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Recent Advances in Magnesium/Lithium Separation and Lithium Extraction

Technologies from Salt Lake Brine

Ying Sun, Qi Wang, Yunhao Wang, Rongping Yun, Xu Xiang

PII: S1383-5866(20)32281-4
DOI: https://doi.org/10.1016/j.seppur.2020.117807
Reference: SEPPUR 117807

To appear in: Separation and Purification Technology

Received Date: 10 June 2020

Revised Date: 1 August 2020
Accepted Date: 11 September 2020

Please cite this article as: Y. Sun, Q. Wang, Y. Wang, R. Yun, X. Xiang, Recent Advances in Magnesium/
Lithium Separation and Lithium Extraction Technologies from Salt Lake Brine, Separation and Purification
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Recent Advances in Magnesium/Lithium Separation and Lithium

Extraction Technologies from Salt Lake Brine

Ying Sun, Qi Wang, Yunhao Wang, Rongping Yun, Xu Xiang*

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical

Technology, Beijing 100029, China

Corresponding author: [email protected] (X. Xiang)

ABSTRACT

Over the past few decades, the demand for lithium resources has increased significantly with

the rapid development and extensive application of lithium-ion batteries. Extracting lithium from salt

lake brine is of significance because of its abundance in brines. Numerous endeavours have addressed

the challenges of magnesium/lithium separation from salt lake brines having high Mg/Li ratios with

the aim of efficiently and sustainably recovering lithium resources. This review focuses on the latest

advances in magnesium/lithium separation and lithium recovery from salt lake brines, including

extraction, adsorption, membrane, and electrochemical methods as well as reaction-coupled

separation technology. The features and adaptabilities of various methods are analysed from the

viewpoint of the chemical structures of related materials, reaction mechanisms, properties, and

applications. Among the available techniques, adsorption methods have great potential to be widely

used. However, membrane methods have attracted attention owing to their low energy consumption

and high separation rates; the advantages and limitations of nanofiltration, electrodialysis, bipolar

membranes, and membrane capacitive deionisation are therefore summarised in this review. As

representative electrochemical methods, the lithium ion capturing system and the rocking-chair

battery system are reviewed, and the roles of various electrode materials in lithium recovery are

analysed. Recently, reaction-coupled separation technology has emerged as an advantageous method

for magnesium/lithium separation and lithium extraction. The ability of this technology to realise

highly efficient magnesium/lithium separation while simultaneously preparing high-value

magnesium-based functional materials from magnesium resources is discussed. The development of

such methods that can comprehensively utilise the magnesium and lithium resources in salt lake brine

is essential for resource sustainability.

Keywords: Lithium extraction; Salt lake brine; Separation technology; Magnesium/lithium

separation; Reaction-coupled separation technology

Contents

1. Introduction ......................................................................................................................................2

2. Advances in magnesium/lithium separation and lithium extraction from salt lake brine ................2

2.1. Extraction methods................................................................................................................2

2.1.1. Neutral extraction .......................................................................................................2

2.1.2. Ionic liquid extraction ................................................................................................2

2.2. Adsorption methods ..............................................................................................................2

2.2.1. Aluminium-based adsorbents .....................................................................................2

2.2.2. Manganese-based adsorbents .....................................................................................2

2.2.3. Titanium-based adsorbents.........................................................................................2

2.3. Membrane methods ...............................................................................................................2

2.3.1. Nanofiltration .............................................................................................................2

2.3.2. Electrodialysis ............................................................................................................2

2.3.3. Bipolar membranes.....................................................................................................2

2.3.4. Membrane capacitive deionisation.............................................................................2

2.4. Electrochemical methods ......................................................................................................2

2.4.1. Lithium ion capturing system.....................................................................................2

2.4.2. Rocking-chair battery system.....................................................................................2

2.5. Reaction-coupled separation technology...............................................................................2

2.5.1. Fundamental principle................................................................................................2

2.5.2. Separation criteria.......................................................................................................2

2.5.3. Applications................................................................................................................2

3. Summary and perspectives...............................................................................................................2

ACKNOWLEDGMENTS....................................................................................................................2

REFERENCES.....................................................................................................................................2
1. Introduction

Lithium, the first metal element in the periodic table, is widely applied in various fields, such

as medicine and aerospace engineering, and used to manufacture various products such as glass

enamels, refrigerants, and greases. The global end-use markets of lithium, as estimated by the United

States Geological Survey (USGS 2020), are shown in Figure 1 [1]. With the application of secondary

batteries in electronic equipment, especially the use of lithium-ion batteries to provide power for

electric vehicles, the consumption of lithium for battery production has increased [2,3], with batteries

now accounting for more than half of the lithium end-use markets. As electronic products have

become an indispensable part of daily life, the demand for lithium-ion batteries will continue to

increase; thus, the market demand for lithium resources is expected to grow sharply, with an increase

of 20% year per year (y/y) [4,5].

Figure 1. Distribution of global end-use markets of lithium.

At present, 80 million tonnes of lithium resources have been identified globally, which are

distributed as shown in Figure 2 [1]. The most abundant lithium resource is continental brine, which

accounts for 59% [6]. Table 1 shows the compositions of the main salt lake brine resources

worldwide. In China, 4.5 million tonnes of lithium resources have been identified, with more than
 80% of the total lithium reserves being found in salt lake brine [7,8]. The cost of producing lithium

from brine is usually 30%–50% less than that of producing it from hard-rock sources [9]. Owing to

the high energy consumption, high cost, and pollution issues associated with the development of ore

resources, the extraction of lithium from salt lake brine is expected to become a major trend in the

industry. Moreover, extracting lithium from brine can solve the resource shortage problem caused

by the increased use of lithium-ion batteries.

Figure 2. Global distribution of identified lithium resources.

Table 1. Compositions of the main salt lake brine resources globally (g/L).

Salt lake brine Li+ Mg2+ K+ Na+ Ca2+ SO42- Cl– Mg/Li Ref.

Atacama Salar Brine, Chile 3.02 17.6 28.2 61.9 0.41 37.9 - 5.8 [10]

Uyuni Salar Brine, Bolivia 0.84 17.6 15.7 105.4 3.33 21.3 - 21.0 [11]

Great Salt Lake, USA 0.04 9.38 5.5 100.8 0.35 19.7 234.5 [12]

Qarhan, China 0.08 115.0 3.73 87.72 0.27 17.72 180.82 1437.5 [7]

Yiliping, China 0.379 24.15 13.34 82.59 0.33 24.60 192.87 63.7 [7]

Longmucuo, China 1.21 89.5 - - - - - 74.0 [13]

West Taijinar, China 0.26 15.36 8.44 102.4 0.19 - - 59.1 [14]

East Taijinar, China 0.14 5.64 3.79 117.03 0.43 - - 40.3 [14]
 Most salt lake brines in China are the magnesium sulphide subtype or the chloride type. In

all brines, the content of lithium is clearly lower than that of magnesium. When the Mg/Li ratio is

lower than 6, lithium can be effectively separated using the chemical precipitation method [15]. For

example, at Zabuye salt lake (China), which is a carbonate-type salt lake, lithium carbonate is

precipitated in a solar pond [16]. However, as the Mg/Li ratio is higher than 6 in most brines, the

simple chemical precipitation method is not applicable because high Mg/Li ratios increase the loss

of lithium and reduce the lithium extraction rate [17]. The greatest challenge in recovering lithium

from a salt lake brine source with a high Mg/Li ratio is efficiently separating Mg2+ and Li+ [6].

Lithium and magnesium, which are alkali/alkaline earth metals, have similar properties owing to

their diagonal relationship in the periodic table [18]. In particular, the radii of Mg2+ and Li+ are

similar, i.e., 72 and 76 pm, respectively [19]. As it remains difficult to recover lithium from salt

lake brine sources with high Mg/Li ratios, researchers in China and abroad continue to search for

economic and efficient recovery processes.

Although many aspects of lithium recovery have been reviewed, previous reports do not

provide a comprehensive assessment of research on sustainable lithium extraction from salt lake

brine . Meshram et al. [20], Swain [6], and Meng et al. [21] reviewed extraction methods for

recovering lithium from different lithium resource types (ore, clay, brine, battery, etc.). However,

these works were deficient in exploring the mechanism of lithium extraction from salt lake brine.

Pramanik et al. [17] focused on the extraction of strategically important elements (platinum-group

metals and lithium) and commented on the extraction methods. However, a detailed classification

and summary of the different methods was not provided and popular techniques, such as adsorption

and electrochemical methods, were omitted. Xu et al. [22] and Li et al. [23] reviewed the use of

lithium ion sieves in adsorption and membrane methods, respectively.

This review summarises recent research progress in lithium extraction from salt lake brine,

with a focus on the extraction methods used for salt lake brine resources with high Mg/Li ratios.

The key technologies include extraction, adsorption, membrane, and electrochemical methods, as
well as a new strategy, reaction-coupled separation technology, which has attracted attention owing

to its unique separation mechanism and excellent lithium recovery ratio. The characteristics and

applicability of the various methods are detailed; the reaction mechanisms and application

performance are reviewed; and directions for future development are suggested.

2. Advances in magnesium/lithium separation and lithium extraction from salt lake brine

The high Mg/Li ratios and high magnesium contents of the salt lakes in China makes the

separation and extraction of lithium challenging, resulting in a dependence on foreign countries for

more than 80% of lithium resources. If imports are blocked, the renewable energy, aerospace, and

nuclear energy industries as well as other related fields will find sourcing lithium a demanding task.

At present, the following problems are associated with the industrialised technology used for

extracting lithium from salt lake brines in China: (i) low lithium recovery rates, resulting in a

serious loss of lithium resources; (ii) production of low-purity lithium salts owing to a lack of core

technology; and (iii) waste of magnesium resources, as the extraction of 1 tonne of lithium salt

produces over 100 tonnes of magnesium salt by-products, resulting in ‘magnesium damage’ to the

salt lake.

2.1. Extraction methods

Extraction methods (or liquid–liquid extractions) use the different solubilities of salts in an

appropriate extraction system to recover lithium. This process is economically feasible when the

concentration of the target element is high [24]. However, separation becomes difficult when the

components of the mixture have similar physical and chemical properties, as is the case for lithium

and magnesium. Liquid–liquid extraction has been widely studied to recover lithium from brines

with high Mg/Li ratios. The process flow chart for lithium recovery by the extraction method is

shown in Figure 3. First, salt lake brine is extracted to form two phases, impurity ions remain in the

aqueous phase and lithium ions are transferred to the organic phase. Second, the stripping tests are

conducted to back-extract the lithium in the organic phase to aqueous phase. At the same time, the
organic phase is recirculated for reuse in the extracting stage. Third, the lithium-rich solution is

purified to get pure lithium solution by evaporation, and the dissolved impurities are removed by

precipitating the contaminants as solid particles. Finally, the lithium as Li2CO3 is precipitated by

adding sodium carbonate as a precipitating agent.

Figure 3. Process flow chart for lithium recovery by the extraction method.

2.1.1. Neutral extraction

In the 1970s, Gabra et al. reported a process for extracting lithium with n-butanol as the

extractant, where the purity of the recovered salt, lithium chloride, reached 99.6% [25]. In addition,

neutral organic phosphorus extractants, such as TBP, were also studied [26]. The TBP/kerosene–

FeCl3 extraction system, in which TBP is the extractant, kerosene is the diluent, and FeCl3 is the co-

extractant, has been widely investigated [27-30]. Shi et al. found that the extraction efficiencies for

the single-stage and three-stage countercurrent extraction of lithium were 80.64% and 99.42%,

respectively, under the optimal conditions [31]. Zhou et al. studied the effects of different diluents

on the extraction efficiency, finding the following order of efficiency: TBP/2-octanol <
TBP/kerosene < TBP/methyl isobutyl ketone (MIBK). In particular, the lithium recovery values of

the TBP in MIBK and TBP in kerosene systems were much larger than those of the TBP in 2-

octanol system [32]. An investigation of the effects of TBP concentration, Fe/Li molar ratio, and

acidity on lithium extraction revealed the optimum conditions to be a TBP concentration of 75%, a

Fe/Li molar ratio of 1.3, and a brine acidity of 0.01 mol/L. Under these conditions, the extraction

rate of Li+ was 67.9%, and the separation factor was 435.5 [33].

Su et al. developed a ternary synergistic solvent extraction system of TBP/FeCl3/P507; the

corresponding mechanism is shown in Figure 4. The stripping process, which used only water,

avoided a high concentration of HCl. Further, the coordination of Fe3+ by P507 and TBP led to the

Li·2TBP·FeCl4 structure being destroyed, which resulted in the effective stripping of lithium. A

lithium extraction rate of 85% was achieved with a negligible loss of Fe3+ [34]. Yu et al. used

multistage centrifugal extraction with an extraction system of 80% triisobutyl phosphate (TIBP) and

20% sulfonated kerosene to solve the problem of recycling the co-extractant (Fe3+). The lithium

recovery rate reached 90.05% after a five-stage centrifugal extraction; the lithium stripping rate was

almost 100% when the volume ratio between the organic and aqueous phases was 2:1 [35]. Li et al.

compared the effects of various organic extractants, such as ethyl acrylate (EA), butyl acetate (BA),

MIBK, diisobutyl ketone (DIBK), N,N-bis(2-ethylhexyl)acetamide (N523), and TBP, on lithium

extraction. The order of lithium extraction ability was N523 > TBP > DIBK > EA > MIBK > BA,

and in all the systems, the formed complexes contained FeCl4 [36]. The removal of Ca2+ and Mg2+

using di(2-ethylhexyl)phosphoric acid as an extractant was studied. With this system, the extraction

sequence was Ca2+ > Mg2+ > Li+ > Na+, and the removal efficiencies of Ca2+ and Mg2+ were 99.05%

and 98.48%, respectively. Moreover, the loss ratio of Li+ was less than 5.22% with multistage

centrifugal extraction [37]. N523 and TBP were used as extractants to study the effect of H3BO3 on

the extraction efficiency of lithium and the separation effect of lithium and magnesium. Using a

centrifugal extractor, the lithium extraction rate reached 96% and the Mg/Li mass ratio was reduced

from 48 to 0.0015. H3BO3 had no significant influence on lithium extraction or the quality of the
stripping liquor; hence, it was not necessary to separate H3BO3 before lithium recovery, which

reduced the separation cost [38].

Figure 4. Mechanism of lithium extraction and stripping by the TBP/FeCl3/P507 system.

(Reprinted with permission from Ref. [34]. Copyright 2020 American Chemical Society.)

Song et al. revealed the lithium extraction mechanism, as shown in Equations (1) and (2)

[39]. As HFeCl4·2TBP only formed at high chloride concentrations, the chloride source is an

important factor for lithium extraction. MgCl2 provides a sufficient chloride ion environment and

can form a strong complex in salt lake brines with a high Mg/Li ratio. In addition, the significant

salting-out of MgCl2 can increase the recovery of lithium. Zhou et al. confirmed the existence of

LiFeCl4 by UV-visible, Raman, and infrared spectroscopy, which indicated that lithium extraction

using the TPB/kerosene/FeCl3 system involved an ion association reaction [40]. They also studied

different chlorides as co-extractants, including ZnCl2 and CrCl3, to replace FeCl3 [41]. During the

extraction process, a 6 mol/L HCl solution is usually applied, which can severely corrode the

equipment. Additionally, if the proportion of TBP in the organic phase is less than 80%, organic

polymerisation will occur, resulting in organic loss and environmental pollution, which will reduce

the process efficiency.

 H+ + FeCl3 + Cl- + 2TBP = HFeCl4·2TBP (1)

Li+ + HFeCl4·2TBP = LiFeCl4·2TBP + H+ (2)

2.1.2. Ionic liquid extraction

Ionic liquids have the advantages of negligible volatility, non-flammability, adjustable

viscosity, and high thermal stability. They are introduced into liquid–liquid extraction systems not

only to replace volatile organic solvents but also as co-extractants [42-46]. This method has high

selectivity for lithium and can handle brine with a high Mg/Li ratio. Gao et al. reported the

extraction of lithium from salt lake brine using TIBP and kerosene with three different ionic liquids,

namely, 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([EMIM][N(TF)2]), 1-

butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([BMIM][TFSI]), and 1-butyl-3-

methylimidazolium hexafluorophosphate ([BMIM][PF6]). The results showed that [EMIM][N(TF)2]

as the extractant provided the best lithium extraction efficiency. Under optimum conditions, the

single-step extraction efficiency of lithium ions was 85.61% [47].

The extraction of lithium from brine by imidazolium-based ionic liquids with different alkyl

chain lengths was studied. Decreasing the alkyl chain length of the imidazolium-based ionic liquid

enhanced the lithium extraction efficiency. The extraction and stripping efficiencies of lithium were

74.14% and 86.37%, respectively, using an n-butyl (C4)-based ionic liquid under the optimum

conditions [48]. Similarly, with 1-alkyl-3-methylimidazolium hexafluorophosphate-based ionic

liquids with varying alkyl chain lengths, such as [C6mim][PF6] and [C8mim][PF6], increasing the

chain length, which increases the hydrophobicity of the ionic liquid, was found to decrease the

extraction efficiency [49]. Using the [C4mim][PF6]/TBP–FeCl3 system, Shi et al. found that the

mechanism of lithium extraction involves a cation exchange process to form [Li·2TBP]+ in the ionic

liquid. In this system, the separation coefficient of Li/Mg was 125, and the extraction efficiency of

lithium was 90.93% [50]. Shi et al. studied the extraction of lithium by functional ionic liquids such
 as [N4444][DEHP], [N8888][DEHP], and [P4444][BTMPP] [51], and found that the ionic liquids

formed 1:1 complexes with Li+. Simultaneously, Cl– formed ion pairs with the ionic liquid

components [52].

The most important characteristics of the various extraction processes to recover lithium

resources from salt lake brine are summarised in Table 2. Among the various extraction systems for

lithium recovery from salt lake brines, the most promising is the TBP–FeCl3 system. However,

owing to technical and economic limitations, these processes are limited to laboratory-scale

research. Therefore, extraction methods currently are not suitable for industrial application.

Table 2. Extraction methods for the recovery of lithium from salt lake brines.

Reagent Condition Effect Ref.

Chloride sources Lithium extraction capacity

TBP MgCl2, CaCl2, NH4Cl; MgCl2 > CaCl2 > NH4Cl; [41]
0.2 mol/L LiCl, Fe/Li = 1.9 DLi+ = 11.4

0.05 mol/L LiCl, Binding capacities

TBP/MIBK Mg/Li = 70 (molar); H+ > Li+ > NH4+ > Ca2+ > Mg2+; [28]
R(O/A) = 1 DLi+ = 7.588, βLi/Mg = 452

Mg/Li = 94.8 (molar),

TBP/MIBK ELi+ = 98.9% [30]
0.036 mol/L B

0.04 mol/L Li+,

TBP/kerosene ELi+ = 88.5%, βLi/Mg = 3924 [33]
Mg/Li = 114 (molar)

Co-extracting capacity
TBP/MIBK Co-extracting agents FeCl3 > ZnCl2 and CrCl3;
TBP/kerosene FeCl3, ZnCl2, CrCl3; Lithium extraction capacity [32]
TBP/2-octanol Mg/Li = 70 (molar) MIBK > kerosene > 2-octanol;
DLi+ = 3.9

TBP/acetophenone/kerosene 0.05 mol/L Li+ DLi+ = 4.08 [29]

Mg/Li = 4.3 (molar);

Na[FeCl4·2TBP] βLi/Mg = 178.4 [39]
Single-rising drop

0.3 mol/L Li+, 3.8 mol/L Mg2+,

TBP/[C4mim][PF6] 0.14 mol/L Na+, 0.05 mol/L K+; DLi+ = 5.01, ELi+ = 90.93% [50]
R(O/A) = 2

0.3 mol/L Li+;

TBP/[C4mim][NTf2] Mg/Li = 12.7 (molar); DLi+ = 6.05, ELi+ = 92.37%, βLi/Mg = 403.33 [31]
R(O/A) = 2
 0.3 mol/L Li+, 3.8 mol/L Mg2+,
TBP/[C4mim][PF6]/NaClO4 0.14 mol/L Na+, 0.04 mol/L K+; ELi+ = 87.28% [49]
R(O/A) = 2

TIBP/[C2mim][NTf2]/kerosene 0.3 mol/L Li+, 0.2 mol/L Na+, DLi+ = 2.84, ELi+ = 73.95%, βLi/Mg = 65.90
TIBP/[C4mim][NTf2]/kerosene 0.3 mol/L K+, 3.2 mol/L Mg2+; DLi+ = 1.66, ELi+ = 62.39%, βLi/Mg = 33.72 [47]
TIBP/[C4mim][PF6]/kerosene R(O/A) = 1 DLi+ = 1.23, ELi+ = 55.22%, βLi/Mg = 43.45

0.07 mol/L Li+, 0.02 mol/L Na+,

[P4444][BTMPP]/toluene 0.01 mol/L K+; ELi+ = 89.70% [51]
R(O/A) = 2

[N4444][DEHP] 0.07 mol/L Li+, 0.02 mol/L Na+, DLi+ = 3.6, ELi+ = 92%
[52]
[N8888][DEHP] 0.01 mol/L K+ DLi+ = 2.1, ELi+ = 82%

Note: DLi+ is the partition coefficient of the lithium ion. ELi+ is the lithium extraction efficiency. βLi/Mg is the

lithium/magnesium separation factor. R(O/A) is the volume ratio between the organic and aqueous phases.

2.2. Adsorption methods

Adsorption methods involve the separation and extraction of lithium from salt lake brine

with a high Mg/Li ratio using lithium-selective adsorbents. The adsorption process for lithium

recovery is outlined in Figure 5. The key aspect of this method is the adsorption material. First, the

lithium adsorption material must have high stability, allowing it to maintain its structure in high-

salinity salt lake brine systems and strong acid elution systems. In particular, it must be able to

adapt to changes in the brine temperature and the mechanical requirements of the adsorption

operation. Second, the lithium adsorption material must have a high selectivity and adsorption

capacity for lithium to efficiently extract lithium from salt lake brine resources with high salinity

and complex compositions. To date, mainly aluminium salt adsorbents and lithium ion sieve

adsorbents (manganese-based and titanium-based) have been studied.

 Figure 5. Adsorption process for lithium recovery.

2.2.1. Aluminium-based adsorbents

The aluminium salt adsorbent with the general chemical formula LiCl·2Al(OH)3·nH2O is a

type of deficient disordered structure generated by the insertion of LiCl into Al(OH)3 to form an

LiAl-layered double hydroxide (LiAl-LDH) (Figure 6) [53,54]. Equation (3) represents the

adsorption and elution principle of this system [55,56]. The aluminium salt adsorbent has selectivity

for lithium because Li+ can enter the Al(OH)3 lattice and occupy the octahedral holes, whereas the

larger alkali and alkaline earth metal ions cannot enter owing to steric effects. Although the ionic

radius of Mg2+ (72 pm) [57,58] is similar to that of Li+ (76 pm) [59], Mg2+ is easily combined with

water molecules to form complex ions ([Mg(H2O)6]2+) with a greatly increased ionic radius of 428

pm [60]. In contrast, Li+ can only form hydrated ions (with a radius of 382 pm), and the hydration

free energy is far less than that of Mg2+ (515 kJ/mol for Li+ and 1922 kJ/mol for Mg2+) [61]. Thus,

during the adsorption process, water molecules are more easily removed from Li+ than from Mg2+,

allowing Li+ adsorption by an aluminium salt adsorbent to realise the separation of magnesium and

lithium.
 Figure 6. Crystal structures of gibbsite (α-Al(OH)3) and LiAl-LDH (Li[Al(OH)3)]2OH·2H2O).

Crystal structure of gibbsite perpendicular to (A) the c and b axes and (B) the b and a axes. Crystal

structure of LiAl-LDH perpendicular to (C) the a and c axes, where the half-filled, red/white

spheres in the interstitial layers indicate half occupancy, and (D) the a and b axes. The aluminium,

oxygen, lithium, and hydrogen atoms are shown as blue, red, green, and white, respectively.

(Reprinted with permission from Ref. [62]. Copyright 2019 American Chemical Society.)

xLiCl + (1– x)LiCl·2Al(OH)3·(n+1)H2O ⇌ LiCl·2Al(OH)3·nH2O + H2O (3)

Kotsupalo et al. studied the LiCl·2Al(OH)3·mH2O adsorbent with structural defects, which

can be used to extract lithium from brine with a high Mg/Li ratio. The adsorption capacity was

approximately 7–8 mg/g, and even when the brine contained a high concentration of MgCl2, the

adsorbent was selective for lithium [63]. On increasing the MgCl2 concentration from 0 to 500 g/L,

the lithium adsorption capacity increased nearly 4 times, indicating the suitability of this aluminium

salt adsorbent for the recovery of lithium from salt lake brine with a high Mg/Li ratio [64].

Paranthaman et al. used a three-stage bench-scale column extraction process to extract lithium.

When an LDH with a Li/Al ratio of 1:1.25 was used as the adsorbent, the recovery rate of lithium

was 91%. Notably, the load–wash–elution process was completed without the consumption of
reagent chemicals or the production of secondary waste [65]. Zhong et al. studied the influence of

the structural stability of Li/Al-LDHs on the adsorption properties. Under excessive lithium

deintercalation, Li+ active sites were generated and the layered Li/Al-LDH structure collapsed,

which resulted in the adsorption capacity fluctuating. Li/Al-LDHs have great potential for the

extraction of lithium from salt lake brine with a high Mg/Li ratio, as the adsorption capacity for Li+

significantly improved in the presence of Mg2+ [66]. However, owing to the difficulties in

separating and recovering the powdered adsorbent, granulation and moulding steps are necessary in

industrial applications, which not only makes the preparation process tedious but also causes the

adsorption performance to rapidly decrease. Researchers have doped aluminium salt adsorbent with

superparamagnetic nanoparticles (Fe3O4 or γ-Fe2O3) to realise controllable recovery using an

external magnetic field, thus avoiding the granulation process [67]. Yu et al. prepared magnetic

LDH-Li/Al (MLDH) by a chemical co-precipitation method with magnetic Fe3O4, which allowed

MLDH to be separated from the solution using a magnetic rod [68]. Varying the MLDH

composition affected the lithium adsorption performance. With an increase in the Fe3O4 content, the

amount of mesopores decreased and pore blocking increased. As a result, the adsorption capacity of

the MLDHs for Li+ decreased, whereas the selectivity increased. When the Fe3O4 content was 13.11

wt%, the adsorption capacity of the MLDH for Li+ was 5.83 mg/g, and an adsorbent recovery of

97% was achieved after the reaction [69].

Jiang et al. packed layered lithium aluminium hydroxides in fixed bed columns to simulate

the adsorption of lithium ions from brine and investigated the lithium breakthrough curves. The

initial lithium concentration, bed height, and feed flow rate were found to have significant effects

on the column adsorption performance. To simulate and predict the lithium adsorption curve, a

homogeneous surface diffusion model was established, which provided technical support for the

design and scale-up of fixed bed column adsorption for lithium extraction from salt lake brine [70].

At present, aluminium salt adsorbents are the only adsorbent materials that have been used

in industrial applications. Although such adsorbents can effectively separate magnesium and
lithium, their adsorption capacities are small and further optimisation is required to achieve

enhanced industrial performance.

2.2.2. Manganese-based adsorbents

Manganese-based adsorbents are a class of ion sieve that has received wide attention. The

behaviour of manganese-based ion sieves is summarized in Figure 7. Lithium ions are introduced

into the manganese compound to form a spinel structure through heat treatment. Subsequently, the

lithium ion is extracted from the spinel structure by acid treatment, with a proton replacing Li+ to

form a lithium ion sieve without changing the crystal structure. In the presence of multiple ions, the

lithium ion sieve has the ability to screen and remember a target ion, which is called the ‘ion sieve

effect’. As an example, the structural diagram of spinel LiMn2O4 (ion sieve precursor) is shown in

Figure 8. This structure belongs to the cubic Fd3m space group, wherein lithium occupies the

tetrahedral (8a) position, Mn3+ and Mn4+ occupy the octahedral (16d) position together, and oxygen

occupies the face centred cubic (32e) position. Thus, the structure is composed of Li–O tetrahedra

and Mn–O octahedra, where each vertex angle is shared by one tetrahedron and three octahedra. Li+

can move in and out of the three-dimensional network structure along the 8a-16c-8a channel, which

is the theoretical basis for lithium ion sieve adsorption/desorption. Currently, there are three

potential explanations for the adsorption mechanism.

(1) An oxidation–reduction mechanism, following Equations (4) and (5) [71]:

2Li[Mn3+Mn4+]O4 + 4H+ → 1.5[Mn24+]O4 + 2Li+ + Mn2+ + 2H2O (4)

[Mn24+]O4 + Li+ + OH– →Li[Mn3+Mn4+]O4 + 0.5H2O + 0.24O2 (5)

(2) An ion exchange mechanism, following Equation (6) [72,73]:

 Li[Mn3+Mn4+]O4 + H+ ⇌ H[Mn3+Mn4+]O4 + Li+ (6)

(3) A compound reaction mechanism [74] in which the adsorption process involves both the

redox and ion exchange mechanisms.

Figure 7. Behaviour of manganese-based ion sieves [75]. (Adapted with permission from Ref. [75].

Copyright 2017 John Wiley & Sons, Ltd.)

Figure 8. (a) Crystal structure of spinel LiMn2O4. Manganese ions reside in the octahedra formed

by oxygen ions. The dotted arrow denotes a lithium diffusion path. (b) Schematic illustration of the

lithium diffusion channel from a tetrahedral 8a site to an adjacent 8a site through an octahedral 16c

vacancy surrounded by six manganese ions in the octahedral 16d gate sites. (Adapted with

permission from Ref. [76]. Copyright 2018 Royal Society of Chemistry.)

At present, research has mainly focused on precursors such as LiMn2O4, Lil.6Mnl.6O4, and

Li4Mn5O12 as well as λ-MnO2 for the formation of manganese-based lithium ion sieves (LMOs) by
acid treatment. Owing to the special electronic structure of Mn3+, the Jahn–Teller effect causes

serious distortion of the lattice structure of an LMO in acidic environments [73]. The electrons of

Mn3+ in the bulk phase are transferred to Mn4+, which is converted to Mn2+ and then dissolves [77].

This LMO dissolution has hindered the industrial application of manganese-based adsorbents. The

manganese-based lithium ion sieves λ-MnO2, MnO2·0.31H2O, and MnO2·0.5H2O, formed from the

precursors LiMn2O4, Lil.33Mnl.67O4, and Lil.6Mnl.6O4, respectively, have theoretical adsorption

capacities of 5.7 mmol/g (39.6 mg/g), 8.5 mmol/g (59.0 mg/g), and 10.5 mmol/g (72.9 mg/g),

respectively [78]. Despite these relatively high theoretical capacities, the corresponding practical

adsorption capacities were relatively small owing to the poor LMO stability and the high

manganese dissolution rate.

LMO modification improved the adsorption capacity and decreased the dissolution loss of

manganese. Most commonly, the spinel structure was modified by doping with transition metals,

such as copper, zinc, iron, nickel, and titanium. The Li–O bond length increased and the Mn–O

bond length decreased owing to the strong ionic bonds formed between the metals and oxygen

atoms, resulting in the lattice constant of the spinel structure shrinking, which enhanced the

structural stability and hindered the dissolution of manganese [79]. Magnesium doping also had a

positive effect on LMOs. For example, Tian et al. prepared LiMg0.56Mn1.50O4 by a soft chemical

method, which exhibited a lithium extraction performance of greater than 95% after recycling five

times [80]. Chitrakar et al. found that the adsorption capacity for Li+ and the chemical stability of

the ion sieve were increased by increasing the Mg/Mn ratio, and the manganese loss rate was less

than 0.25 wt%. Additionally, magnesium doping accelerated the adsorption equilibrium, with the

adsorption capacity reaching 23–25 mg/g within 24 h, resulting in an improved lithium recovery

efficiency [81]. The calcination method was used to synthesise a nickel-doped adsorbent. As more

H+ sites were introduced in the material, the amount of negative charge on the surface increased and

thus the extent of Li+ exchange increased. In addition, the specific surface area and pore volume of

the nickel-doped ion sieve increased, making Li+ diffusion easier [82]. Kim et al. grew magnetic
Fe3O4 on the surface of an LMO ion sieve, which changed the spinel structure to hinder the Li+

transport channel [83]. Iron doping reduced the loss of Mn3+ by dissolution and was beneficial for

the recovery of the ion sieve adsorbent owing to its magnetic properties [84,85].

The lithium adsorption/desorption ability could also be enhanced by changing the synthesis

method. Zhang et al. synthesised a nanorod ion sieve with an increased specific surface area of 70

m2/g. The length of the internal diffusion path in the bulk phase was decreased, which not only

improved the Li+ adsorption capacity but also decreased the time required to reach equilibrium [86].

Zandevakili et al. studied the effects of six parameters (lithium source, manganese source, oxidant,

Li/Mn molar ratio, calcination temperature, and time) on the performance of spinel lithium ion

sieves. It was found that the lithium source and the oxidant were the most important parameters,

followed by the Li/Mn molar ratio and the calcination conditions [87,88]. The lithium ion sieve

produced using LiOH as the lithium source has a higher adsorption capacity than that produced

using Li2CO3, and the adsorption capacity was positively correlated with the Li/Mn ratio during

calcination [89]. When LiOH was used as the lithium source and Na2S2O8 as the oxidant at 450 °C

for 6 h, the produced ion sieve had a Li+ adsorption capacity of 9.11 mmol/g [87].

Wang et al. studied the performance of an LMO with chitosan granulation and ethylene

glycol diglycidyl ether cross-linked spherical materials. This adsorbent exhibited an equilibrium

adsorption capacity for Li+ of 8.98 mg/g with an Li+ separation factor greater than 51 [90].

Manganese-based lithium ion sieves have excellent selectivity for Li+ in solution and can

adsorb Li+ from brines with high Mg/Li ratios and low Li+ concentrations, but the industrial

application of LMOs is hindered by manganese dissolution during desorption. However, various

modified manganese-based adsorbents show good application prospects.

2.2.3. Titanium-based adsorbents

Compared with LMOs, there have been fewer studies on titanium-based ion sieves, with

most research work focused on layered Li2TiO3 or spinel Li4Ti5O12. As shown in Figure 9(a), the
structure of layered Li2TiO3 consists of a (Li) layer and a (LiTi2) layer. The (Li) layer is only

occupied by lithium atoms, accounting for 75% of the total lithium. The (LiTi2) layer is occupied by

2/3 Ti and 1/3 Li, accounting for remaining 25% of the total lithium [91]. H2TiO3, which is formed

from layered Li2TiO3 by replacing the lithium ions with protons, can be used to extract lithium from

salt lake brine (Figure 9(b–d)). Because the Li+ activity of the (Li) layer is higher than that of the

(LiTi2) layer, Li+ in (Li) layer is exchanged first to form H[Li1/3Ti2/3]O2 and then Li+ in the (LiTi2)

layer is exchanged, finally forming H[H1/3Ti2/3]O2 [92]. The adsorption/desorption process of

lithium can be expressed by Equations (7)–(9). Owing to the very narrow interlayer exchange sites,

cations with ion radiuses larger than that of Li+ cannot enter the (Li) layer of H2TiO3, resulting in

selectivity with the order of Li+ >> Na+ > Mg2+ > Ca2+ > K+. The subsequent replacement of lithium

ions with protons can be used to recover lithium resources and simultaneously regenerate layered

H2TiO3.

Figure 9.(a) Crystal structure of the layered Li2TiO3, (b, c) after pickling, (d) after lithium exchange

(Li as purple ball, H as yellow ball, O as red ball, Ti as grey ball)

(Reprinted with permission from Ref. [93]. Copyright 2015 Springer-Verlag Berlin Heidelberg.)
 Li[Li1/3Ti2/3]O2 + H+ = H[Li1/3Ti2/3]O2 + Li+ (7)

H[Li1/3Ti2/3]O2 + 1/3H+ = H[H1/3Ti2/3]O2 + 1/3Li+ (8)

H[H1/3Ti2/3]O2 + xLi+ = H1-xLix[H1/3Ti2/3]O2 + xH+ (9)

Chitrakar et al. demonstrated that Li2TiO3 in salt lake brine typically required 1 day to reach

adsorption equilibrium, with the Li+ adsorption capacity reaching 32.6 mg/g at pH 6.5 [91]. The

separation coefficients of Li+ and other cations were greater than 100 [94]. For Mg2+, the separation

coefficient of Li+ was 4783, indicating that Li2TiO3 can achieve good magnesium/lithium

separation from salt lake brine [95]. Li2TiO3 underwent structural rearrangement during acid

leaching, especially at high concentrations of chloride ions, which can result in a transformation

into rutile TiO2, thereby reducing the adsorption capacity for Li+ [96,97]. He et al. studied the

influence of the preparation and adsorption conditions on performance and found that the maximum

adsorption capacity of H2TiO3 for lithium reached 57.8 mg/g under the optimal conditions [93]. The

synthesis method of the Li2TiO3 precursor affected the dissolution rate of titanium. Shi et al.

prepared Li2TiO3 by a solid-state reaction; this adsorbent achieved a lithium extraction rate of up to

99% during acid leaching but exhibited a titanium dissolution rate of 0.17% [98]. Zhang et al. used

a sol–gel method to reduce the dissolution rate of titanium to 0.07%, although the extraction rate of

lithium also decreased to 78.9% [99]. H2TiO3 synthesised from an anatase structure was found to

have a maximum adsorption capacity of 39.2 mg/g [97]. However, He et al. optimized the reaction

conditions by studying the preparation of the adsorbent and the adsorption conditions, achieving an

adsorption capacity of 57.8 mg/g [93]. Lawagon et al. showed that avoiding the serious

accumulation of H+ can increase the capacity for Li+, obtaining a maximum adsorption capacity of

94.5 mg/g under the optimal conditions [100]. The H2TiO3 lithium ion sieve showed not only good

adsorption ability but also stable cycling performance. After more than 100 extraction cycles, the

capacity loss was less than 10% [101]. Although β-Li2TiO3 had a high theoretical adsorption

capacity (142.9 mg/g Li+), the observed adsorption capacity was only 40% of the theoretical value
owing to an insufficient Li+ content and the agglomeration of particles caused by the high

temperature used to synthesise β-Li2TiO3 [102]. Iron-doped Li2TiO3 ion sieves were effectively

separated from a suspension without lithium adsorption capacity loss. Fe/Ti-0.15(H) exhibited

excellent large-scale and continuous magnetic recovery (96%) and a superior lithium adsorption

capacity (53 mg/g) [103].

Lin et al. synthesised a Li2TiO3 ion sieve by solid-phase calcination and a hydrothermal

method. Powdered H2TiO3 granulated by poly(vinyl chloride) (PVC) was used as a binder and

polyethylene glycol (PEG-6000) was used as a porogen to prepare a polyporous structure, which

improved the adsorption performance. The adsorption capacity of this adsorbent was 12.84 mg/g

and the equilibrium time was approximately 12 h [104].

Spinel Li4Ti5O12 is a titanium-based lithium ion sieve with a large lithium adsorption

capacity and good cycling performance. The crystal structure is shown in Figure 10. Li4Ti5O12 has a

stable structure with strong Ti–O bonds and good acid resistance, but it usually contains the rutile

TiO2 phase and the Li2TiO3 phase, which decrease the structural stability and adsorption capacity

[105]. The potential adsorption/desorption mechanisms for titanium-based ion sieves with spinel

structure are the same as those of LMOs, namely, (I) redox mechanism, (II) ion exchange

mechanism, and (III) composite mechanism [22].

Figure 10. Crystal structure of spinel Li4Ti5O12. The yellow tetrahedra represent lithium and the

green octahedra represent disordered lithium and titanium. (Adapted with permission from Ref.

[106]. Copyright 2015 Royal Society of Chemistry.)

 Dong et al. used poly(methyl methacrylate) colloidal crystal templates to prepare Li4Ti5O12

with a lithium adsorption capacity of 56.81 mg/g, high selectivity, and excellent acid stability [107].

Moazeni et al. synthesised a Li4Ti5O12 precursor by a two-step hydrothermal method, and a

nanotube lithium ion sieve with a high Li+ adsorption capacity or 5.5 mmol/g (38.18 mg/g) was

obtained after washing with acid in a 120 mg/L lithium solution [108].

As a new type of high-performance green adsorbent, the lithium ion sieve is suitable for the

future development of the process of lithium extraction from salt lake brines with high Mg/Li ratios.

The excellent lithium selectivity, higher theoretical lithium adsorption capacity, and superior

cycling performance of these adsorbents have attracted considerable attention. Table 3 summarises

the performance of various adsorbents for lithium recovery from salt lake brine. At present, the

challenges associated with lithium ion sieves include the following. (I) There is a huge gap between

the actual adsorption capacity and the theoretical adsorption capacity, likely caused by the

incomplete Li+ desorption during the elution of the adsorbent precursor as well as a decrease in

effective Li+ vacancies owing to the blockage of the adsorption channel during the cycling process.

(II) During the elution process, the core skeleton of the powdered lithium ion sieve adsorbent will

be lost by dissolution in the solution. An appropriate granulation method and an increased

adsorption capacity are critical for the industrial application of ion sieve adsorbents.

Table 3. Performance of various ion sieve adsorbents for lithium recovery from salt lake
brine.

Precursor Solution Adsorption capacity (mg/g) Ref.

LiCl·2Al(OH)3·nH2O CLi+ = 350 mg/L 3.0 [64]

MLDHs CLi+ = 397.14 mg/L

5.83 [69]
(Fe3O4/LiAl-LDHs) Mg/Li = 284 (mass ratio)

CLi+ = 17 mg/L
Nanostructured MnO2 62.46 [109]
Mg/Li = 2517 (mass ratio)

CLi+ = 69.4 mg/L

LiMn2O4 20.48 [110]
Mg/Li = 3.5
 CLi+ = 118 mg/L
Li1.36Mn1.63O4 63.16 [88]
Mg/Li = 3.5

LiMg0.56Mn1.50O4 CLi+ = 200 mg/L 37.4 [80]

CLi+ = 1630 mg/L

Li1.33FexMn1.67-xO4 28 [84]
Mg/Li = 17.8 (mass ratio)

Li2TiO3 CLi+ = 1630 mg/L 32.7 [91]

β-Li2TiO3 CLi+ = 2 g/L 76.7 [102]

Li4Ti5O12 CLi+ = 120 mg/L 39.43 [108]

2.3. Membrane methods

Membrane methods are an emerging technology with considerable promise for lithium

recovery from salt lake brine with high energy efficiency and continuous operation. Depending on

the driving force, these methods can be classified as nanofiltration (pressure driven) or

electrodialysis (electrical potential driven). The bipolar membrane and the membrane capacitive

deionisation system offer improvements over the traditional electrodialysis process and have thus

received widespread attention. Numerous membrane structures have been developed to extract and

separate lithium from salt lake brines with high Mg/Li ratios. Membrane materials with high

selectivity, low energy consumption, and good cycling performance are essential for industrial

application.

2.3.1. Nanofiltration

Nanofiltration, a pressure-driven membrane separation process influenced by the Donnan

effect and the size-screening effect, showed better retention performance for multivalent ions and

better permeability for monovalent ions [111]. However, in actual operation, nanofiltration

membranes could not completely separate magnesium and lithium, although the Mg/Li ratio in salt

lake brine was significantly reduced, thus decreasing the separation difficulty in subsequent lithium

extraction processes. Membrane fouling was encountered during the ion separation process by
nanofiltration, and the separation efficiency was reduced after extended operation times. Therefore,

this technology should be combined with other separation methods in practical applications to

increase the service life, reduce the separation cost, and improve the separation efficiency [23].

Bi et al. studied the 3B02S nanofiltration membrane, which showed good rejection for Mg2+,

recovered lithium from brine with a high Mg/Li ratio, and reduced the Mg/Li ratio [112]. Somrani

et al. treated brine diluted 10 times using a commercial NF90 membrane. The results showed 100%

rejection of Mg2+ with a rejection rate for Li+ or Na+ of 10%–30%. The separation efficiency of Li+

and Mg2+ was 85%, but the NF90 membrane was unsuitable for lithium/sodium separation and

membrane fouling was observed inside the membrane [113]. Yang et al. studied a DK nanofiltration

membrane using a simulated solution with a high Mg/Li ratio, achieving a good separation effect

for magnesium and lithium. The Mg/Li ratio and the initial lithium concentration had little effect on

the separation process, whereas the operating pressure and flux had substation effects [114]. The

lithium yield and separation rate with magnesium were both increased by increasing the operating

pressure, with 92% rejection of magnesium observed at 3.5 MPa. However, the separation

efficiency decreased with increasing temperature. Moreover, there was a competitive relationship

between Li+ and other monovalent ions (Na+ and K+). When the concentration ratio between the

concentrate and permeate solutions was 4, the lithium yield reached 99%, but the membrane flux

and separation efficiency were low [115]. Li et al. investigated the effect of pH on the separation of

Mg2+/Li+. At a low pH, the separation of Li+ and Mg2+ was improved owing to the enhanced

dielectric exclusion of multivalent ions [116]. The pH value of the solution was critical in a two-

stage nanofiltration process. In particular, the Mg2+/Li+ ratio decreased from 13.25 to 0.17 at pH 3.5

using the two-stage nanofiltration process [117]. Sun et al. detailed the effects of the operating time,

operating pressure, feed temperature, pH, Mg/Li ratio, and other ions on the separation of

magnesium/lithium using DL-2540NF. Increasing the operating pressure and decreasing the feed

temperature and pH value were found to increase the Mg2+ rejection rate, which is beneficial for

magnesium/lithium separation. By contrast, increasing the Mg/Li ratio and the presence of
competitive monovalent ions (such as Na+ and K+) increased the rejection rate of Li+, which is not

conducive to magnesium/lithium separation. The addition of divalent Ca2+ had minimal effect on

the separation of magnesium/lithium [14].

Li et al. synthesised polyamide composite nanofiltration membrane for magnesium/lithium

separation, which showed a retention order of MgCl2 > MgSO4 > NaCl > LiCl. When the MgCl2

concentration was 2 g/L and the initial Mg/Li ratio was 20, the nanofiltration process decreased the

Mg/Li ratio to 7.7. When the isoelectric point was less than 9.5, the membrane surface was

positively charged (the isoelectric point of the commercial NF90 membrane is 3.6); therefore, the

performance of the synthetic nanofiltration membrane was better than that of NF90 [118]. A

nanofiltration membrane modified with EDTA had a positively charged surface that could form

complexes with divalent cations such as Mg2+, providing a separation factor for magnesium and

lithium of 9.2 [119]. Zhang et al. prepared a nanofiltration membrane modified with hydroxyl-

containing multiwalled carbon nanotubes to treat brine with a Mg2+/Li+ mass ratio of 14. The

separation factor for magnesium and lithium was 10.4, with excellent bivalent rejection (above

97%) and high permeability [120]. Guo et al. constructed a novel polymer-functionalised metal–

organic framework (MOF) nanofiltration membrane with high selectivity to achieve extremely fast

and selective Li+ separation. The nanofiltration membrane showed excellent separation selectivity;

the separation factor was as high as 1815 [121]. Wang et al. developed a series of MOF membranes

to separate lithium from monovalent-ion-rich solutions. ZIF-8 increased the mobility of Li+ while

decreasing that of K+ and Na+, resulting in high selectivity for Li+ over K+ and Na+ [122].

The performance of nanofiltration membranes is mainly affected by Donnan and steric

effects, and the processes for separating and extracting lithium from brine are not economical

because nanofiltration membranes have a large resistance to mass transfer. Therefore, a new

nanofiltration membrane should be developed to reduce the cost of lithium separation. In addition,

membrane fouling decreases membrane permeability and selectivity, which hinder the lithium

recovery process. Nanofiltration membranes with positively charged surfaces are more efficient for
the separation of multivalent cations, which is particularly crucial for the separation of magnesium

and lithium. Owing to the limitations of nanofiltration, these membranes can be coupled with other

separation processes to realise the extraction of lithium from salt lake brine.

2.3.2. Electrodialysis

During electrodialysis, ions migrate in a solution through a membrane under an electric

field; this phenomenon is widely used in fields such as saltwater desalination, industrial effluent

treatment, and organic acid production [123]. A schematic diagram of the electrodialysis process

using alternately placed cation and anion exchange membranes is shown in Figure 11. The cations

pass through the cation exchange membrane under the electric field, whereas the anions migrate to

the electrode through the anion exchange membrane. The replacement of standard ion exchange

membranes with monovalent-selective ion exchange membranes allowed ions with different

charges (such as Li+ and Mg2+) to be separated during electrodialysis [124]. The principle of

electrodialysis for the separation of monovalent ions is that monovalent cations (e.g. Li+, Na+, and

K+) migrate to the concentrating compartment through the monovalent-selective cation exchange

membrane, whereas divalent cations (e.g. Ca2+ and Mg2+) are blocked and remain in the desalting

compartment [11]. Selective ion exchange membranes are of great significance for the application

of electrodialysis to the extraction of lithium from salt lake brines with high Mg/Li ratios.

Figure 11. Schematic illustration of an electrodialysis (ED) stack. (Adapted with permission from

Ref. [125]. Copyright 2014 American Chemical Society.)

 Nie et al. studied the extraction of Li+ from salt lake brine with a Mg2+/Li+ mass ratio of 150

by electrodialysis using the CSO cation selective exchange membrane (CEM; Selemion, Asahi

Glass, Japan). This membrane gave an Li+ recovery as high as 95.3% and the Mg2+/Li+ mass ratio

was reduced to 8 [126]. Sun et al. used molecular dynamics equilibrium calculations to simulate the

diffusion process of Li+ and Mg2+. Mg2+ was easily adsorbed on the sulfonic groups in CEM, which

shielded the electrostatic attraction between Li+ and the sulfonic groups to enhance the diffusion

ability of Li+. Because the interaction energies of the sulfonic groups with monovalent and divalent

ions were significantly different, the Mg/Li ratio could be reduced effectively [127]. Ji et al. also

demonstrated the reduction of the Mg/Li ratio of simulated brine from 60 to 7 using a monovalent-

selective ion exchange membrane. They investigated the effects of the voltage, the feed solution

velocity, and the solution pH on the separation process. Under optimal conditions, the recovery of

lithium was 72.46% and the current efficiency was 8.68% [128]. Liu et al. studied the

electrodialysis process parameters, such as the initial lithium concentration in the feed solution, the

electrolyte temperature, the distance between the anode and cathode, and the operation time,

achieving an Li+ exchange capacity of 38.9 mg/g under the optimal conditions [129]. A study of the

operating conditions and feed characteristics showed that the constant-voltage mode was more

conducive to the recovery of lithium during electrodialysis [130]. The influence of various

coexisting ions (monovalent cations, e.g. K+, Na+, and anions, e.g. SO42–, HCO3–) on lithium

migration was investigated. K+ was found to have a significant effect because of its relatively small

hydration ion radius [131], whereas the anions mainly affected Mg2+ migration owing to the strong

attraction of this cation to SO42– and its reaction with HCO3– to form MgHCO3+. Therefore, Li+

showed greater competitive migration than Mg2+ with coexisting monovalent cations [132]. Ge et

al. replaced the selective ion exchange membrane with a nanofiltration membrane, which resulted in

an almost two-fold increase of the Mg2+ selectivity [133].

 Liu et al. reported a new sandwiched liquid membrane electrodialysis system that included

an anode chamber, a cathode chamber, and a liquid membrane chamber consisting of an ionic liquid

as the lithium ion carrier and two cation exchange membranes. With [C4mim][TFSI] as the liquid

membrane system, the Mg/Li ratio in West Taijinair salt lake brine decreased from 53 to 0.26, and

K+ and Ca2+ were almost completely blocked, resulting in separation from Li+. However, the high

concentration of Na+ easily competed with Li+ for the migration channel [134].

The electrodialysis process exhibits low energy consumption (40–270 Wh/mol Li+) and can

be used to directly treat salt lake brine with a high Mg/Li ratio (approximately 400) and a high Mg2+

concentration (close to saturation) without dilution. Further, this process can achieve excellent

magnesium/lithium separation in salt lake brines with various concentrations. Although

electrodialysis with a monovalent-selective ion exchange membrane can effectively remove

divalent ions, the efficient recovery of lithium from brines with coexisting monovalent ions (Na+,

K+, etc.) remains challenging.

2.3.3. Bipolar membranes

The introduction of a bipolar membrane into the electrodialysis system induces the

dissociation of water into H+ and OH– ions under the electrical field, allowing lithium to be

recovered as LiOH from salt lake brine (Figure 12). This system significantly improved the

processing capacity by introducing more membranes but also had low energy and capital costs,

making it a viable and promising option for lithium extraction.

Figure 12. Schematic illustration of the bipolar membrane electrodialysis (BMED) stack. (Adapted

with permission from Ref. [125]. Copyright 2014 American Chemical Society.)

Using bipolar membrane electrodialysis, LiOH with a high purity of 95% was produced

from Li2CO3 solutions [135]. Bunani et al. investigated the influence of the process conditions on

lithium recovery [136]. Hwang et al. found that larger sample volumes required more time to reach

a stable state. Additionally, it was found that the electrical potential should not be too high because

the density of lithium ion desorption did not increase with the increasing current [137]. Jiang et al.

reported a bipolar membrane for the extraction of lithium from brine by electrodialysis, where

Li2CO3 powder with a purity of 98% was obtained using a Na2CO3 precipitation treatment. This

system was cost-effective at a current density of 30 mA/cm2 and a feed concentration of 0.18 M,

resulting in an economical and environmentally friendly process [125].

2.3.4. Membrane capacitive deionisation

In capacitive deionisation (CDI), the anions and cations are selectively adsorbed on the

electrode from the solution under an electric field, using a system structure similar to that employed

for electrodialysis [138-140]. In membrane capacitive deionisation (MCDI), which is based on CDI,

the electrode surfaces are covered with a pair of anion and cation exchange membranes (Figure 13).

This setup can achieve higher desalination, regeneration, and energy efficiencies owing to the

selectivity of the ion exchange membrane [141]. The anions and cations exist in different areas
during the deionisation process to avoid scaling. Shi et al. recovered lithium from magnesium-rich

brine, as Mg2+ was blocked by the monovalent-selective cation exchange membrane and Li+ was

adsorbed on the cathode through the exchange membrane. When the Mg2+/Li+ ratio was 20, the

lithium selectivity coefficient was more than 2 [142].

Figure 13. (a) Experimental setup for the MCDI process and (b) schematic design of the MCDI

cell. Schematic diagrams of the (c) adsorption and (d) desorption processes in the MCDI system.

(Reprinted with permission from Ref. [142]. Copyright 2018 Elsevier.)

An adsorbent can be applied as the electrode material during MCDI for the extraction of

lithium resources from salt lake brine, which can solve the problem of adsorbent dissolution. Thus,

MCDI not only achieves high lithium ion selectivity but also improves the efficiency of the

adsorbent. Ryu et al. used a spinel-type lithium manganese oxide (LiMn2O4) as the electrode to

accelerate the adsorption reaction with electrostatic field assistance. This system showed good

reproducibility and durability in repeated adsorption and desorption cycles [143]. They also studied

the desorption process, that is, the recovery of lithium from the adsorbent using an electrostatic field

without an acidic solution. Although the desorption efficiency was only approximately 45% of that

achieved with the traditional desorption process using acidic solution, it overcame the shortcomings
of the conventional desorption process and exhibited potential advantages [144]. Using manganese

oxide containing 5% titanium dioxide, which enhanced the electrical conductivity, as a material for

lithium ion extraction, the adsorption capacity for LiCl reached 36 mg/g [145]. Siekierka et al.

compared the lithium extraction performance of different types of anion exchange membranes, i.e. a

PVC-aminated anion exchange membrane and an industrial AMX-408 membrane. The combination

of PVC-diethylene tetra-amine and lithium-manganese-titanium oxide (LMTO) selective adsorbents

increased the adsorption capacity for Li+ by 60% and resulted in lower energy consumption (0.08

WH/g) [146]. A polyvinylidene fluoride film was modified with ethylene diamine to increase the

number of amino groups, which could form complexes with chloride ions. In the presence of

coexisting ions, this system achieved an adsorption capacity of more than 30 mg/g. During the

desorption step, the desorption efficiency was 96% and the current efficiency was greater than 90%

[147]. They also studied the operation mode, i.e. CV-RCV-ZVC and CV-ZVC-RCV sequences

(where CV is constant voltage, RCV is desorption under a reversing voltage, and ZVC is zero

charge voltage). The CV-ZVC-RCV sequence produced an enriched stream of lithium ions and

removed up to 73% of the captured lithium with a total energy consumption of 0.183 Wh/g

adsorbed salt [148]. Lee et al. studied the selective recovery of lithium from aqueous solutions

containing different cations (Li+, Na+, K+, Ca2+, and Mg2+). The observed order of selectivity was

Li+ >> Mg2+ > Ca2+ > K+ > Na+ because the electrical force of a divalent ion is stronger than that of

a monovalent ion, resulting in divalent ions moving more rapidly and forming thicker diffusion

layers on the electrode surface, which can interfere with lithium ion migration [149].

MCDI is widely used as a desalination technology and has broad application prospects

because of its low energy consumption and high efficiency. However, further developments are still

required for the practical application of MCDI to the extraction of lithium from salt lake brine. In

particular, further investigation of the lithium capture electrode is necessary to improve the recovery

of lithium. As a novel technology with a high ion separation rate, a high regeneration efficiency,
antifouling ability, low energy consumption, and environmental friendliness, MCDI is expected to

become an effective method for extracting lithium from salt lake brine.

Although membrane separation technology is a feasible process, its development has been

restricted by high operating costs. Therefore, future advancements in membrane technology should

include improvement in separation efficiency, material stability, membrane fouling control, and

membrane design. Among membrane separation methods, MCDI is the most promising technology

and the further development of highly selective membrane materials is crucial.

2.4. Electrochemical methods

The electrochemical method, which is used for Li+ intercalation/deintercalation in lithium-

ion batteries, presents unique features that allow the working electrode to be applied as an ion sieve

to capture Li+ from brine and release it into the recovered solution. In this way, this method can stop

acid elution from occurring during ion sieve dissolution. In electrochemical systems, it is especially

important that the ion sieve exhibits enhanced cycling performance. In addition, the working

electrode requires excellent selectivity, a high lithium capacity, long-term stability, and low energy

consumption.

2.4.1. Lithium ion capturing systems

In the early 1990s, Kanoh et al. reported electrochemical capture of lithium cations from

source solution to battery material for the first time [150, 151]. The capture process is based on the

intercalation of lithium, which is the most widely used working mechanism for rechargeable

lithium-ion batteries. The process of capturing and releasing lithium ions can be summarized as

8λ-MnO2+4Li++6H2O→4LiMn2O4+ O2+4H3O+ (10)

2LiMn2O4+2H3O+→4λ-MnO2+H2 +2H2O+2Li+ (11)

The Li+ was captured on the work electrode, while the anion was trapped on the counter

electrode in the electrochemical device. Kim et al. used LiMn2O4–zinc (LMO–Zn) battery system

battery system to selectively recover lithium, with an energy consumption of 6.3Wh mol−1. In the
battery system, the Zn was used as the counter electrode where the lithium capture reaction occurs

spontaneously with the oxidation of the zinc electrode. The chemical reaction equation is shown in

Equation 12.

2 λ-MnO2 + Li+ + Zn(s) = LiMn2O4 + Zn2++ e- (12)

Li+ solution with high purity was obtained in the reverse step; at the same time, Zn2+ was

reduced and intercalated into a zinc electrode without a side reaction and electrode potential change

[152].

Xu et al. synthesized a self-supporting λ-MnO2 electrode by potentiostatic treatment of

LiMn2O4 without the need for a high temperature and organic binder. The battery system shows a

higher lithium ion transfer efficiency, larger capacity and longer cycle ability, while the energy

consumption is estimated to be approximately 4.14 Wh/mol Li [153]. Lee et al. reported a

rechargeable battery system composed of a λ-MnO2 cationic electrode and Ag anionic electrode,

where Li+ and Cl- were captured by the respective electrode (Figure 14). The concentration of Li+

increased significantly with the circulation in the recovered solution, while the concentration of the

other cations did not increase, such as Na+, K+, Mg2+ [154]. An electroactive lithium ion imprinted

hybrid film is composed of λ-MnO2/PPy/PSS core-shell nanorods. The PSS-doped PPy acted as the

cation exchange component and conductive cross-linking agent, while λ-MnO2 acted as a

recognition component. Due to the low ion transfer resistance and high electric driving force, the

novel material has excellent separation performance and recyclability [155]. Lawagon et al. studied

Li1-xNi1/3Co1/3Mn1/3O2 (NCM) and the Ag electrode for lithium extraction from salt lake brine by

electrochemical processes. The system has stable performance, and the energy consumption is as

low as 2.60 Wh/mol Li+. The working principle is consistent with that of a lithium-ion battery

[156]. To reduce costs, the electrodes such as activated carbon are used instead of Ag electrodes.

Kim et al. proposed a MnO2/activated carbon hybrid supercapacitor system to extract lithium, and

the results showed that it has a relatively low energy consumption (4.2 Wh/mol Li) and excellent

stability [157]. The battery system consists of a λ-MnO2 cathode and polypyrrole (PPy) anode to
separate lithium. When PPy was doped with small counterions such as Cl-, NO3-, ClO4-, it always

shows the anion exchange property, and the theoretical lithium capacity is 39 mg/g [158, 159]. To

solve the corrosion of electrode materials, Zhao et al. prepared a core-shell microsphere

(rGO/NCM) with graphite gauze modified LiNi0.6Co0.2Mn0.2O2. The electron transport took place in

graphite gauze, which effectively reduced the probability of the NCM lattice collapsing. The

desalination battery composed of rGO/NCM and AC extracted 93% of the lithium ions, and the

extraction capacity was 13.84 mg/g and consumed 1.4 Wh/mol Li+ [160]. They studied the

extraction of lithium resources from brine by a hybrid supercapacitor composed of

LiNi0.038Mo0.012Mn1.95O4 (LNMMO) and an AC anode. The extraction amount was 14.4 mg/g, and

97.2% of the Li was captured by energy, consuming 7.91 Wh/mol Li+ [161].

Figure 14. Schematic of the lithium ion capturing process in source water (1st step,

discharging process) and the lithium ion releasing process in a reservoir solution (2ndstep, charging

process).

(Reprinted with permission from Ref. [154]. Copyright 2013 Royal Society of Chemistry.)

LiFePO4 is a cathode material for lithium-ion batteries with good chemical stability,

economic friendliness and excellent reversibility. In Lithium ion capturing system, the Li+ was

captured on the work electrode, while the anion was trapped on the counter electrode in the

electrochemical device when the LiFePO4 reacts as the work electrode. Zhao et al. learned that
LiFePO4 remains stable in a wide pH range in aqueous solution, and shows good reversible

performance [15,162]. In the LiFePO4-Ag system, Li+ was embedded in FePO4 to form LiFePO4 at

the cathode and Cl- was captured to form AgCl in the anode (Ag). When lithium was recovered,

LiFePO4 was restored to FePO4 and AgCl returned to Ag by applying the reverse voltage. It can be

used to recover Li from salt lake brine with high sodium or magnesium [163, 164]. The reaction is

as follows

FePO4+LiCl+Ag→LiFePO4+AgCl (13)

LiFePO4+AgCl→FePO4+ Ag+LiCl (14)

The LiFePO4 electrode was used to the capture Li+, and the nickel hexacyanoferrate

(NiHCF) electrode was used as the Li+-exclusion electrode (Figure 15). To ensure that the NiHCF

electrode does not react with Li+, the cation concentration should be controlled, such as Na+, K+

(Equation 15). This process can produce a high-purity lithium rich solution in shorter time [165].

FeIIIPO4 + M1/nKNiFeII(CN)6 + LiCl = LiFeIIPO4 + KNiFeIII(CN)6+ 1/nMCln (15)

Figure 15. The Li exchange recovery process based on LFP and NiHCF electrodes using

Atacama brine or sea water as the recovery solution.

 (Reprinted with permission from Ref. [165]. Copyright 2015 Wiley.)

2.4.2. Rocking-chair battery system

The rocking-chair battery is that the lithium ions are inserted/extracted from positive and

negative electrodes of the battery during charging and discharging, and it shakes similar to a

rocking chair. Li+ can be selectively absorbed from the brine in the cathode chamber; meanwhile,

Li+ is desorbed to the anode chamber. Lithium ions has good reversibility in positive and negative

electrodes. According to the working principle of the rocking-chair battery, the electrochemical

lithium extraction system was constructed, which consists of a rich-lithium adsorption material, an

electrolyte, an anion exchange membrane, salt lake brine, and a poor-lithium adsorption material.

Lithium was selectively extracted from salt lake brine using a LiFePO4/FePO4 electrode. In

this method, Li+ is selectively absorbed by FePO4 from brine (Li++e-+FePO4 = LiFePO4). At the

same time, Li is desorbed from LiFePO4(LiFePO4- e- = Li+ + FePO4) and efficiently enriched. The

Li+ from brine be inserted into the negative electrode (FePO4) to form LiFePO4 through adjusting

the potential, while lithium from the positive electrode (LiFePO4) will be released to the

electrolyte .The anion exchange membrane prevents lithium ions from entering the cathode

compartment from the anode compartment, so lithium ions are enriched in the anode electrolyte

(Figure 16). After the cycle is over, the positive and negative electrodes are exchanged and the

electrolysis process is restarted. Lithium can be continuously extracted from the brine and enriched

in the anolyte (full of supporting electrolyte) [166]. When the Mg/Li ratio is as high as 110 in brine,

25% of lithium can be extracted in one cycle. He et al. proved that lithium can also be selectively

extracted at a lithium concentration as low as 60 mg/L, and LiFePO4 has shown excellent cycling

performance [166]. Additionally, LiMn2O4 and Li1-xMn2O4 as electrodes were studied (Figure 17),

and the energy consumption was 18.6 Wh/mol Li [167].

 Figure 16. Structure of the LiFePO4/FePO4 for lithium extraction.

(Reprinted with permission from Ref. [166]. Copyright 2018 Wiley.)

Figure 17. Structure of the LiMn2O4/Li1-xMn2O4 for lithium extraction: (a) 1st step and (b)

2nd step.

(Reprinted with permission from Ref. [167]. Copyright 2017 Elsevier)

These electrochemical methods for lithium extraction are simple and sustainable. In

particular, the rocking-chair battery systems realise high selectivity and low recovery costs for

extracting lithium from salt lake brine. Although these systems require further optimisation and the

chemical reactions at the electrodes need to be elucidated to avoid side reactions, the low energy

consumption and high efficiency of electrochemical methods are broadly advantageous for

industrial application to lithium extraction from salt lake brine.

2.5. Reaction-coupled separation technology

Reaction-coupled separation technology generally refers to a system that simultaneously

realizes a chemical reaction and physical separation. The key characteristics of this technology are

as follows. (1) Products with inhibition effects are separated during the reaction process, which can

improve the overall yield and treatment capacity. (2) Adverse substances are eliminated during the

reaction process, which allows a high reaction rate to be maintained. (3) Heat generated during the

reaction promotes the separation process and thus reduces energy consumption. (4) Subsequent

separation process is simplified, which reduces production costs. This technology has been widely

researched for applications in reactive distillation [168,169], reaction–membrane separation [170-

173], and bioreaction separation [174,175].

Our group has proposed the use of reaction-coupled separation technology to solve the

problems associated with magnesium/lithium separation and lithium extraction from salt lake brines

with high Mg/Li ratios. Based on the lattice selectivity and ion recognition of LDHs, magnesium-

based functional materials (MgAl-LDHs) were produced with the simultaneous extraction of

lithium resources, and the reaction process was strengthened using a micro-liquid membrane

reactor. MgAl-LDHs are widely used in UV shielding [176-178], gas barriers [179-181], PVC

thermal stability [182-184], flame-retardant applications [185-187], photoelectrochemical materials

[188-192], and other fields [193-195]. Therefore, lithium resources can be recovered efficiently and

the simultaneously produced magnesium resources can be fully utilised, which makes the reaction-

coupled separation technology sustainable.

2.5.1. Fundamental principle

LDHs are a type of anionic layered materials with the general formula [M1-
z+M 3+(OH) ]q+A n–·yH O. When z = 2, M2+ and M3+ represent divalent and trivalent metal ions,
x x 2 q/n 2

respectively, which make up the MO6 octahedra in the LDH layers. An– is an anion in the interlayer,

such as CO32–, Cl–, or NO3– [196]. Owing to the variety of layer cations and interlayer anions
available, the LDH family is huge, and MgAl-LDH is a representative example. However, when z =

1, M+ and M3+ are limited to Li+ and Al3+, respectively, to form LiAl-LDHs. The structural

diagrams of MgAl-LDHs and LiAl-LDHs are shown in Figure 18.

Figure 18. Structural diagrams of two types of LDHs. Side and top views of (a) MgAl-LDHs and (b)

LiAl-LDHs. (Reprinted with permission from Ref. [197]. Copyright 2019 Elsevier.)

LiAl-LDHs are a special type of LDHs, in which the layer is formed by lithium ions

embedded in the octahedral vacancy of AlO6 [198]. Na+ cannot enter this vacancy to form vacancy-

type LDHs. Consequently, in the presence of coexisting cations, LiAl-LDHs have the ability to

selectively recognise lithium ions by ion imprinting. The structural differences between MgAl-

LDHs and LiAl-LDHs lead to lattice selectivity and ion recognition towards Mg2+ and Li+,

respectively.

2.5.2. Separation criteria

The criteria for magnesium/lithium separation in salt lake brine were studied both

experimentally and with theoretical simulations [197]. When the initial Mg/Al molar ratio

decreased from 2 to 1, the lithium content increased sharply in the solid phase, where it existed as
LiAl-LDHs, to greatly decrease the extraction rate of lithium (Figure 19). When the Mg/Al ratio

was 2, only MgAl-LDHs were produced, even when the Mg/Li mass ratio was varied, and the

lithium content in the solid phase was less than 0.1%, that is, the separation of magnesium and

lithium was independent of the initial lithium concentration. The theoretical simulation results

revealed that Al3+ preferred to combine with Mg2+ to form MgAl-LDH clusters when the molar

ratio of Mg/Al was 2 or more. However, Li+ could be added to the cluster to form a LiAl-LDH layer

at a Mg/Al ratio lower than 2. Varying the amount of Li+ did not change the formed clusters. Thus,

the theoretical simulation results agreed well with the experimental data. The boundary condition

for the separation of magnesium and lithium was determined to be a Mg/Al molar ratio of 2, which

provides a theoretical basis for the application of reaction-coupled separation technology to

resource recovery from salt lake brine.

Figure 19. Schematic diagram of the boundary conditions for the efficient separation of magnesium

and lithium from salt lake brine by reaction-coupled separation technology. (Reprinted with

permission from Ref. [197]. Copyright 2019 Elsevier.)

2.5.3. Applications

The reaction-coupled separation technology was applied to brine with a high Mg/Li ratio to

co-precipitate Mg2+ ions and foreign Al3+ with an alkali solution to form MgAl-LDHs [199]. Mg2+

almost completely entered the solid phase, while Li+ remained in the solution. The flow sheet for

magnesium/lithium separation and the synthesis of MgAl-LDHs is shown in Figure 20. Using a

micro-liquid membrane reactor to strengthen the reaction process, the influence of the reaction

conditions on the separation performance was clarified by studying the nucleation and

crystallisation processes. The lithium loss, Mg/Li ratio, and secondary particle size were used as the

determination criteria in combination with the zeta potential to optimise the process parameters.

MgAl-LDH with a high crystallinity and large zeta potential was formed to hinder agglomeration

and reduce the loss of lithium. The Mg/Li ratio was reduced from 12.66 (mass ratio) to 0.08 in the

solution, and the lithium recovery was more than 90%. Thus, the reaction-coupled separation

technology realised the efficient separation of magnesium/lithium and the magnesium resources

were effectively utilised, providing useful guidance for the environmentally friendly and sustainable

extraction of magnesium and lithium resources from salt lake brines with high Mg/Li ratios.

Figure 20. Flow sheet for magnesium/lithium separation and the synthesis of MgAl-LDHs.

(Reprinted with permission from Ref. [199]. Copyright 2018 American Chemical Society.)
 The introduction of a large amount of Na+ during the separation of magnesium and lithium

using reaction-coupled separation technology (Na/Li = 48.7) greatly reduced the concentration of

Li+ (from 6.75 to 0.675 g/L), which increased the difficulty of lithium extraction. Lithium ions were

selectively inserted into the solid phase through the selective capture ability of LiAl-LDHs, while

sodium ions remained in the liquid phase [200]. Thus, the highly efficient separation of lithium and

sodium was achieved by adjusting the separation conditions. Under the optimised conditions, the

recovery of lithium was over 96%. The application of reaction-coupled separation technology to the

extraction of lithium from brine with a high Na/Li ratio confirmed that LiAl-LDHs played a key

role in the selective capture of lithium ions and broadened the applicability of this method.

To obtain a lithium solution from salt lake brine that can directly produce a lithium salt to

meet the growing demand for lithium products, Xiang et al recovered lithium from LiAl-LDHs via a

mild solution chemistry process (Figure 21) [201]. LiAl-LDH is a vacancy-embedded structure, and

lithium ions are released from the ordered lattice vacancies in the AlO6 octahedra. The solid LiAl-

LDH phase was gradually transformed to the Al(OH)3 phase, and Li+ was released into the aqueous

solution. Following the thermal reaction of highly crystalline LiAl-LDHs, no Al3+ was detected in

the liquid phase because the Al–O bonds were not easily broken, indicating that lithium and

aluminium were completely separated. Optimizing the slurry concentration, reaction temperature,

and reaction time achieved a lithium recovery of 86.2% with a Li+ concentration of 141.6 mg/L in

the filtrate. As this reaction was carried out in an aqueous medium under mild conditions, it is

suitable for engineering scale-up as a new technology for extracting lithium resources from salt lake

brine.
 Figure 21. Flowchart for lithium recovery from LiAl-LDHs via a mild solution chemistry process.

(Reprinted with permission from Ref. [201]. Copyright 2019 MDPI.)

In view of the critical scientific and technical issues associated with the extraction of lithium

from salt lake brines with high Mg/Li ratios, we proposed reaction-coupled separation technology to

extract lithium and magnesium, simultaneously preparing magnesium-based functional materials

(LDHs) and high-value, high-purity lithium products. Controlling and strengthening the preparation

process for magnesium-based LDHs also improved the utilisation rate of the salt lake magnesium

resources, which solved the key problem of efficiently managing idle magnesium resources. In

2019, A 100-tonne-scale pilot plant with reaction-coupled separation technology was built at

Qarhan salt lake, Qinghai Province, and a trial run was successfully completed. The lithium

extraction rate was as high as 90%, and battery-grade and high-purity lithium carbonate were

prepared. This plant can provide a theoretical and design basis, and offer technical support for

further scale-up preparation (kilotonne production line) and the large-scale industrialisation of

magnesium-based functional materials. This technology will break the foreign monopoly on high-

purity lithium salts, and thus can significantly reduce external dependence, while simultaneously

providing widely used magnesium-based functional materials. In this way, a sustainable

development mode can be built for the coordinated and comprehensive utilisation of magnesium

and lithium resources.

3. Summary and perspectives

At present, the main approaches available for lithium extraction from salt lake brine are

extraction, adsorption, membrane, and electrochemical methods, as well as the emerging reaction-

coupled separation technology. The main issues that require attention during lithium recovery are as

follows: (i) applicability of the method, (ii) concentration of lithium ions in the brine, (iii) Mg/Li

mass ratio, and (iv) effects of other ions. Depending on the specific properties of the salt lake brine,

an appropriate lithium extraction technology need to be selected by considering the Mg/Li ratio, the

anion type (Cl–, SO42–, and others), and the coexistence of monovalent cations (K+, Na+, etc.), as

shown in Table 4.

Table 4. General selection principles of lithium extraction technologies based on brine

properties.
Membrane Reaction-coupled
Lithium extraction
Extraction Adsorption Pressure- Electrical- Electrochemical separation
technology
driven potential-driven technology

Mg/Li ratio High High High Low Low High

Cl–type brine √ √ √ √ √ √
SO42– (and other
anions) type brine
× √ √ √ √ √
Coexistence of
monovalent cations
√ √ × √ √ √
Note: High refers to salt lake brine with a high Mg/Li ratio (generally higher than 10), whereas low refers to salt lake brine with a

low Mg/Li ratio. The symbol √ indicates that the technology is applicable to salt lake brine with the given properties, whereas the

symbol × indicates that the technology is not suitable.

Several basic principles in terms of the brine properties can be applied for the selection of

lithium extraction technology.

(1) Extraction of lithium from brine with a low Mg/Li ratio is possible using electrical-

potential-driven membrane and electrochemical methods. As magnesium ions have a greater charge

than lithium ions, under the action of an electric field, they can move quickly and form a thick

diffusion layer, thereby interfering with lithium ion extraction at higher Mg/Li ratios.

(2) Adsorption methods are more advantageous for brine with high Mg/Li ratios.
 (3) When the anions in brine are mainly Cl–, all the extraction technologies described in this

review are applicable. However, when SO42– or other anions are predominant, the extraction

methods cannot be applied. Generally, the extraction of lithium proceeds via the formation of

HFeCl4·2TBP (where TBP is tributyl phosphate) as an intermediate product; therefore, the

existence of a high Cl– concentration is beneficial for lithium recovery using extraction methods.

(4) The monovalent cations in brine have a great influence on pressure-driven membrane

methods (nanofiltration). At present, nanofiltration can only effectively reduce the Mg/Li ratio, but

it cannot separate lithium ions from other monovalent ions.

(5) The brine properties have little influence on the reaction-coupled separation technology

and, thus, its applicability is more extensive.

In summary, the adsorption method is safe, reliable, and efficient. Although LMO is an ion-

imprinting selective adsorption material, dissolution loss has limited its application to lithium

recovery from salt lake brine; however, by combining this adsorbent with electrochemical methods,

Mn leaching can be avoided. Overall, the development of high efficiency adsorbents continues to be

an important trend for lithium resource recovery. Membrane methods have received attention as a

new type of extraction technology with low energy consumption and good selectivity. In particular,

MCDI utilises the selectivity of electrode materials and an ion exchange membrane to achieve

selective lithium recovery with an improved recovery rate. However, further improvement of the

performance of membrane and electrode materials should be the subject of future research. As the

reaction-coupled separation technology, which is based on the lattice selectivity of LDHs, considers

both the production of high-purity lithium solutions and the effective utilisation of magnesium

resources, it is considered an environmentally friendly and sustainable method. With its high lithium

recovery rate and the comprehensive utilisation of magnesium resources, this unique separation

technology is considered greatly beneficial for industrial applications.

The recovery of lithium from salt lake brine with high Mg/Li ratios is a subject that researchers

continue to explore. While attempts to improve the recovery rate and selectivity are important, the
utilisation and development of other accompanying resources should also be further considered to

develop sustainable technology for lithium extraction from salt lake brine.

ACKNOWLEDGMENTS

This work was supported by the National Natural Science Foundation of China (grant U1707603),

the Innovative Research Groups of National Natural Science Foundation of China (grant

21521005), the Fundamental Research Funds for the Central Universities.

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 Graphical Abstract

This review highlights the recent advances and the current state-of-the-art in Mg/Li separation
and lithium extraction technologies from salt lake brine. It provides new insights to this field from
the view of resource sustainability.
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.

☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests: