cycles, the adsorption
capacity for Li+ ions still maintained at 82.9 % of the initial value, which
indicated that this LiMn2O4/λ-MnO2 ESIX film had great potential to
recover lithium from the brines.
Wang et al. [65] composited the lithium ion sieve H1.6Mn1.6O4 with
rGO to obtain an H1.6Mn1.6O4/rGO hybrid ESIX film via a simple vac­
uum filtration method and applied in the recovering of lithium ion with
low concentration from the aqueous solutions. It was found that the Li+
capacity achieved 38.78 mg g− 1 with an adsorption equilibrium time of
5 h. Even though the initial Li + concentration in this aqueous solution
was only 10 ppm, the adsorption capacity still reached to 4.46 mg g− 1.
Moreover, after 5-cycle test, the adsorption capacity of lithium ion still
maintained 99% of the initial value. Fig. 5 illustrates the Li + adsorption
and desorption in the H1.6Mn1.6O4/rGO hybrid ESIX film, in which the
electrical driving force and the rGO facilitated the aggregation of ion in
the hybrid ESIX film surface and improved ion transport efficiency. In
general, Mg2+, Na+ and other cations could be also absorbed on this film
surface together with Li+, nevertheless, due to the high selectivity of
H1.6Mn1.6O4 towards Li+, more Li+ ions were adsorbed on it at first.
Moreover, in the structure of the H1.6Mn1.6O4/rGO hybrid ESIX film,
the lattice protons also existed, the ion exchange between H+ and Li+
could more easily occur, as shown in the following reactions (4) and (5).
R − H + + Li+ →R − Li+ + H + (4)
R − Li+ + H + →R − H + + Li+ (5)
where R represents an assumed immutable portion of this H1.6Mn1.6O4/
rGO hybrid film. However, the valence state of manganese will be
changed by the applied potential, thus, the following ion exchanges may
occur during the ESIX process:
(6)
′ ′
R − Mn(Ⅳ) + e− + Li+ →R − Mn(III) − Li
(7)
′ ′
R − Mn(III) − Li – e− →R − Mn(Ⅳ) + Li+
J. Wang et al.
where R′ stands for an assumed immutable portion of the H1.6Mn1.6O4/
rGO hybrid film.
In addition, Wang et al. [66] also fabricated a new electroactive
composite film consisting of PPy and one kind of Cu-MOF (MOF: Metal
Organic Frameworks) named as HKUST-1, which were combined
together by the in-situ coordination with the unipolar pulse
electro-erosion method. When it was applied in the recovering of lithium
ion with the low concentration from the liquid solution using the ESIX
process, it was found that this as-synthesized PPy/HKUST-1 complex
film had high Li+ adsorption capacity up to 37.55 mg g− 1 and its time to
reach the adsorption equilibrium was also as short as 25 min, which
identified the sieving function of vacant sites in the composite as well as
the outstanding affinity of this composite to the Li+.
Zhang et al. [67] combined the electrochemical adsorption experi­
ment and the density functional theory calculations to systematically
study the synergistic effect from λ-MnO2 and graphene in the composite
film for the adsorption of Li+ in terms of Li + ion selectivity, ion con­
ductivity and electron conductivity. The DFT calculation results were
consistent with the experimental data. Herein, from the DFT calculation
results, the high electronic conductivity of this λ-MnO2/Graphene film
was attributed to the presence of graphene and the high hybridization of
the O and Mn atoms in the λ-MnO2 whereas the excellent ion conduc­
tivity was ascribed to the low diffusion energy barrier, small L Mn–O and
large average d Li–O. Moreover, the Li+ diffusion energy barrier was
much lower than those of Na+ and Mg2+, leading to the higher diffusion
selectivity to lithium ion.
Briefly, the ESIX technique with low cost and high effectiveness has
been successfully applied for the recovering of lithium ions from the
aqueous solution. Especially, it can be used for the recovery of low
concentration of lithium ions. Furthermore, no secondary waste is pro­
duced by using this method. The key to this technique is to obtain the
special electroactive ESIX film with high selectivity and ion exchange
capacity to the lithium ions. In addition, besides for the recovery of
lithium ions, the ESIX technique also can be applied in many other fields
such as separation of those toxic ions [68], supercapacitors [69] and
electrochemical ion sensors [70]. Until now, this technique used for the
lithium ions recovery from the liquid sources is still at the early stage
and further studies are necessary for the industrial applications. Espe­
cially, it is important to develop and design the ESIX film with high
selectivity for lithium ion, which can effectively suppress the interfer­
ence from other ions particularly including Na+ and Mg2+ ions in the sea
water and lake brines.
2.2. Electrodialysis (ED) process
Electrodialysis is an electrochemically separating technique based on
membrane, which has been extensively applied in the seawater desali­
nation, the recovery of NaCl from the brackish water and sea, and the
metal resources extraction from the salt-lake brine, concentrated brines
and sea water [37,71,72]. The diagrammatic sketch of this typical
electrodialysis is shown as Fig. 6. One can see that it is made up of a
sequence of anionic and cationic exchange membranes, which are
alternately installed between the cathode and anode. However, a
pre-treatment process is needed to avert the membrane blockage by
some solids in the aqueous solution.
As illustrated in Fig. 6, during the process, those target ions are
selectively passed through the semi-permeable membrane from the
dilution chamber to the concentration chamber under the electrical
driving force applied between the two electrodes. Herein, the ion
permeable membrane plays the key role in the ion separation. Cation
migrates towards the cathode by passing through the negatively charged
cationic exchange membrane whereas the anion migrates to an anode by
passing through positively charged anionic exchange membranes, which
results in different concentrations in the diluted and concentrated
compartments [73,74]. Such an electrodialysis technology has many
excellent advantages including simple operation, environment-friendly,
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
Fig. 6. Schematic diagram of the electrodialysis process [17].
and energy saving. Nowadays, it is also attracting the increasing atten­
tion for water purification and the metal ion recovery, especially.
For the recovery of Li+, the development of membrane with high
selectivity to Li+ in the electrodialysis system is also the main challenge
in this technology. Many researches also indicated that the electrodial­
ysis method could be used to recover Li+ in the aqueous solutions even
with a low lithium concentration. Table 1 summaries the developed
membranes applied in the electrodialysis technology for the recovering
of Li+.
2.2.1. Cationic and anionic membranes-based electrodialysis (C/AMED)
In Table 1, both the anionic exchange membrane AR204SXR412 and
the cationic exchange membrane CR67-MK111 belong to the commer­
cial membranes supplied by Arak Petrochemical Complex Company,
which have been applied in the four-compartment electrodialysis cell.
Parsa’ group [74] studied the effects of operating potential, initial
feeding concentration and other operation parameters on the recovering
of Li+ from the liquid solution, and found that about 20 % of Li+ was
recovered from Li-containing solutions, and the highest Li+ ion con­
centration obtained in the cathode compartment reached a value of
7654 ppm. Liu et al. [47] proposed an electrolysis method using a novel
anion exchange membrane (MA-7500) to extract lithium ion from the
salt-lake brines with a high ratio of Mg-to-Li. Fig. 7(a) displays dia­
grammatic sketch of this electrodialysis cell, which is categorized to two
slots by the anionic exchange membrane, where LiFePO4 and FePO4
were acted as the cathode and anode, respectively. One slot was full of
salt-lake brines whereas the other was filled with the Mg2+-excluding
electrolyte. Meanwhile, the cathode was placed in Mg2+-excluding
electrolyte, and the anode was immersed into the brine. Under the
electrical driving force, Li + ions in the brines were embedded in the
FePO4 to generate LiFePO4, and meanwhile, Li + ions were released to
Mg2+-excluding electrolyte to regenerate the FePO4. That is to say, in
this process, FePO4 reacted with Li + to form LiFePO4 whereas LiFePO4
was decomposed into Li+ and FePO4. Meanwhile, anions transferred
from the salt-lake brine to the electrolyte without Mg2+ to keep the
charge balance since the cation cannot pass through the anionic ex­
change membrane in this case. As such, Li + can be selectively extracted
from the brines to the electrolyte solution without the Mg2+ ions. They
also investigated the Li+ ion exchange capacity from several aspects
including the initial Li concentration, the surface density of the active
substrate, the distance between the two electrodes, electrolyte temper­
ature and the electrolysis time. As a result, in the optimum operating
conditions with the pH value under 8 for the anolyte, an outstanding Li+
J. Wang et al. Renewable and Sustainable Energy Reviews 154 (2022) 111813

Table 1
Characteristics of various membranes for Li + recovery in electrodialysis technology.
Membranes Suppliers Thickness (μm) R (Ω cm2) BS (MPa) IEC (meq g− 1) T max (◦ C) Ref.

AR204SXR412 Arak Petrochemical Complex (USA) 500 0.7 2.8 [74]

CR67-MK111 500 0.7 2.4
CIMS ASTOM company (Japan) 150 3.0 ≥0.10 40 [75]
ACS 130 2.4 ≥0.15 40
CMB ASTOM Co. Ltd 210 4.5 ≥0.40 60 [76,
AHA 220 4.1 ≥0.90 60 77]
NEOSEPTA BP-1E 220 ≥0.40
PC SK ~2.5 0.4–0.5 50 [34]
PC Acid 60 160–200 ~2 0.4–0.5 60
PC bip 200–350 40
JAM–II–05 Beijing Tingrun Membrane Technology Development Co. Ltd., 160–230 4–8 1.8–2.2 [78,
(China) 79]
JCM–II–05 160–230 1–3 2.0–2.9
Neospeta CMX Tokuyama Co. (Japan) 164 2.91 1.62
Neosepta BP-1 200–350

Note: R: resistance; IEC: ion exchange capacity; T max: operating maximum temperature; BS: burst strength.

Fig. 7. (a) Schematic illustration of an electrolysis cell with the anion exchange membrane (MA-7500) [47]; (b) Structure of the bipolar membrane; (c) Flow diagram
for the separation and recovery of lithium and boron in an electrodialysis process using the BP-1E bipolar membrane [76].

7
J. Wang et al.
ion exchange capacity of 38.9 mg g− 1 was obtained, which confirmed
that the membrane-based electrolysis technique was also suitable for the
extracting of lithium from the salt-lake brines.
Ji et al. [75] also applied the electrodialysis system equipped with
the permselective ionic exchange membrane of CIMS (cation ion ex­
change membrane) and ACS (anion ion exchange membrane) to recover
lithium ions from the brines with high Mg-to-Li ratio. Basically, it is
found that Li+ recovery ratio was 75.44 %, and at a Mg/Li ratio of 92, a
highest value of lithium recovery ratio reached to 71.42%. Thereafter, Ji
et al. [80] investigated the Li+ recovery from a mixed-salts system
containing Li+, Mg2+, Na+, SO42− , HCO3− and others by using the
analogous electrodialysis system and further demonstrated that the
electrodialysis system had a broad applicability for the extraction of Li
from the brine.
In short, for cationic and anionic membranes based electrodialysis, it
is vital to provide highly selective lithium recovery from the liquid
source even with a low concentration of lithium and high concentrations
of other ions.
2.2.2. Bipolar membrane-based electrodialysis (BMED)
As shown in Fig. 7(b), bipolar membrane is a special kind of layered
ionic exchange membrane composed of several cationic exchange layers
and anionic exchange layers with the hydrophilic polymer interface
between them. Such a bipolar membrane-based electrodialysis (BMED)
technology is an electrodialysis process in combination with bipolar
membranes, which is considered as an environment-friendly and sus­
tainable process [76]. In this process, the H2O molecule in a hydrophilic
layer can be split into hydrogen protons and OH− ion under the direct
current electric field, which is the representative property of the bipolar
membrane [17,34,76,81]. Meanwhile, the cation in the salt solution can
migrate towards the cathode by passing through the cationic exchange
membrane whereas on the contrary these anions in salt solutions can
migrate towards the anode by passing through the anionic exchange
membrane. As such, these anions and cations combine with hydroxide
ion and hydrogen proton to generate the relevant base and acid,
respectively, without adding any chemicals [77]. Herein, the bipolar
membrane should possess excellent properties such as high
perm-selectivity, high current efficiency, low electrical resistance, low
voltage drop, and excellent chemical and mechanical stability [77]. In
addition, the BMED method can not only dramatically enhance the
processing capacity through the addition of more membranes, but also
avoid using the lime, which effectively reduces the environmental
pollution. The BMED method has been used to recover the dilute Li+ ions
in those brines with a high ratio of Mg-to-Li.
Jiang and co-workers [78] studied the feasibility of bipolar
membrane-based electrodialysis for the production of LiOH from the
lake brine in a laboratory scale, in which the bipolar membrane named
as Neosepta BP-1 was provided by a Japanese company. Taking the cost
of investment and energy consumption into consideration, the cost of
this process was evaluated to be roughly 2.59 dollars per kilogram of
lithium production when the feeding concentration was 0.18 mol L− 1
with a current density of 30 mA cm− 2 indicating the low
energy-consuming as well as the high current efficiency. Hwang et al.
[79] also utilized the bipolar membrane of Neosepta BP-1 to design the
electrodialysis system for lithium recovery. Based on the four factors of
voltage, pH, rate of flow, and the number of bipolar membrane sheets,
they evaluated this desorption process. In the Li+ ion desorption process,
it was found that a lower pH could result in a higher desorption rate. For
example, when pH was 3 or lower, a desorption rate as high as about
85% was achieved. Furthermore, an optimal current efficiency was ob­
tained at an operating potential of 6.5 V per sheet. Meanwhile, the Li+
desorption efficiency was roughly 70 %. Moreover, as a flow rate per
unit area was 0.44 mL cm− 2 min with an applied voltage of at least 6.0 V
per sheet, about 30 min was taken to reach the equilibrium desorption,
which was much faster than those under other flow rates. In addition, as
the sheet number of the bipolar membranes was 4 with a pH value of 4 or
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
lower, the Li+ adsorbed into lithium manganese oxide might influence
desorption efficiency. Under the optimal operation conditions, this
design for the recovery of Li+ could save roughly 180 min time when
comparing with the chemical desorption way.
Bunani et al. [76] also investigated the simultaneous recovery and
separation of Li and B from the aqueous solutions using the electrodi­
alysis process where the BP-1E (a kind of bipolar membrane) was
applied as illustrated in Fig. 7(c). By investigation of three factors, i.e.,
the operating voltage, coexisting ions in the aqueous solution and Li and
B initial concentrations, it was found that as the Li and B mass transfer
rates increased continuously until the operating potential reached a
maximum limited potential, indicating that the mass transfer in this
process followed Fick’s first law. However, the operating voltage and the
initial Li+ concentration had little effects on the Li and B permeations in
the membrane. Meanwhile, although Na+ and Cl− could also permeate
the membrane at the same time, no effect of co-existing Na+ and Cl− on
the Li and B permeations in the membrane was observed. Moreover, Li
and B separation efficiency was as high as >90%. In addition, with the
increase of an operating potential, its current efficiency related to Li and
B decreased gradually whereas the consumption of the specific power
was increased accompanying along the increase of operating potential.
Bunani and co-workers [34] also developed a lab-scale PCCell elec­
trodialysis process with a four-chamber system to study the separation
and recovery of Li and B in the aqueous solution. Through investigation
of the effects of operating voltage, pH and initial sample volume for the
behavior during one BMED process, it was found that the performance
was improved with the increasing of operating electrical voltage, but
degraded with the increasing of the initial sample volume. Under an
optimal condition with the applied voltage of 15 V and the initial sample
volume of 0.5 L, the Li+ ion separation factor reached 99.6% with a
recovery efficiency of 88.3%. Meanwhile, the increase in pH would have
significant effect on the separation factor and recovery efficiency of
boron but no obvious effect on those of lithium. In addition, the amount
of sample also affected its processing time. The larger amount of sample
was, the longer it took till reaching the steady state. İpekçi et al. [77]
used an Astom Acilyzer EX3B model electrodialysis equipment to study
simultaneously separation and recovery of Li and B from the liquid so­
lution. In a laboratory-scale experiment, they tested the performances
under three different electrical potentials and found an optimum voltage
of 30 V, by which the highest recovery efficiencies of B and Li, namely
50% and 62%, were achieved with the B and Li separation factors of
86.9% and 94.7%, separately. Meanwhile, at this applied electrical po­
tential, the consumption of specific power was about 7.9 kW h m− 3.
Briefly, the BMED technique can not only significantly improve the
capacity through introducing more membranes, but also avoid to use
lime, which always results in the environmental pollution. Additionally,
the BMED technique is suitable to treat the brine with the high ratio of
Mg/Li and low concentration of lithium.
2.2.3. Ionic liquid membrane-based electrodialysis (ILMED)
Ionic liquids are considered as promising solutions and have been
applied for the solvent extraction field due to the high stability and
selectivity with the ignorable volatilization. Particularly, those func­
tionalized ionic liquids containing special metallic coordination groups
have already been successfully applied for the extracting of Li from the
sea water [37]. For instance, Hoshino [82–84] investigated a novel
method for recovering of Li from the sea water via an electrodialysis
process combined with one ion liquid membrane, in which the ionic
liquid named as N-methyl-N-propylpiperidium bis (tri­
fluoromethanesulfonyl) imide (PP13-TFSI) was used to combine with
the electrodialysis process. It was found that the TFSI functional groups
in the PP13-TFSI had high lithium-ion conductivity. As such, only Li+ in
the sea water significantly permeated into the cathode side from the
anode side during the electrodialysis process whereas other ions
including Mg2+, K+, Na + as well as Ca2+ ions were difficult to permeate
this membrane. Therefore, Li+ can be selectively concentrated in the
J. Wang et al.
side of cathode and recovered (see Fig. 8(a)). Herein, the ion liquid
impregnated membrane was used. The measurement of ion concentra­
tion in the cathode part as a function of dialysis time indicated that the
lithium-ion concentration would increase as time. As such, at an oper­
ating potential of 2 V, 5.94% of lithium-ion concentration was achieved
in 2 h. Furthermore, under the same conditions (i.e., 2 V, 2 h), when
both the sides of an impregnating film were coated by the Nafion 324 for
the preventing of the ion liquid from flowing out, the lithium-ion con­
centration was further increased to 22.2%. In addition, the electrodial­
ysis combined with the PP13-TFSI ion liquid membrane exhibited
excellent energy efficiency, and it is also easily scalable. As such, it could
be used in the recovering of Li from the sea water. Meanwhile, N,N,
N-trimethyl-N-propylammonium-bis(trifluoromethanesulfonyl) imide
(TMPA-TFSI) was also applied as an ion liquid in a membrane, but a
lower lithium ion conductivity than other ionic liquids was observed
[84]. In this case, when the ionic liquid TMPA-TFSI-based electrodialysis
method was applied to recover Li from the sea water, only the main ions
including K+, Na+, Ca2+, Mg2+ ions in the sea water significantly
permeated into the cathode side from the anode side but the Li + ions
were difficult to permeate this membrane. Thereby, the Li+ ions
remained in the anode side and could be recovered at an operating
potential in the range of 2–3 V (see Fig. 8(b)). In order to accurately
measure the Li+ ion recovery characteristics, the man-made concen­
tration sea water without Mg2+ and Ca2+ can be added into the anodic
side whereas the solutions without any main ions are introduced into the
cathodic side. Meanwhile, SELEMION™ CMV membrane was also used
to cover the both sides of the ionic liquid membrane to prevent the ionic
liquid from flowing out. As a result, with the addition of Mg2+ ions into
the anodic side to control the permeation rate of lithium, the lithium
recovery rate was increased from 38% to 63%. To prevent the PP13-TFSI
from flowing out, Hoshino [85] also used the SELEMION™ CMV
membrane to cover the both sides of the ionic liquid membrane. This
process was similar as that shown in Fig. 8(a). After 2 h of electrodial­
ysis, the Li+ concentration was found to be increased to 24.5% with an
applied dialysis voltage of 2 V.
Conclusively, the electrodialysis with cationic and anionic mem­
branes, bipolar membrane, and ionic liquid membrane have paid great
attention in recent years. From the perspective of energy and capital
cost, it should be a viable and potential option for the extraction of
lithium from the liquid sources in the future. It is calculated that the
energy consumption of this process was ca. 1.8 Wh/mol Li+, lower than
Fig. 8. Schematic illustration of two mechanisms for the ion-liquid membrane-based electrodialysis: (a) Lithium ion permeates through the liquid membrane while
other cations are blocked and (b) Lithium ion is blocked by the liquid membrane while other cation permeates through liquid membrane driven by the electric
forces [5].
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
that of the cationic and anionic membranes based electrodialysis. In
addition, ionic liquid membrane based electrodialysis combining the
electrodialysis and solvent extraction has the advantages of high selec­
tivity, low energy consumption, and good cyclic performance, which
should be also a potential technique for the lithium extraction from the
salt-lake brines.
2.3. Battery-like electrochemical process
A battery-like electrochemical (BLE) technology based on ion-
capturing electrodes has also been applied in the effective extraction
of Li+ with low energy-consuming. In this technology, the electrode
should have high selectivity to lithium, high lithium capacity, long-term
stability and low energy consumption. Recently, many researchers have
tried to improve the battery-like electrochemical technology for the
lithium recovery. For example, Marchini et al. [86] used a LiMn2O4
(LMO)-based lithium intercalation electrode with a PPy-based electrode
for the reversible adsorption/desorption of chloride and selectively
extracting lithium chloride from the natural salt-lake brines. Theoreti­
cally, with an LMO charge capacity of 147 mA h g− 1, the maximum Li
recovery mass can reach up to 39 mg g− 1. However, during the fabri­
cation of electrodes, some oxide particles were found to be agglomer­
ated, resulting in the segregation of carbon black particles and LMO
particles on the surface, which led to a poor electric contact with current
collectors, thereby finally reducing the efficiency of lithium recovery.
Thusly, the theoretical maximum Li recovering mass was not achieved in
this study. Missoni et al. [87] also investigated a LiMn2O4-PPy based
electrochemical battery for the selectively extracting of LiCl from the
natural brines. Under the total battery voltage less than 1 V, the Li + ions
were reproducibly intercalated into LixMn2O4 whereas the chloride ions
into the oxidized PPy. This process was successfully attained over 200
cycles. Meanwhile, the charge efficiency reached up to 50% with a lower
energy consumption in the range of 5–10 W h mol− 1. Zhao et al. [16]
reported a highly selective system based on the electrodes of LiM­
n2O4/Li1-xMn2O4 for the lithium recovery. In this system, LiMn2O4, as
the positive electrode, deintercalation/intercalation, whereas
Li1-xMn2O4, as the negative electrode, exhibited high selectivity towards
Li+. They investigated the influences of potential, temperature, coex­
isting ions and specific energy consumption on the lithium extraction
efficiency, and found that the lithium extraction capacity reached a
maximum value of 34.31 mg g− 1 (LiMn2O4) with a maximum energy
 J. Wang et al.
consumption under a voltage of 1.2 V. Meanwhile, the higher operation
temperature was, the quicker its corresponding extract rate was, yet the
larger its energy-consuming also was. Moreover, it was found that this
system remained high selectivity towards lithium ion even in the coex­
istence of Na+, K+, Ca2+ and Mg2+. Additionally, to research the pos­
sibility of this system applied in a practical process, the brine solutions
and concentrated seawater samples were used. For the brine solutions,
the extract capacity of lithium ion was around 22 mg g− 1, suggesting
that 22.5 % of lithium ions from brines can be recovered at a time.
Besides, it needed to take 18.0 W h per mole Li extraction. For the
concentrated seawater solutions, Li+ extraction capacity was approxi­
mately 21 mg g− 1, which indicated that 14.0 % of Li+ ions in the
seawater can be exacted at a time. Meanwhile, it required to take 18.6
W h per mole Li extraction. Furthermore, it was found that the structures
of electrodes were almost invariant after a five-cycle test, indicating that
the electrodes can be repetitively used. Lawagon et al. [40] introduced a
new electrochemical Li + ion recovery system by combining the Li1− x
Ni1/3Co1/3Mn1/3O2(NCM)/Ag electrode pair. It was found that the
delithiated NCM/Ag electrode had high Li+ ion selectivity and high
stability in the liquid circumstance. In their experiments, a
three-electrode system in one glassy cell with a volume of 40 mL was
used with an operating temperature of 25 ◦ C (see Fig. 9). Firstly, in the
brine solution, a negative current was used for promoting the insertion
of Li+ ions into NCM lattice and simultaneously for the capturing of the
chloride ions on the Ag electrode, which was the Step 1 in Fig. 9. After
the effluxion, in order to remove the remaining brine, the electrode was
rapidly immersed into the deionized water. Then, the electrodes were
soon placed into one smaller cell containing 10 mL of 30 mmol L− 1
lithium chloride electrolyte as the receiving solution. In the smaller cell,
the positive current was used for the extracting of Li+ ions from the NCM
electrode and simultaneously desorbing of chloride ions from the Ag
electrode, which was the Step 2 in Fig. 9. Herein, the current density (i)
applied in both steps (i was ±0.50–1.5 mA cm− 2) and the operating time
(10–30 min) for each step was changed to maximize the recovering of
lithium ions with the lowest energy consumption. As a result, when the
current density applied in both steps was ±0.25 mA cm− 2 and the
operation time was 20 min for each step, the yield of Li+ reached 96.4%
with an energy-consuming of 2.60 W h mol− 1. Moreover, this NCM/Ag
electrode pair exhibited high stability and the enriched LiCl solution can
be continuously obtained during the cycling operation, which suggested
that the NCM/Ag electrode pair based electrochemical process could be
a promising and high-throughput lithium-ion recovery process with a
low energy consumption.
Kim et al. [88] applied another electrochemical setup with the
Fig. 9. Conceptual illustration of the Li1− xNi1/3Co1/3Mn1/3O2/Ag electrochemical process for the lithium-ion recovery. (The cells were not drawn in proportion; The
feed volume of the simulated brine was 40 mL; The smaller reactor with the volume of 10 mL including 30 mM lithium chloride was operated at the room tem­
perature of 25 ◦ C [40].
10
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
λ-MnO2/Ag electrode pair to rapidly and selectively recover Li+ ions in
the brine desalination with 2–3 times higher concentrations of the
concentrated seawater for the first time. Fig. 10 schematically illustrated
this electrochemical Li+ ion recovery system consisting of λ-MnO2 and
Ag electrodes. As shown in Fig. 10(a), in desalinated brine, lithium ion
and Cl− could be captured by λ-MnO2 electrode and Ag electrode,
separately. Afterwards, these ions preserved in the electrode were
released to the standard solution containing 30 mmol L− 1 KCl to recover
Li+ and Cl− ions and simultaneously regenerate the electrode for
continuously operating (see Fig. 10(b)). In order to capture lithium and
chloride ions together from the brine, the constant current densities of
− 20, − 10 as well as − 5 μA cm− 2 were separately applied on the elec­
trochemical cell. When the applied potential was 0.2 V, it was found that
the Ag and λ-MnO2 were separately converted into AgClx and LixMn2O4
(x was equal to 0–1). After a substantially short period of operation, the
cell was washed by the distilled water for removing the residual ions.
Meanwhile, the Li+ and Cl− ions stored on the electrodes were released
to the recovering solutions. At that moment, a positive current density of
0.2 mA cm− 2 would be applied on a battery system to obtain a battery
potential of 0.9 V for the regeneration of electrodes to the beginning
states. In comparison to the traditional adsorption and electrodialysis
processes, this battery-like electrochemical process could rapidly and
selectively recover lithium from the desalination brine and did not need
any acids and harmful chemicals in the recovering process, which is
similar as the ESIX process. In addition, the Li+ ions obtained from this
system could have higher purity with a higher Li+ ion concentration in
the recovering solutions through the continuous operating. It was found
that the purity of lithium ions could reach up to 99.0% in the final re­
covery solution including 190 mmol L− 1 of lithium ions with only less
energy consumption (namely, 3.07 W h g− 1 Li). Thus, this λ-MnO2/Ag
electrode pair-based electrochemical process could be a promising way
to recover Li from the brine and sea water.
Summarily, such a battery-like electrochemical system presents a
considerable feasibility with excellent performance in lithium extraction
from brines. Their principle is to capture lithium ion from the brine and
release it into the recovery solution. As a promising technique, it is
required to optimize the critical factors including the synthesis of highly
effective electrode with good selectivity, competitive lithium capacity,
long-term stability, and lower energy consumption.
2.4. Other electrochemical processes
In addition to the previously mentioned electrochemical methods to
recover lithium from the aqueous solutions, other electrochemical
J. Wang et al. Renewable and Sustainable Energy Reviews 154 (2022) 111813

Fig. 10. Schematic diagram of the Li recovering process from these desalinated brines using a λ-MnO2/Ag electrochemical system: (a) Li+ ion capturing step
(discharging) and (b) the lithium ion releasing step (charging) [88].

processes have been also proposed. For instance, as illustrated in Fig. 11,
Ryu et al. [89] proposed a concept to combine a spinel type of LiMn2O4
adsorbent with the electrostatic field to recover Li + ions. This process
mainly includes three steps. The first step is an adsorption step where Li+
ions are adsorbed by a lithium selective adsorbent layer. The aim of the
second step is to remove other ions which were not adsorbed by the
adsorbent layer through washing with the deionized water. The elec­
trostatic field is applied in the third step to force Li+ ions releasing from
the adsorbent layer to the solution and then these Li+ ions were attracted
by the opposite electrode with the anion exchange membrane. However,
due to the ion selectivity of anion exchange membrane, Li+ ion migra­
tion could be disturbed, which can result in the final effluent containing
the concentrated Li+ ions. The feasibility of this method was investi­
gated through the experiments. Compared with the conventional
desorption process using acid solutions, this method avoided using the
toxic agents and did not cause the environmental pollution. Though the
desorption efficiency was relatively low (about 45%), this method could
still be a feasible alternative.
Ryu et al. [90] combined a hydrophilic PVA binder with the LiMn2O4
adsorbent to improve the above lithium recovering system, in which the
electrostatic field assistance was also used. The experimental results
exhibited that when the applied potential was within the range between
0 and 1.0 V, the adsorbed amount of Li+ by the electrostatic field
assistance would gradually increase. However, as the potential was over
1.5 V, the adsorbed amount of Li+ would slightly decrease. Herein, the
electrostatic field assistance effectively improved the adsorption per­
formance for lithium when compared with the physical adsorption.
Simultaneously, the adsorption time reaching the equilibrium state by

Fig. 11. Schematic illustration of the lithium-ion recovery assisted by the electrostatic field: (a) the graphite sheet as the current collector; (b) the selective adsorbent
Li electrode; (c) the anionic exchange membrane, and (d) the activated carbon electrode [89].

11
J. Wang et al.
the electrostatic field assistance was shorter than that by the physical
adsorption process. These results confirmed the acceleration effect of the
electrostatic field assistance. Additionally, this system also demon­
strated excellent durability as well as reproducibility during the
repeated adsorbing/desorbing cycles. In short, owing to the reduced
time for the adsorbing as well as the desorbing processes and the eco­
nomic feasibility, this system was considered as one alternative way for
the recovering of lithium from the liquid solution.
Kim and his group [91] proposed one λ-MnO2/activated carbon
(AC)-based supercapacitor-like system for the recovering of Li+. As
shown in Fig. 12(a), in this system, the λ-MnO2 composite-based elec­
trode as well as the AC electrode covered by the anionic exchange
membrane were applied as the positive and negative electrodes, sepa­
rately, and there existed one nylon spacer between them. The operation
for the recovery of Li+ ions by this system included the discharging and
charging processes as shown in Fig. 12(b). During the discharging step,
the invariant current density of − 0.5 mA cm− 2 would be used and
flowed from the positive electrode into the negative electrode. As such,
Cl− ions migrated into the negative electrode side via passing through an
anionic exchange membrane, and simultaneously a double layer can be
constructed in the activated carbon composite negative electrode sur­
face. Meanwhile, Li+ ions migrated to the λ-MnO2 composite positive
electrode, and intercalated into lattice of the spinel λ-MnO2. During the
charging step, the invariant current density of 0.5 mA cm− 2 was used for
Fig. 12. (a) Schematic illustration of the continuous Li recovering system containing (1) the activated carbon composite electrode, (2) the anionic exchange
membrane, (3) a nylon spacer and (4) the λ-MnO2 composite electrode in the reactor; (b) Schematic illustration of discharging and charging reactions during the
lithium recovery process [91].
12
Renewable and Sustainable Energy Reviews 154 (2022) 111813
this reactor. The Li + ions were deintercalated from the spinel structure
while the Cl− ions were released from the surface of activated carbon
composite. Based on the experimental results, it was confirmed that this
supercapacitor-type system for the lithium recovery had high selectivity
with relatively low energy consumption (only 4.2 W h mol− 1 lithium)
and excellent stability.
Based on the above-mentioned discussions, the various electro­
chemical technologies are considered as promising ones for the lithium
recovery and their advantages are summarized in Fig. 13. Among them,
the ESIX technique presents high selectivity to lithium ion even in the
case of low concentration. However, since it is still on the way of
development, future researches are still needed, especially the rational
developing and designing of various electroactive materials with high
selectivity to the lithium ion to suppress the interference from other co-
existing ions including Na+ and Mg2+ ions in the seawater and lake
brines. Additionally, combining the ESIX technique with other process
such as membrane separation of lithium ion with good selectivity may
also be a potential approach to promote the lithium recovery from liquid
sources. Generally, C/AMED and BMED techniques have been investi­
gated for the lithium recovery from the solutions with the lithium con­
centration higher than 100 mg/L, while ILMED and ESIX techniques are
used for the lithium recovery from the lithium-containing solutions with
a lower concentration. In addition, ED technique is also suitable for the
lithium recovery from the seawater or concentrated seawater. However,
J. Wang et al.
Fig. 13. The advantages of the various electrochemical technologies for
lithium recovery.
compared with ESIX technique, the ED technique needs relatively higher
applied voltage [92]. To date, most of the researches about the ED-based
technologies for lithium recover have been conducted at bench-scale,
and majority of them generally used the simulated brine solutions to
do the research. Apart from that, the impact of membrane fouling and
scaling is still not resolved. From a practical perspective, it is required to
develop the membrane with high selectivity to the lithium ion with less
membrane fouling in the further work. While, the BLE technique re­
quires costly equipment when compared with ED and ESIX ones, which
will increase capital cost related with the process. In addition, the BLE is
an emerging technology, which was seldomly reported for the applica­
tion in the lithium recovery. In the future research, it should pay more
attention on the influences from the composition of the feed solution,
the better arrangement of electrode pairs, the optimization of the cur­
rent density and the applied potential for a given system. As such, it will
make BLE technique become a strong competitor in the application for
the lithium recovery from liquid sources. For the large-scale application,
even though there still exist some issues in the electrochemical system to
affect the performance, due to their simple operation, sustainability,
high efficiency, and low energy consumption, they are important tech­
niques for the effectively recovery of lithium from the liquid sources in
the future.
3. Conclusions and perspective
With an ever-growing application of Li-ion battery in the electrical as
well as electronics devices and hybrid electric vehicles, the lithium re­
covery from the liquid-state lithium resource such as the salt-lake brine,
geothermal brines, as well as even sea water is becoming more and more
important to guarantee the reliable lithium supply nowadays. Various
typically potential electrochemical technologies for the recovering of Li
developed in recent year were critically reviewed above. Electrically
switching ionic exchange process is an environmental benign ionic
separating technology for the recovering of low-concentration lithium.
It has excellent lithium recovery capacity and efficiency, non-existence
of toxic chemical consumptions as well as waste solution discharging.
Electrodialysis is another emerging technology to adequately recover
lithium from seawater with the lean concentration of lithium. The
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Renewable and Sustainable Energy Reviews 154 (2022) 111813
advantages of electrodialysis are high purity of the products (more than
95%), high extracting efficiency (>80%) as well as low energy con­
sumption. Battery-like electrochemical technology based on the target
ion recognition electrodes could be also applied in extracting Li from the
aqueous solution effectively and selectively. Its advantages include low
energy-consuming as well as high selectivity toward Li. Other electro­
chemical technologies for the recovering of Li include the electrostatic
field assistance system and the supercapacitor-like system, but their
recovery efficiencies are still low.
Although many progresses have been proposed for the lithium re­
covery using the electrochemical technologies, there still exist the
following challenges. (1) The processing mechanisms, especially the
selective separation mechanisms of the related materials, are still lack­
ing and only reported by a few researchers. Density functional theory
(DFT) approach and other theoretical analysis methods [93–95] for
understanding the selective adsorbing and desorbing of lithium ion
should be applied to clarify these mechanisms from electron and mo­
lecular level. Furthermore, some in situ/operando characterization
technologies [96] including in situ spectroscopy technology shall be used
to study the state changes of electroactive materials. In particular,
combining DFT theoretical calculations with in situ/operando charac­
terization techniques will be a strong way to understand the mechanism.
For example, Permien et al. [97] employed Operando X-ray diffraction
and X-ray absorption spectroscopy to simultaneously record the struc­
tural and electronic alterations happening during Li uptaking. Mean­
while, DFT calculations can be used to theoretically study the structure
and stability. Combining these results should in-depth understand the
separation mechanism. (2) Even though these electrochemical technol­
ogies are technically feasible, operating cost and energy consumption
are still the main challenge for the industrialization and commerciali­
zation. (3) The liquid lithium resources are greatly abundant. However,
how to effective, selective and continuous separation of lithium with an
ultralow concentration per unit volume in the presence of other ions
with high concentrations such as magnesium ions, sodium ions, and
potassium ions is still full of challenge. (4) It is critical to develop new
materials for electrodes and membranes with high lithium selectivity,
long-term stability and low price. (5) Almost all reported materials are in
the laboratory scale, and it should be vital for the practical application to
scale them up as well as assess their behavior in the large scale.
Overall, further researches on the lithium recovery from the liquid
lithium resources using the electrochemical technologies should focus
more on the following aspects: (1) The processing mechanisms of the
lithium recovery from the molecular scale as well as the electronic level
combining the experimental phenomenon and results with the theoret­
ical analysis should be revealed, which will provide useful directions to
the design and selection of suitable electroactive materials. (2) More
efforts must be paid to the designing and developing of novel material
for electrodes and membranes with high lithium selectivity, long-term
stability, low energy consumption and low price. (3) The novel elec­
trochemical technologies such as the membrane combined with the
electrostatic field assistance method, the electrode materials combined
with the supercapacitor method should be further studied so that they
show more excellent performance and environment-friendly for the
recovering of Li. (4) It is worth noting that these comprehensive analysis
of these electrochemical technologies in the lithium recovery is impor­
tant for the understanding of the process mechanism and the comparison
of their different performances. Energy consumption, system stability,
operation cost and product quality should be considered in the
comprehensive analysis. If the future studies on the lithium recovery
process can comprehensively address the mentioned issues, it is ex­
pected that the electrochemical lithium recovery technology can be
applied in practice in near future.
Declaration of competing interest
The authors declare that they have no known competing financial
J. Wang et al. Renewable and Sustainable Energy Reviews 154 (2022) 111813

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