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Review

Progress in electrochemical lithium ion pumping for lithium recovery

Guolang Zhou, Linlin Chen, Yanhong Chao, Xiaowei Li, Guiling Luo,
Wenshuai Zhu

PII: S2095-4956(20)30762-2
DOI: https://doi.org/10.1016/j.jechem.2020.11.012
Reference: JECHEM 1687

To appear in: Journal of Energy Chemistry

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Revised Date: 2 November 2020
Accepted Date: 3 November 2020

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Review

Progress in electrochemical lithium ion pumping for lithium

recovery

Guolang Zhoua, Linlin Chena, Yanhong Chaob, *, Xiaowei Lia, Guiling Luoa, Wenshuai
Zhua,c *

a School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang

212013, Jiangsu, China
b School of Pharmacy, Jiangsu University, Zhenjiang 212013, Jiangsu, China
c Jiangsu Topfine New Materials Science & Technology Co., Ltd., Zhenjiang 212013,

Jiangsu, China
*Corresponding authors.

E–mail addresses: [email protected] (Y. H. Chao); [email protected]. cn (W. S. Zhu).

ABSTRACT

Accelerating the development of lithium resources has attracted a great deal of attention

with the explosive growth of new energy vehicles. As a new technology,

electrochemical lithium ion pumping (ELIP) is featured by environment–friendly, low

energy consumption and high efficiency. This review summarizes the research progress

in ELIP, and focuses on the evaluation methods, electrode materials and

electrochemical systems of ELIP. It can be concluded that ELIP is expected to achieve

an industrial application and has a promising prospect. In addition, challenges and

perspective of electrochemical lithium extraction are also highlighted.

Keywords: Electrochemistry; Lithium ion pumping; Recovery; Seawater/brine

1
Guolang Zhou received his bachelor’s degree in 2019 from Huaiyin Normal
University. He is currently pursuing his master’s degree under Professor Wenshuai
Zhu’s supervision. His research interest is electrochemical ion separation and
purification, especially lithium ion extraction in salt–lake brine and seawater.

Linlin Chen got her PhD from Jiangsu University in 2018. She is currently a
postdoctoral in Professor Wenshuai Zhu’s research group in Jiangsu University. Her
research interests include the efficient recovery of valuable metals in waste lithium–ion
batteries, lithium extraction from brine and electrocatalytic water splitting.

Yanhong Chao received her PhD. degree from Jiangsu University in 2014. Currently,
she is a full professor at the Jiangsu University. She has published more than 60 papers
with over 2000 citations (h–index: 26). Her research interests include the synthesis and
application of ionic liquids and 2D materials for adsorption separation pollutants.

2
Xiaowei Li received her master’s degree in 2017 from Jiangsu University. She is
currently pursuing her PhD degree under the supervision of Professor Wenshuai Zhu at
Jiangsu University. Her current interests include the synthesis, characterization of
lithium ionic sieve for lithium recovery from seawater/brine.

Guiling Luo received her master’s degree in 2020 from Hainan Normal University.
She is currently pursuing her PhD degree under the supervision of Professor Yanhong
Cao at Jiangsu University. Her current interests include the synthesis, characterization
of electrode modified material for lithium recovery from seawater/brine.

Wenshuai Zhu received his PhD degree from Jiangsu University in 2009. Currently,
he is a full professor at the Jiangsu University. He has published over 200 peer–
reviewed journal papers with more than 6800 total citations and an h–index of 47. His
research interests include the synthesis and application of ionic liquids and 2D materials,
deep desulfurization of fuels and energy metal recovery, focusing on adsorption method,
extraction method and electrochemical method for the recovery of metal lithium.

3
1. Introduction

Lithium and its compounds, as a kind of natural resource with important economic

value, have been extensively employed in metallurgy, aerospace, ceramics, special

glass, nuclear fusion fuel and other fields [1–3]. In recent years, the importance of

lithium has been further enhanced with the widespread use of lithium–ion batteries in

portable electronic devices, new energy vehicles and power storage. Global lithium

production has increased dramatically since 2016, and had surged to 85,000 tons in

2018, more than doubled in 2016 [4]. By 2025, staggering 140,000 tons lithium is

expected to be consumed by lithium–ion batteries and other industries, which may

further aggravate the contradiction between lithium supply and demand. Lithium is

sourced mainly through ore and salt–lake brine, the content of lithium in brine is

approximately twice that in ore. Lithium extraction from ores suffers from high energy

consumption and technical complexities, which requires a series of steps such as

crushing, roasting, acid leaching and precipitation. It is estimated that the cost of

recovering lithium from ore is twice as much as from brine [1,5]. Therefore, developing

an economical and environmental–friendly salt–lake lithium recovery technology to

cope with the possible lithium shortage crisis is particularly important.

Currently, the lime soda evaporation process is mainly employed in industry. In

this process, brine was pumped into a pond and evaporated for 12 to 18 months until

the lithium–ion concentration reaches 6000 ppm. Magnesium was removed with lime

and the insoluble lithium carbonate can be precipitated with sodium carbonate.

Drawbacks in addition to the long time–consuming, are the large water consumption,

4
and significant environmental impact. In recent years, a number of new techniques for

lithium recovery such as adsorption [6,7], extraction [8], ion exchange [9,10],

membrane electroosmosis [11], reaction–coupled separation technology [12–15] and

etc. have been proposed with the continuous breakthroughs in lithium recovery research.

Among them, the extraction method requires the use of a large amount of organic

solvents, which is harmful to the environment; the membrane electroosmosis method

and the ion exchange method have high production costs. The lithium ion sieve

adsorption method and reaction coupling separation technology based on the adsorption

principle have the potential for large–scale industrial application, but they still face

problems such as large adsorbent dissolution and serious corrosion to equipment. More

recently, ELIP method with high efficiency, friendly environment and simple operation

has been widely concerned by researchers based on the existing problems. Table 1

shows the comparison of adsorption method and ELIP method. Compared with the

adsorption method, the electrode material of the ELIP method has lower dissolution

loss and higher cycle stability, while maintaining high adsorption efficiency and low

corrosion to equipment. Kanoh and his team first reported the feasibility of

electrochemical lithium ion pumping based on the principle of lithium–ion batteries

[16]. They used –MnO2–modified platinum electrode as a working electrode, calomel

electrode and platinum wire electrode as reference electrode and counter electrode

respectively. XRD confirms that lithium manganate and manganese dioxide were

formed in the process of charging and discharging, accompanying with the insertion

and desertion of lithium ions.

5
 Table 1. Comparison of adsorption method and ELIP method.

Materials Adsorption Adsorpti Dissolutio Desorption method Stability Reference

capacity on time n loss

Adsorption method

H2TiO3 23 mg/g 5h 0.5 % 0.6 M K2S2O8 elution 95% (5 cycles) [7]

H1.6Mn1.6O4 34 mg/g 40 h NR 0.5 M HCl elution 82.87% (20 cycles) [17]

Fe3O4–HMO 29.9 mg/g 25 h 6.22 % 0.05 M HCl elution 65% (5 cycles) [18]

–MnO2 35 mg/g 20 min 14.5 % 0.1 M HCl elution NR [19]

H0.23Li0.77Ti2O4 9.5 mg/g 24 h 0.1 % 0.5 M HCl elution 39% (3 cycles) [20]

H1.6Mn1.6O4 10.3 mg/g 24 h 6% 0.5 M HCl elution 96% (10 cycles) [21]

ELIP method

–MnO2/Pt 11 mg/g 2.5 h <0.1 % Cyclic voltammetry 100% (5 cycles) [22]

LiFePO4/FePO4 38.93 mg/g 10 h <0.1 % Constant voltage 87% (31 cycles) [23]

LiFePO4/FePO4 38.6 mg/g 10 h <0.1 % Constant voltage 100% (20 cycles) [24]

H1.6Mn1.6O4 38.78 mg/g 8h <0.1 % Constant voltage 99% (5 cycles) [25]

LiMn2O4+Li4Ti5O12 34.2 mg/g 30 min <0.1 % Constant voltage 100% (14 cycles) [26]

Due to the bottleneck of lithium–ion battery commercialization and technological

development, the ELIP technology developed slowly from the first paper published by

Kanoh to the LiFePO4/Ag battery system proposed by Pasta in 2012 [3]. After 2012,

with the rapid development of nanomaterials and the widespread application of lithium–

ion batteries, ELIP technology has received more and more attention. Electrode

materials and electrochemical systems of ELIP have been summarized in the form of a

chart in Fig.1. It is foreseeable that ELIP technology will play an important role in

ensuring energy security, and will also attract more and more researchers to participate

in this research.

This work comprehensively reviews the development of electrochemical lithium

recovery technology based on electrochemical lithium ion pumping. It mainly

introduces the concept, evaluation methods, electrode materials and different

electrochemical systems of electrochemical lithium ion pumping. In addition,

challenges and future research directions are also discussed.

6
Fig. 1. Summary illustration of categories of electrode materials and electrochemical

systems of ELIP (LFP, LMO, LMTO, HKUST–1, LNMO and LNCMO represent

LiFePO4, LiMn2O4, Ti doped LiMn2O4, metal organic framework Cu3(BTC)2,

Li1−xNi0.5Mn1.5O4 and Li1−xNi0.33Co1/3Mn1/3O2 respectively).

2. Basic theory of electrochemical lithium ion pumping

2.1 Concept of ELIP

With the development of LiFePO4–based electrochemical lithium recovery

technology, Fabio La Mantia's research group proposed the concept of electrochemical

ion pumping in lithium recovery. Subsequently, Jeyong Yoon’s group gave the

definition of electrochemical ion separation (EIONS), that is “EIONS is categorized as

a novel process that utilizes an external field, solid agent and often barrier to realize ion

separation’’. Therefore, we believe that the electrochemical lithium ion pumping can

be defined as follows: electrochemical lithium ion pumping is a novel process that

utilizes external electric field, lithium adsorbent and often ion–exchange membrane to

7
separate lithium from mixing components in the liquid phase. The basic parts of ELIP

includes electrode, electrolyte and external power supply. It's worth noting that ion

exchange membrane is often used to construct different types of ELIP devices. In

addition, unlike other types of adsorbents (such as activated carbon), at least one of the

two electrodes used in ELIP technology has a specific lithium ion transmission channel

(lithium ions can be inserted into the corresponding lattice during the extraction process,

such as LiMn2O4). When a certain voltage is applied to the system, lithium–ion and

counter ion present in the feed mixing components are separated as they are captured

by the positive and negative electrodes, respectively. When a reverse voltage is applied

to the system, the captured lithium–ion and counter ion can be released back to the

electrolyte regenerating new electrodes. Fig. 2 shows the mechanism of ELIP with

LiMn2O4/Ag electrode as an example. Compared with other lithium–ion recovery

methods, this method is being actively studied as a promising next–generation lithium–

ion separation technology due to its environmental friendliness, high efficiency, simple

operation and low energy consumption.

Fig. 2. The mechanism of ELIP (Take LiMn2O4/Ag electrode as an example).

8
2.2 Evaluation method of ELIP

Different researchers usually used different parameters to evaluate the

performance of ELIP, due to the diversity of electrode materials and devices. However,

some key parameters, such as selectivity, adsorption capacity, energy consumption,

stability and energy efficiency, are widely used by most scholars.

2.2.1 Selectivity

The selectivity of lithium–ion to other coexisting cations gives an indication of

how much Li–ion could be captured without co–incorporated other cations. There are

five different formulas for selectivity representation. Table S1 shows the advantages,

disadvantages and application scenario of several metrics for the selectivity.

Based on the concentration of recovery solution [4,27–31]

𝐶Li
𝛼Li
M = 𝐶M (1)

Where 𝐶Li and 𝐶M represent the concentration of Li+ and coexisting cations

(mainly Na+, K+, Ca2+ or Mg2+) in the recovery solution respectively. Although the

value of 𝛼Li +
M depends on the concentration of Li and other cations in recovery solution,

M also greatly affected by different source solution. For example, higher concentration
𝛼Li

of co–cations in the source solution will increase the co–intercalation of co–cations and

decrease the value of 𝛼Li

M. The components of different salt lakes or different regions of

the same salt–lake are not the same, so this evaluation method has some limitations.

Based on purity

9
 𝐶Li
𝐴Li = ∑𝐶 (2)
M

Similar to formula 1, this formula is also based on the concentration of ions in the

recovery solution. Where 𝐶Li and 𝐶M represent the concentration of Li+ and sum

concentrations of all metal ions respectively. A purity of 99% of lithium carbonate is

required by industrial production, so the purity calculated by this formula is directly

related to industrial production, which is of great significance [4].

Based on distribution coefficients [27,28]:

𝐾Li
D
𝛼Li
M = 𝐾M (3)
D

𝑄f
𝐾D = 𝐶f (4)
(𝐶0 - 𝐶f)
𝑄f = 𝑚 𝑉f (5)

Where 𝐾D, 𝑄f, 𝐶0, 𝐶f and 𝑉f represent distribution coefficients, insertion capacity

of the lithium capturing electrode, initial concentration, final concentration and volume

of brine, respectively. Although the effect of brine concentration has been taken into

account by this formula, it ignores the effect of the concentration of lithium and other

metal ions in the recovery solution. In addition, the 𝑄f of other metal ions are difficult

to calculate accurately [4].

Based on the separation coefficient

Researchers proposed the separation factor to represent the selectivity [27,28],

since the previous formula failed to take into account both the brine and the recovery

solution.
𝐶Li 𝐶Li
SF = (𝐶M)recov ery/(𝐶M)feed (6)

Separation factor essentially reflects the purity of lithium in the brine and the recovery

10
solution, and it can be intuitively seen how many times the lithium purity changes

before and after extraction.

Based on adsorption capacity

Recently, researchers developed a flow ELIP device based on a modified

commercial capacitive desalination device due to the cathode [32,33]. In order to obtain

the adsorption capacity of the electrode material for different cations, a conductivity

meter is placed at the water outlet to obtain the relationship of conductivity with time,

which can then be obtained by mathematical transformation. The adsorption capacity

of the electrode of flow ELIP device for different ions can not only reflect the

adsorption performance of different ions, but also indirectly reflect the selectivity of the

electrode materials to lithium ions. The selectivity of lithium ion to other coexisting

ions can be calculated with the following formula.

𝑄Li
𝛼Li
M = 𝑄M (7)

Where QLi and QM respresent adsorption capacity of Li and other coexisting ions

respectively. Therefore, this method can be used to evaluate the selectivity of electrode

materials to lithium ions [32,34].

Although there are many formulas for calculating selectivity at present, each

formula has its advantages and disadvantages. For ELIP device, the selectivity of

lithium ions is not only related to the concentration of ions in brine and recovery

solution, but also can be greatly influenced by other factors such as the applied current,

voltage, adsorption and desorption time, and device type. However, there is no formula

that can take all these factors into account currently, so if the academic community can

11
provide all these parameters in their research, it will be very helpful to compare

different work.

2.2.2 Energy consumption

Compared with other lithium recovery methods, the energy consumption will be a

challenge for ELIP, so it is important to reduce the energy consumption. The consumed

energy of per mole Li+ can be calculated by circular integration of voltage profile. The

formula is as follows:
∫Δ𝐸 d𝑞
𝑊= 𝑉𝐶Li
(8)

Similarly, the consumed energy at constant voltage can be calculated using the

following formula:
𝑡
MLiE∫0𝐼(𝑡 )d𝑡
𝑊= 3.6𝑄𝑚
(9)

Where W is the energy consumption (Wh mol-1), MLi is the molar mass of Li (g

mol-1), Q is the extraction capacity of the Li and m is the effective mass of the electrode.

The energy required for the peristaltic pump and electrode transfer processes is not

further considered here.

The energy efficiency is an important parameter reflecting the energy utilization

rate. The calculation formula of energy efficiency is as follows:

𝑄theo
𝜂= 𝑊 × 100% (10)

The theoretical energy consumption (𝑄theo) can be derived through the following

process [3]:

12
Fig. 3. The schematic diagram of Li recovery process.
Fig. 3 shows the schematic diagram of Li+ recovery process. The Gibbs free energy

change for the transferring of species i from system 1 to system 2 is equal to the sum

of the Gibbs free energy changes of the two systems in isothermal conditions.
𝛥𝐺𝑖
𝑅𝑇 = 𝑉1𝑐1,𝐹,𝑖𝑙𝑛 𝑐1,𝐹,𝑖 ― 𝑉1𝑐1,𝐼,𝑖𝑙𝑛 𝑐1,𝐼,𝑖 + 𝑉2𝑐2,𝐹,𝑖𝑙𝑛 𝑐2,𝐹,𝑖 ― 𝑉2𝑐2,𝐼,𝑖𝑙𝑛 𝑐2,𝐼,𝑖 (11)

Where V represents the volume, ci represents the concentration of the species i, the

subscript 1 and 2 refer to the system 1 and 2, respectively, and the subscript I and F

refer to the initial and final state, respectively. The mass of the transferred species

conforms to the following equation:

𝑉1𝑐1,𝐼,𝑖 ― 𝑉1𝑐1,𝐹,𝑖 = 𝑉2𝑐2,𝐹,𝑖 ― 𝑉2𝑐2,𝐼,𝑖 = Δ𝑛𝑖 (12)

Where Δni represents the total transferred amount of species i. Substituting equation (12)

into equation (11) and performing mathematical simplification, the following equation

can be obtained:
𝛥𝐺𝑖 𝑐1,𝐹,𝑖 𝑐2,𝐹,𝑖 𝑐2,𝐹,𝑖
𝑅𝑇 = 𝑉1𝑐1,𝐼,𝑖𝑙𝑛 𝑐1,𝐼,𝑖 + 𝑉2𝑐2,𝐼,𝑖𝑙𝑛 𝑐2,𝐼,𝑖 +𝛥𝑛𝑖𝑙𝑛 𝑐1,𝐹,𝑖 (13)

If the total transferred amount of species i is small with respect to its initial amount in

system 1 and big with respect to its initial amount in the system 2, then equal (13) can

13
be simplified with the following formula [3]:
𝑐2,𝐹,𝑖
𝑄theo = Δ𝐺𝑖 = Δ𝑛𝑖𝑅𝑇𝑙𝑛 𝑐1,𝐹,𝑖 (14)

So, coulombic efficiency (𝜂) can be calculated from the following formula:
𝑐2,𝐹,𝑖
𝑉𝐶LiΔ𝑛𝑖𝑅𝑇𝑙𝑛 𝑐
1,𝐹,𝑖
𝜂= ∫Δ𝐸d𝑞
× 100% (15)
𝑐2,𝐹,𝑖
3.6𝑄𝑚Δ𝑛𝑖𝑅𝑇𝑙𝑛 𝑐
1,𝐹,𝑖
𝜂= 𝑡 × 100% (16)
MLiE∫0𝐼(𝑡)d𝑡

2.2.3 Adsorption capacity

The inserted capacity and extracted capacity are key parameter reflecting the

ability of the electrode to extract lithium ions, and can be calculated using the following

formula [23]:
𝑐0𝑉0 ― 𝑐s𝑉s
―1
𝑄insert = 𝑊e = mg ⋅ gadsorbent (17)

Where co, Vo, cs, Vs and We represent initial concentration of Li+ in source solution,

initial volume of source solution, final concentration of Li+ in source solution, final

volume of source solution and molar mass of adsorbent, respectively. This formula

calculates the inserted capacity based on the change of lithium concentration in brine

before and after extraction. Similar to the calculation formula of the inserted capacity,

the extracted capacity can be calculated by the following formula:

𝑐s𝑉s ― 𝑐0𝑉0
―1
𝑄extrct = 𝑊e = mg ⋅ gadsorbent (18)

Where c and V represent concentration and volume in recovery solution, respectively.

14
2.2.4 Cyclic stability

The cycle life of the electrode can be calculated using the following four formulas (19)

–(22): [22,23,27,28,35,36]

𝐼𝑝eak ― 𝑛
Retention of peak current = 𝐼𝑝𝑒𝑎𝑘 ― 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 × 100% (19)
𝐼𝑖𝑡 ― 𝑛
Retention of current = 𝐼𝑖𝑡 ― 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 × 100% (20)
𝐶𝑛
Retention of capacity = 𝐶𝑖𝑛𝑖𝑡𝑖𝑎𝑙 × 100% (21)
𝑄𝑛
Retention of adsorption capacity = 𝑄𝑖𝑛𝑖𝑡𝑖𝑎𝑙 × 100% (22)

Formulas (19)–(22) are calculated based on cyclic voltammetry test, i–t test,

constant current charge and discharge test and extraction and release experiment.

Although the cyclic voltammetry test, i–t test and constant current charge and discharge

test can reflect the cyclic stability of the electrode to a certain extent. However, these

characterization methods do not accurately reflect the extraction amount and selectivity

of lithium ions by the electrodes in actual extraction and release. In addition, different

researchers use different cyclic stability test methods, and even many researchers do

not provide electrode cycle stability data, which makes comparison between different

research work difficult. Therefore, if the academic community can provide the cycle

stability data based on the adsorption amount of the ELIP electrode, it will be beneficial

to the development of this field.

3. Electrode materials

The performance of electrochemical lithium recovery mainly depends on two

15
electrode materials: one is the Li–insertion material, another is used to form the return

circuit or to capture corresponded negative ions(counter electrode) [37].The former is

common to those utilized as cathode electrodes in Li–ion battery. In this part, electrode

materials used in ELIP are reviewed.

3.1 Working electrode

When lithium–ion is inserted into the crystal structure of the lithium–ion

intercalation material, redox reaction will occur in the bulk electrode. Generally

speaking, aqueous lithium–ion battery cathode materials based on the intercalation

mechanism can be used for ELIP. A variety of lithium–ion intercalation materials have

been developed for aqueous lithium–ion batteries. Stable potential window and the

working redox potential of water and various lithium insertion materials are shown in

Fig. 4. The materials whose working potential lies between the H2 and O2 evolution

potentials are suitable for the aqueous Li ion battery. In addition, the electrode materials

should be carefully selected according to the pH value, which is closely related to H2

and O2 evolution potential in aqueous system [38]. Based on the above analysis, among

the common electrode materials for lithium–ion batteries, only the parts marked in

green in Fig. 4 are suitable for working in aqueous system. In order to ensure the

selectivity of the electrode material to lithium ions, the working electrode suitable for

use in ELIP is usually the cathode materials of the lithium ion battery. Therefore,

LiFePO4, LiMn2O4 and LiV3O8 are suitable for using as the working electrode of ELIP.

16
Fig. 4. Potential diagram of the stable potential window of water and the working redox

potential of various materials. Reproduced with permission from reference

[38].Copyright 2014 American Chemical Society.

In 1983, Thackeray et al. first proposed using spinel lithium manganate for

lithium–ion batteries [39]. Subsequently, lithium manganate has been extensively

studied as electrode material for lithium–ion batteries. Different particle sizes, different

morphology, surface modification, and doped lithium manganate have been reported.

Spinel lithium manganate is the first electrode material used in ELIP [16,22]. LiMn2O4

belongs to the spinel structure with a spatial group of Fd3m, in which lithium and

manganese ions occupy 8a tetrahedron and 16d octahedron of cubic tightly packed

oxygen ions, respectively [40–43]. During the charging process, lithium ions are

removed from LiMn2O4 to form –MnO2, and LiMn2O4 is formed again during

discharge. The mutual transformation of LiMn2O4 and –MnO2 realizes the extraction

and release of lithium ions. LiMn2O4 and –MnO2 electrodes are two different states of

the same electrode. There are three mechanisms of recovering lithium ions from

brine/sea water by –MnO2 electrode, which are ion–exchange mechanism, redox

17
mechanism and complex mechanism. According to the complex mechanism, during the

lithium recovery process of –MnO2, not only Li–H exchange occurs, but also the

disproportionation reaction will occur at the octahedral position at 16 d, generating Mn

Ⅳ and MnⅡ. Because MnⅡ is water–soluble, it leads to the dissolution of manganese

ions, the collapse of spinel structures and the reduction of capacity [44].

Fig. 5. (a) The relationship between lithium–ion concentration and charging and

discharging curves. Reproduced with permission from reference [35]. (b). CV curves

of LiMn2O4 at different scan rate. Reproduced with permission from reference [35].

Copyright 2018 Wiley.

Fig. 5(a) shows the relationship between lithium–ion concentration and time in the

charging and discharging process [35]. During the discharge process, the lithium–ion

enters the LiMn2O4 electrode directionally to complete the recovery process. During

the charging process, the lithium ions are released from the LiMn2O4 electrode to

complete the desorption process. Some lithium ions will be embedded in the tetrahedral

position 8a, while Mn will be changed from Mn Ⅳ to Mn Ⅳ 0.5Mn Ⅲ 0.5 forming

Li0.5Mn2O4 during the discharge process. Subsequently, more lithium ions will be

embedded in the 8a site of the lattice. At the same time, Li0.5Mn2O4 will further

18
transform to the low–valence–state to form LiMn2O4. The corresponding reaction

process can be represented by the following two equations [35]. The two pairs of

obvious redox peaks in CV curves (Fig. 5b) confirmed the above mechanism further.

4λ ― MnO2 +Li + + e ―  2Li0.5Mn2O4 (23)2Li0.5Mn2O4 +Li +

+ e ―  2LiMn2O4 (24)

During the charging process, the oxidation of manganese ions and the release of

lithium ions occur simultaneously, which is equivalent to the reverse process of the

discharge process. In 1997, Padhi proposed using lithium iron phosphate as the cathode

material of lithium–ion battery [45]. After that, lithium iron phosphate has attracted

much attention from researchers because of its low price and environmental friendliness.

Lithium iron phosphate is a typical orthogonal olivine structure belongs to pama space

group, and its cell parameters are a= 0.6008 nm, b=1.0334 nm, c=0.4693 nm. The

whole crystal structure is composed of PO4 tetrahedron, FeO6 and LiO6 octahedron. It

has a one–dimensional diffusion channel that allows lithium ions to be inserted into the

octahedron. The reaction equations during charging and discharging process are as

follows:

FePO4 +Li + + e ―  LiFeO4 (25)

In this process, LiFePO4 and FePO4 are involved in the reaction. During the charging

process, Li migrates from the FeO6 layer of LiFePO4 to form FePO4. On the contrary,

Li+ will return to the positive pole and form LiFePO4 phase in discharging process.

Larger lattice distortion of lithium iron phosphate will not form during the transition of

two phases, so it has a longer cycle life. Extensive research on lithium iron phosphate

19
in lithium–ion batteries provides a strong theoretical support for ELIP [46,47]. In 2012,

Pasta proposed an ELIP system based on lithium iron phosphate for Li recovery [3].

The details are described in 4.3.

In recent years, with the rapid development of lithium–ion battery technology,

many new electrode materials have been developed which provide strong theoretical

support for ELIP. Fig. 6(a) shows the Li–insertion materials applicated in ELIP recently.

In addition to the traditional lithium manganate and lithium iron phosphate, doped

electrode materials and metal organic frames have been reported [27,28,48–50].

However, compared with the traditional electrode materials, the doped electrode

materials have a lower adsorption capacity of lithium ions. Metal organic frame

materials (HKUST–1) have a lower selectivity of lithium ions (Fig. 6b). Increasing the

adsorption capacity of doped electrode materials and improving the selectivity of metal

organic frame materials should be the main research focus in the future work.

Fig. 6. The proportion (a) and adsorption capacity (b) of different lithium intercalation

materials. (All data acquired from mathematical statistics of published literature listed

in Table 2)

20
3.2 Counter electrodes

Counter electrode is an important component of the ELIP devices. However, most

of the researches focus on the development of lithium selective electrode and pay less

attention to counter electrode. There are two functions of counter electrode: (1) capture

anions and keep electrical neutral of the solution; (2) form a closed circuit. Therefore,

the opposite electrode will have a great influence on the energy consumption and

adsorption capacity of the ELIP device. As can be seen from the Fig. 7, there are five

types of counter electrodes used in the ELIP device: carbon materials, metal, prussian

blue analogue, conducting polymer and redox couple.

20.51% 2.56%
12.82%

7.69%
7.69%

2.56%
2.56%
2.56%
2.56%

38.46%

Zn Pt I2 PPy SS
AC Ag NiHCF BDD PANI

Fig. 7. The proportion of different materials of counter electrode. (All data acquired

from mathematical statistics of published literature listed in Table 2)

Compared with other counter electrode materials, activated carbon is widely used

by researchers due to its low cost, environmental friendliness, good electrical

conductivity and large specific surface area [51,52]. However, activated carbon has no

selectivity for lithium ions, and the activated carbon electrode must be matched with a

corresponding ion exchange membrane to prevent lithium ions from being adsorbed on

the electrode [32,34]. As early as 1991, Kanoh et al. proposed using of platinum

21
electrode in electrochemical lithium recovery process [16,22]. Water will be

decomposed in platinum electrode and consume more energy in this process.

Meanwhile, platinum electrode is expensive, which limits its commercial application.

Unlike the platinum electrode, the silver electrode can capture the chloride ions in the

solution to form AgCl, which facilitates the embedding of the lithium ions into the

crystal lattice of the lithium ion adsorbent, thus enhancing the extraction performance

[27,28]. It is worth noting that when the concentration of chloride ions is too high, the

silver electrode is prone to form complexes, resulting in electrode loss [53]. Compared

with silver and platinum, the price advantage of zinc electrode and stainless steel

electrode is obvious. During charging and discharging, the zinc electrode or stainless

steel electrode will react as follows: M ↔ Mn+ + ne-. Conductive polymer is a scientific

field newly appearing in the period of the 21th century. At present, the conductive

polymers used in ELIP mainly include polypyrrole, polyaniline and doped conductive

polymers [44,54]. Prussian blue analogues are more prone to Na insertion than lithium,

so they are widely used as lithium repellent electrodes in electrochemical lithium

extraction [55,56]. Kim et al. suggested a new counter electrode that place platinum in

acetonitrile solution containing I-/I3-. Unfortunately, the authors did not elaborate

further on the electrode [29].

4. Electrochemical systems

The core components of ELIP system are the positive electrode, negative electrode,

separator and electrolyte. The different combinations between them constitute a variety
22
of ELIP devices. Although different types of devices all use electric fields to assist in

the process of Li recovery, the reactions that occur on the electrodes and the direction

of ions movement in the solution are different, resulting in huge differences in recovery

performance. In the past 20 years, researchers have conducted a lot of research on ELIP

systems. According to the type of reaction, there are five types of ELIP systems, namely:

Water split battery system, Rocking chair battery system, Salt–capturing battery system,

Ion exchange battery system and Hybrid capacitor system. As can be seen from Table

S2, compared to other ELIP systems, the salt–capturing battery system and the hybrid

capacitor system have obvious advantages. The detailed reported results of various

ELIP systems are summarized in Table 2.

23
Table 2. A summary of ELIP–based electrochemistry lithium recovery technology.
N Working Counter Configuration Feed solution Electrical Adsorption Energy Selectivity Cycling Referen
o. electrode electrode behavior capacity (mg g-1) (Wh mol-1) performance ce

Water split battery

 –MnO2 Pt 3 electrodes 10 mM LiCl Constant voltage No report No report High selectivity 85% (4 cycles) [16]
(stationary)
 –MnO2 Pt 3 electrodes Geothermal water Constant voltage 11 33 High selectivity 100% (5 cycles) [22]
(stationary)
 –MnO2 Pt 3 electrodes 30 mg/L LiCl Constant voltage 35.2 No report Li/Na=46 99% (5 cycles) [57]
(stationary) (–0.2 V)
4 LiMn2O4 Boron– 2 electrodes Factory waste Constant current 22.7 61 Li/Na=88 Slight degrease [58]
doped (stationary) water (25–125 mA) (5 cycles)
diamond
5 HKUST–1 Stainless No report 5 ppm Li+ Constant voltage 37.55 No report High No report [48]
steel

Salt capture battery

6 LiFePO4 Ag 2 electrodes High Li/Na Constant current No report 1 High selectivity for No report [3]
(stationary) (0.5 mA/cm2) Na+
 –MnO2 Ag 2 electrodes Simulate real Constant current No report 1 High selectivity from 87% (20 cycles) [31]
(stationary) brine (0.5 mA/cm2) the second cycle
8 LiFePO4 Ag 2 electrodes 1 M LiCl Constant current No report 4.29 Depends on current No report [59]
(stationary)
9 LiMn2O4 PPy 3 electrodes Real brine Constant voltage No report 5-10 No report 78% (100 [54]
(stationary) (0.6–1.1 V) cycles)

24
10 Li1- Ag 3 electrodes 30 mM Li+, Na+, Constant current 10.92 2.6 Depends on test No degrease (20 [27]
Ni0.33Co1/3Mn1/3O
x (stationary) K , Mg , Ca
+ 2+ 2+ (0.25 mA/cm ) 2 conditions cycles)

11 Li1-xMn2O4 LiMn2O4 3 electrodes Real brine Constant voltage No report No report No report No report [60]
(stationary) (1.2 V)
12 LiMn2O4 PPy 3 electrodes Real brine Constant voltage No report No report No report No report [54]
(stationary) (0.6-1.1 V)
 –MnO2 Ag 2 electrodes (flow) Concentrated sea Constant current No report 21.3 No report No report [61]
water (0.5 mA/cm ) 2

14 Li1-xNi0.5Mn1.5O4 Ag 3 electrodes 30 mM Li , Na ,
+ + Constant current 9.002 1.29–1.44 High 100% (50 [28]
(stationary) K , Mg , Ca
+ 2+ 2+ cycles)
 –MnO2 Ag 2 electrodes 50 mM Li + Constant current 14 No report Li-Na) = 38.78, Li-K) = 82.8 (50 cycles) [30]
(stationary) (50 mA/g) 35.63, Li-Mg) =
29.04, Li-Ca) = 120.08
16 LixMn2O4 PANI 2 electrodes Real brine Constant voltage No report 3.95 Low selectivity for 78% (200 [44]
(stationary) （0.2–0.7 V） Na+ cycles)
17 LiMn2O4 Ag 2 electrodes 30 mM Li+, Na+, Constant current No report 4.14 No report 82.3% (100 [35]
(stationary) K , Mg , Ca
+ 2+ 2+ (50mA/g) cycles)
 –MnO2 Ag 2 electrodes Concentrated sea Constant current No report No report KLi/Na=724, No report [62]
(stationary) water KLi/Mg=373, KLi/Ca=158

Rocking chair battery

19 LiMn2O4 –MnO2 2 electrodes 30 mM Li+ Constant voltage 24.5 No report No report No decrease (30 [63]
(stationary) （0.75 V） cycles)
20 FePO4 LiFePO4 2 electrodes 200 ppm Li ， + Constant voltage 38.9 No report No report No report [11]
(stationary) 500 ppm Na+ (1 V)

25
21 FePO4 LiFePO4 2 electrodes Mg/Li=20, Constant voltage 38.93 No report (Li/Mg) = 7.26 87% (31 cycles) [23]
(stationary) 220 ppm LiCl (1 V)
22 FePO4 LiFePO4 2 electrodes 220 ppm Li , + Constant voltage 24.1 No report Reduce Mg/Li from 100% (16 [36]
(stationary) 3675 ppm Na+, (1 V) 493 to 0.30, Na/Li cycles)
3792 ppm K+ from 16.7 to 0.19

23 FePO4 LiFePO4 2 electrodes 200 ppm Li+, 500 Constant voltage 38.6 No report Depends on voltage 100% (20 [24]
(stationary) ppm Na + (0.25 V) cycles)
24 Li1-xMn2O4 LiMn2O4 2 electrodes Simulated brine Constant voltage 34.1 18–19 (Li-Na) = 300, (Li-Mg) = Slight degrease [64]
(stationary) (1.2 V) 70, (Li-Ca) = 110 (5 cycles)
25 H1.6Mn1.6O4 H1.6Mn1.6O4 2 electrodes Mixture of Li+, Constant voltage 38.78 No report Li/Na=10.39, 99% (5 cycles) [25]
(stationary) Na+, Mg2+ Li/Mg=10.23
26 Li1-xMn2O4 LiMn2O4 2 electrodes (flow) Real brine Constant current 35 0.56 No report No report [65]
27 FePO4 LiFePO4 3 electrodes Geothermal water Constant voltage 17.1 No report No report No report [66]
(stationary)

Hybrid capacitor
28 LiMn2O4 AC 2 electrodes (flow) 60 ppm LiOH Constant voltage 8.7 No report No report No report [67]
(3.5 V)
29 LiMn2O4 AC 2 electrodes (flow) 50 ppm LiOH Constant voltage 1.36 No report No report No apparent [68]
(1 V) change after 5
cycles
 –MnO2 AC 2 electrodes (flow) 10 mM LiCl Constant voltage 20 No report No report No report [69]
(1 V)
31 LiMn2O4 AC 2 electrodes (flow) 30 mM Li , Na ,+ + Constant current No report 4.2 Very high 96% (50 cycles) [70]
K , Mg , Ca
+ 2+ 2+ (0.5 mA/cm ) 2

26
32 LiMn2O4 AC 2 electrodes (flow) Simulate real Constant voltage 0.00243 3.33 Li+＞ More than [71]
brine (1 V) Mg >Ca >K >Na
2+ 2+ + + 100% (after 5
cycles)
33 LiMn2O4+Li4Ti5O AC+PPy 2 electrodes (flow) 10 mM Li+ Constant voltage 36.9 No report Li+ 36.9 mg/g, Na+ No report [72]

12 (0.7 V) 18.09 mg/g, K+ 9.07

mg/g
34 LiMn2O4+Li4Ti5O AC 2 electrodes (flow) 10 mM Li+ Constant voltage 34.2 0.56 Li+ 34.2 mg/g, Na+ 9.8 More than [26]

12 mg/g, K 8.6 mg/g

+ 100% (after 14
cycles)
35 LiNi0.038Mo0.012Mn AC 2 electrodes semi 1 M Li , Na , K .
+ + + Constant current 14.4 7.91 Li 97.2% No decrease [49]

1.95O4 flow) Mg , Ca
2+ 2+

36 Li–FeO–Mn2O3 AC 2 electrodes (flow) 30 ppm Li+, 6000 Constant voltage 32 No report 16 mg/g Na+, 0 mg/g No decrease (30 [32]
ppm Na + K + cycles)
37 LiNi0.6Co0.2Mn0.2 AC 2 electrodes (semi Real brine Constant current 13.84 1.4 High No decrease (30 [50]
O2 flow) (0.5–1.25 mA) cycles)
38 LiMn2O4+Li4Ti5O AC 2 electrodes (flow) Pure LiCl Constant voltage 30 No report No report 96% (3 cycles) [52]

12

39 LiMn2O4+Li4Ti5O AC 2 electrodes (flow) Geothermal brine Constant voltage 800 24.91 KCl 16 mg/g, NaCl 11 No apparent [73]

12 mg/g change after 3

cycles
40 LiMn2O4+Li4Ti5O AC 2 electrodes (flow) 10 mM LiCl Constant voltage 36 0.102–0.157 KCl 16 mg/g, NaCl 11 No apparent [34]

12 （0.25–1.5 V） kWh/m 3 mg/g change after 3

cycles
41 LiMn2O4+Li4Ti5O AC 2 electrodes (flow) Geothermal brine Constant voltage 800 1.27 Highest selectivity for No apparent [51]

12 Li+ change after 3

cycles

27
Ion exchange battery
42 LiFePO4 I2/I3- 3 electrodes 500 mM Na+, Constant current No report No report Reduce Li/Na from 100% (5 h, [29]
(stationary) 5mM Li + (1.3 mA g )
-1 0.01 to 43 based on i–t
curve)
 –MnO2 KNiFe(CN) 2 electrodes (flow) Simulate real Constant current No report No report No report No report [74]

6 brine
44 LiFePO4 KNiFe(CN) 2 electrodes Real brine Constant current No report No report Increase Li+ from 98.6% (68 [55]

6 (stationary) (0.5 mA/cm )2 4.13% to 11.2% cycles)

 –MnO2 KNiFe(CN) 2 electrodes 0.1 M Li + Constant current No report 3.6 Li/Na =57， No decrease [75]

6 (stationary) Li/Mg=1600 (100 cycles)

46 LiMn2O4 Zn 2 electrodes Real brine Constant current No report 6.3 Low selectivity for 73% (100 [76]
(stationary) (0.5 mA/cm )2 Na + cycles)
47 LiMn2O4 KNiFe(CN) 2 electrodes (flow) 1 mM LiCl and Constant current No report No report 94% Li solution No report [77]

6 100mM NaCl
48 LiMn2O4 KNiFe(CN) 2 electrodes Real brine Constant current 27.2 1.76 High 37.4% (200 [78]

6 (stationary) cycles)

28
4.1 Water split battery system

In this kind of system, when Li+ is captured by working electrode, H2O will be

split at the counter electrode simultaneously. Kanoh et al report a rechargeable battery

system consisting of –MnO2 electrode and Pt electrode [16,22]. The principle of this

system is shown in Fig. 8. During charging, lithium ions are intercalated into the crystal

lattice of –MnO2, and the reactions of Mn Ⅳ to Mn Ⅲ occur simultaneously. Since the

counter electrode is inert platinum and φθ（O2/H2O） < φθ（Cl2/Cl ― ）, the reaction on

the counter electrode is:

1 1
2H2O ― e ―  4O2 + H + (26)

The total electrode reaction can be expressed by the following formula:

1 1
2λ ― MnO2 + 2H2O + Li +  4O2 +LiMn2O4 + H + (27)

Similarly, the lithium ion removal reaction occurs during the discharge process, which

corresponds to the reverse reaction during the charging process.

Fig. 8. The principle of water split battery system, (a)charge, (b) discharge.

Kanoh et al. found that the extraction amount of lithium ions in 0.1 mM lithium

chloride solution is very small, and the extraction capacity increases with the increase

of the concentration of the lithium chloride solution. The presence of alkaline earth
29
metal ions has a strong inhibitory effect on the extraction of lithium ions. Kim et al.

improved the system during the treatment of wastewater from the battery recycling

plant [58]. They use MnO2 as the working electrode and boron–doped diamond (BDD)

as the counter electrode in the recovery process of lithium ions. Organic pollutants in

wastewater can also be degraded by this system while extracting lithium ions. During

lithium ions release process, they used stainless steel as the counter electrode. The

reaction on stainless steel electrode was consistent with the reaction on the platinum

electrode proposed by Kanoh et al. A lithium solution with a purity of 98.6% can be

obtained, and organic pollutants in wastewater are reduced by 65% through this system.

As an adsorbent material with excellent performance, MOF has attracted extensive

attention from researchers. Wang et al. deposited a new electroactive polypyrrole (PPy)

–HKUST–1 metal organic framework (MOF) composite membrane electrode [48]. Due

to the sieve function of the voids and the excellent affinity of the membrane for Li ions,

the adsorption capacity of the composite membrane electrode to lithium ions can reach

37.55 mg/g in 25 minutes. Based on the research above, with the continuous deepening

of the research on the working electrode of the water splitting battery system, the

extraction performance of lithium ions has been continuously improved. However, this

system uses platinum or stainless steel as counter electrode, water decomposition will

occur during the extraction or release process, which further consumes energy and is

not suitable for industrial applications.

30
4.2 Rocking chair battery system

Aqueous lithium–ion batteries have made considerable progress since Dahn first

proposed water–based lithium–ion batteries in 1994 [79–81]. The aqueous lithium–ion

battery combines two lithium insertion materials, and the electrolyte uses a neutral

lithium salt solution. During charging and discharging, lithium ions move back and

forth between the two electrodes, so it is called the rocking chair battery [82,83].

Inspired by this, Zhao et al. used LiFePO4/FePO4, as the electrode material which is

stable in aqueous solution. For the first time, the rocking chair battery system was

applied to ELIP (Fig. 9) [23].

+ _
LiFePO4 FePO4
Permselective
membrane

Cl-
Li+ Li+
Li+
Cl-
Li+ Li+
Supporting Cl-
Li+
Li+
Li+ Brine
electrolyte Cl- Li+
Li+
Cl- Li+
Li+
Li+

Fig. 9. The principle of rocking chair battery system. Reproduced with permission from

reference [23]. Copyright 2013 Elsevier.

By applying a voltage, Li+ in the brine is inserted into the negative electrode FePO4

31
to form LiFePO4. At the same time, the lithium in the positive electrode LiFePO4 is

released into the recovery solution. Meanwhile, the initial state can be obtained by

interchanged positions of the two electrodes. By continuously repeating the above

process, Li+ can be continuously extracted from the brine to recovery solution.

Experimental results show that when the Mg/Li ratio of brine is as high as 110, 25% of

lithium can still be extracted in one cycle. Lithium ions in brine can be concentrated to

432 ppm through 10 cycles, and the single extraction amount of the optimized electrode

is close to the theoretical capacity [24,36]. These results indicate that this new

technology is more likely to be commercialized than traditional methods. Similarly,

Zhao et al. used LiMn2O4/Li1-xMn2O4 electric pairs to design a rocking chair battery

system based on lithium manganate [64]. The researchers systematically studied the

effects of potential, temperature, and coexisting ions on lithium extraction, and using

this system to extract lithium from brine and concentrated seawater. At a voltage of 1.2

V, the adsorption capacity of lithium ions can reach 34.3 mg/g. It can still maintain high

extraction capacity and selectivity to lithium ions in simulated brine and concentrated

seawater. However, this system also has shortcomings: (1) the lithium manganate

electrode will slightly dissolve during charging and discharging, (2) the adsorption

capacity will decrease significantly after multiple cycles of use. At present, the

electrode materials used in aqueous lithium–ion batteries mainly include lithium cobalt

oxide, lithium nickel oxide, lithium manganate, lithium iron phosphate and lithium

titanate [84]. In theory, almost all electrode materials for aqueous lithium–ion batteries

have important reference value for ELIP, because the mechanism of ELIP based on

32
rocking chair battery system is similar to that of lithium–ion batteries. In short, the

rocking chair battery system has shown very good development prospects in ELIP.

Exploring rocking chair battery systems based on lithium nickelate, lithium vanadate,

lithium titanate and lithium cobaltate to optimize the experimental conditions, and to

select electrode materials with excellent performance for electrochemical lithium ion

extraction is of great significance.

4.3 Salt–capturing battery system

Unlike the previously mentioned electrochemical system, this system can capture

the corresponding anions while recovering lithium ions, avoiding the decomposition of

water on the counter electrode. This system is featured by high selectivity and low

energy consumption. A high–efficiency battery system consisting of a lithium–ion

capture electrode (LiFePO4) and a Cl- trap electrode (Ag) has also been proposed to

recover lithium from high Na/Li brine (Fig. 10) [3,59]. It converts sodium–rich brine

(Li/Na = 1: 100) into a lithium–rich solution (Li/Na=5: 1) with an energy of only 144

Wh/kg of Li recovered, using lithium iron phosphate as the lithium extraction electrode.

The salt–capturing system using –MnO2 as the lithium extraction electrode and Ag as

the counter electrode has also received extensive attention from researchers. Lee and

Kim et al. studied the lithium extraction performance of the –MnO2/Ag system under

static and flowing conditions, respectively [31,61]. Only a small amount of energy (3.07

Wh/g Li) was used to obtain a lithium–ion recovery solution containing 190 mM Li+,

and the purity of Li+ was increased to 99.0% by continuous operation of the system.

33
Traditionally, electrode of ELIP mainly was prepared by a slurry–coated method. This

method requires adding conductive carbon and binder to the slurry which will reduce

the electrode's selectivity for lithium ions. Xu et al. reported a self–supported –MnO2

film electrode in salt capture battery system [35]. In this study, Mn(OH)2 was first

deposited on titanium foil or graphite sheet by electrodeposition, and then Mn(OH)2

was oxidized to Mn3O4 in the air. Subsequently, lithium manganate with spinel

structure was synthesized by hydrothermal method. Finally, lithium is removed by

constant potential to form –MnO2. In a 30 mM lithium–ion solution, the adsorption

capacity of the self–supporting –MnO2 membrane electrode is twice that of slurry–

coated MnO2 electrode at a current density of 50 mA/g, which indicates that the self–

supporting membrane electrode has higher lithium extraction performance than slurry–

coated electrode.

34
 Step 1
Li+ Capture
LFP Ag LFP Ag

Brine
Exchange

Exchange
Solution

Solution
Step 4

Step 2
LFP Ag LFP Ag
Recovery
solution

Li+ Release
Step 3
Li+ Cl- Na+

Fig. 10. The principle of Salt–capturing battery system. Reproduced with permission

from reference [3]. Copyright 2012 Royal Society Chemistry.

With the continuous development of conductive polymers, new salt–capturing

electrodes such as polyaniline and polypyrrole have been developed to replace

expensive silver electrodes [44,54,60]. Cao and Marchini et al. found that salt–capturing

battery system using polymer as a chloride ion capturing electrode has a high selectivity

for lithium ions, but its cycle stability is slightly worse than that of traditional Ag

electrode [44]. Du et al. synthesized the electroactive lithium ion imprinted hybrid

membrane composed of λ–MnO2/PPy/PSS using unipolar pulse electrodeposition

technology [57]. Combined with polystyrene sulfonate (PSS), PPy exhibits cation

35
exchange properties and acts as a conductive crosslinking agent. In this hybrid

membrane, PSS–doped PPy serves as a cation exchange component, and λ–MnO2

serves as a recognition component. Due to the low ion transfer resistance and high

electrical driving force, the lithium ion adsorption capacity of the composite membrane

is as high as 35.2 mg/g. Inspired by binary and ternary lithium–ion batteries, Lawagon

et al. designed two lithium–ion extraction electrodes, Li1-xNi0.33Co0.33Mn0.33O2 and Li1-

xNi0.5Mn1.5O4, and using Ag as a counter electrode to examine the lithium–ion recovery

performance in detail [27,28]. Although the adsorption capacity of this system is much

lower than that of traditional lithium manganate and lithium iron phosphate, but it is

expected to obtain lithium chloride solutions close to industrial requirements through

multiple cycles and optimization of conditions.

In short, the salt–capturing battery system is an ELIP system with excellent

performance. Exploring high–performance chloride ion capture electrodes to replace

silver electrodes, while actively exploring new lithium–ion capture electrodes and

optimizing operating conditions should become the main research direction in the future.

4.4 Ion exchange battery system

According to the principle of electrical neutrality, when lithium ions are captured

by an electrode, anion will be captured or cation will be released on the counter

electrode at the same time [85]. The salt–capturing battery system described in 4.3

belongs to the former. Therefore, researchers have developed various counter

electrodes for balancing charges to ensure that the electrolyte is electrically neutral

36
[55,74,75]. Kim et al. dissolved iodine in acetonitrile solution, and made full use of the

reversibility of the I−/I3- redox couple to prepare a counter electrode with excellent

cycling performance [29]. In order to improve the lithium–ion extraction performance

of the ion exchange battery system, Kim et al. modified the carbon–coated LiFePO4

with dopamine to enhance the wettability of the LiFePO4 electrode. The

electrochemical process can be expressed by the following formula:

3I- + 2Li+ + 2FePO4  I3- + 2LiFePO4 (28)

When voltage is applied to the system, I- is oxidized to I3-, and at the same time,

Fe Ⅱ is reduced to Fe Ⅲ , and lithium ions are captured to form LiFePO4. When the

opposite voltage is applied, lithium ions are released, and the reverse reaction of the

above occurs. Test results show that this system has excellent lithium ion extraction

capacity and cycle performance. After one cycle, Li/Na can be enlarged by 4300 times

(Li/Na in the original solution = 0.01 and Li/Na on the final electrode = 43). In addition,

for seawater with extremely low Li concentration, this system can still operate normally.

Prussian blue and its analogs are coordination framework compounds closely related to

the structure of perovskite. Prussian blue and its analogs will undergo redox reactions

during the electrochemical insertion/extraction of various ions (Li+, Na+, K+, Mg2+, Ca2+,

etc.). Therefore, Prussian blue and its analogs have been widely studied in rechargeable

metal–ion battery [86–88]. Inspired by this, Trûcoli et al. proposed to use LiFePO4 as a

lithium–ion capture electrode and NiHCF as a lithium–ion repulsion electrode (Fig. 11)

[55]. The (de–)intercalation reaction of the system can be expressed by the following

formula:

37
FeⅢPO4 + M1/nKNiFeⅡ(CN)6 + LiCl  LiFeⅡPO4 + KNiFeⅢ(CN)6 + 1/nMCln (29)

In order to reduce the adsorption of lithium ions by the NiHCF electrode, the

concentration of Na+ and K+ must be controlled within an appropriate range.

1st Step

Li+ capturing
in LFP from
brines and
Na+- K+
releasing
from
NiHCF to
brines
High
volume

FeⅢPO4 NiHCFeⅡ Li+ LiFeⅡPO4 NiHCFeⅢ

4st Step Na+ 2st Step
Solution Increase of Reduction Solution
K+
exchange volume of volume exchange
Mg2+
Cl-

Low
volume
Li+releasing
to recovery
solution (sea
water or
FeⅢPO4 NiHCFeⅡ Atacama) LiFeⅡPO4 NiHCFeⅢ
and K+, Na+
capturing

3st Step

Fig. 11. The principle of ion exchange battery system. Reproduced with permission

from reference [55]. Copyright 2015 Wiley.

Experimental results show that the energy consumption of this system is close to that

using silver as the counter electrode, so NiHCF can be used as an alternative electrode

for Ag in ELIP. In addition, Trûcoli et al. also combined lithium manganate and NiHCF

into an ion exchange battery system, and systematically studied the lithium–ion

38
extraction performance [75]. The lithium manganate/NiHCF system shows a high

selectivity for lithium ions. The purity of lithium can be increased from 4.1% to 96%

in one cycle, and the time used is less than 7.4 hours. Kim et al. proposed the LiMn2O4–

Zn ion exchange battery system and studied its electrochemical lithium extraction

performance [76]. The system uses an anion exchange membrane to separate the

positive and negative electrodes, and the electrolyte on the side of the zinc electrode

uses zinc chloride solution. The extraction process of lithium ions is a spontaneous

reaction. When lithium ions enter the MnO2 lattice, zinc will be converted into zinc ions

and released into the solution to balance the negative charge formed by the lack of

lithium ions. When lithium ions are released into the solution, zinc ions are converted

to zinc. The experimental results show that the cheap metal zinc can replace the

expensive metal platinum, silver and unstable conductive polymer as a new type of

ELIP counter electrode. However, compared with other ELIP systems, the energy

consumption of the system is greater. Optimizing the experimental conditions of the

system and improving the reversibility of the zinc electrode will help solve this problem.

4.5 Hybrid capacitor system

In recent years, the development of hybrid capacitor desalination (HCDI) and

membrane capacitor desalination (MCDI) technology has provided a new idea for ELIP

[89–92]. Since the traditional lithium ion sieve adsorption process must be treated with

acid during the desorption process, it will cause certain corrosion to the equipment. At

the same time, acid–treating will also cause the dissolution loss of the adsorbent. To

39
solve this problem, Ryu et al. proposed an electric field assisted desorption process

[67]. Activated carbon (used as counter electrode), adsorbent (working electrode), and

the flowing low–concentration lithium solution (electrolyte) can be assembled into an

electric field assisted desorption device to release Li+. The two electrodes are separated

by an anion exchange membrane to prevent the lithium ions desorbed on the adsorbent

from being re–adsorbed by the activated carbon electrode. The results show that

although the resolution is only 45% of the traditional desorption method, the desorption

process does not require the use of hydrochloric acid, which is a green and

environmentally friendly new technology [33,68,71]. When electric field is applied to

the two electrodes of the electrolytic cell, the lithium ions will move to the negative

electrode since lithium ion is positively charged. If a lithium–ion sieve is coated on the

negative electrode, the electric field may accelerate the adsorption process. Siekierka

et al. adopted titanium–doped lithium manganate as an adsorbent and a new type of

anion exchange membrane–coated activated carbon as a counter electrode to adsorb

lithium ions in flowing brine [32,34,51,52,73]. Under optimized conditions, the

adsorption capacity of the system for lithium ions can reach 30 mg/g, and the current

efficiency exceeds 90%. Excitingly, this system can directly extract and release lithium

ions with a desorption efficiency of up to 96%. Because the system uses a flow–type

ELIP process, which is similar to the device required for industrialization, it has good

application prospects. In order to ensure the selectivity of the electrode to lithium ions,

it is usually necessary to combine a high–performance ion exchange membrane.

However, high–performance ion exchange membranes are expensive and have a short

40
service life.

Fig. 12. The principle of hybrid capacitor system. Reproduced with permission from

reference [49]. Copyright 2019 Elsevier.

In order to solve this problem, Zhao et al. proposed semi–flow

LiNi0.038Mo0.012Mn1.95O4(LNMMO)/AC system for lithium–ion recovery (Fig. 12) [49].

Zhao et al. first synthesized LNMMO with perfect crystal structure and morphology by

high–temperature solid–phase synthesis and then prepared electrode by mixing

LNMMO, activated carbon and binder according to a certain ratio. In brine and pure

lithium chloride solution, two pairs of obvious redox peaks appear in the CV curve,

indicating that the system has undergone a two–step reaction during the extraction

process. The reaction process are as follows [49]:

LiNi0.03Mo0.01Mn1.96O4 - xe- - xLi+  Li1-xNi0.33Mo0.01Mn1.96O4 (30)

41
Li1-xNi0.03Mo0.01Mn1.96O4 - ye- - yLi+  Li1-x-yNi0.33Mo0.01Mn1.96O4 (x+y<1) (31)

With a LNMMO/AC system, lithium was selectively recovered with a purity of 97.2%

and adsorption capacity of 14.4 mg/g. Although the activated carbon electrode has a

high adsorption capacity, it is not selective for lithium ions and usually used as counter

electrode after modification.

5. Conclusion and prospect

Electrochemical recovery of lithium from brine by ELIP to ensure a reliable supply

of lithium has become an increasing trend. As an emerging technology, the research on

ELIP is in infant. In summary, three aspects should be further paid deep attention：

1. At present, researchers have proposed five kinds of ELIP systems. Compared with

the other three types ELIP systems, the salt–capture battery system and the hybrid

capacitor system have lower energy consumption and do not need to use expensive ion

exchange membranes, which has greater advantages. However, the existing ELIP

systems still have a lot of room for improvement in terms of selectivity, energy

consumption, and adsorption capacity. The operating conditions of these five ELIP

systems, such as voltage, current, brine concentration, and recovery liquid

concentration, should be optimized to obtain the best recovery conditions. The flow

type ELIP system is closer to industrialized lithium recovery device. At present, the

research on the flow ELIP is still in the laboratory stage. The research on its energy

consumption mainly considers the consumption of electricity. However, in practical

applications, the mechanical energy required to drive the liquid flow is also an
42
important factor that cannot be ignored. It is of great significance to optimize the

process and reduce the mechanical energy required by the flow ELIP system.

2. With the rapid development of material chemistry and lithium–ion batteries, many

emerging electrode materials have been continuously studied, but few electrode

materials are used for ELIP. Finding electrode materials with high selectivity to lithium

ions, low energy consumption, wide working redox potential in aqueous electrolytes,

environmentally friendly, and inexpensive electrode materials is of great significance

to ELIP. According to the stable potential window of water and the potential diagram

of the working redox potential of various materials, lithium vanadate can also be used

as the working electrode material of ELIP. Further exploring the role of lithium

vanadate in ELIP, it is possible to develop a higher performance ELIP system. Other

electrode materials that are stable in aqueous electrolytes, such as V2O5, NiHCF,

CuHCF and some organic polymers can be used as the counter electrode of ELIP.

3. Although detailed calculations of the thermodynamic energy consumption of ELIP

system have been carried out in some literatures, the study of kinetic energy

consumption is not comprehensive. Compared with the thermodynamic process of

ELIP, it is more important to study the dynamic process of ELIP. Because kinetic

energy consumption can be reduced by optimizing experimental conditions.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant

numbers 21878133, 21908082 and 21722604), the Natural Science Foundation of

43
Jiangsu Province (BK20190854), the China Postdoctoral Science Foundation

(2020M671364), the Postgraduate Research & Practice Innovation Program of Jiangsu

Province (KYCX19_1622) and the Science & Technology Foundation of Zhenjiang

(GY2020027).

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Graphical Abstract

This review provides a systematic summary of electrochemical lithium ion pumping

(ELIP) for lithium recovery, aiming at helping to understand the working mechanism

of ELIP and guiding the design of advanced electrochemical Li recovery devices.

Declaration of interests

☒ 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.

47
☐The authors declare the following financial interests/personal relationships which

may be considered as potential competing interests:

Highlights:
 Basic theory of electrochemical lithium ion pumping was summarized.
 Lithium recovery systems of electrochemical lithium ion pumping are reviewed.
 Various types of positive and negative materials are summarized in detail.
 The main challenges and future directions of electrochemical lithium ion pumping
are discussed.

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49