Geoscience Frontiers 14 (2023) 101485

Contents lists available at ScienceDirect

Geoscience Frontiers
journal homepage: www.elsevier.com/locate/gsf

Research Paper

Lithium extraction from salt lakes with different hydrochemical types in

the Tibet Plateau
Tao Ding a, Mianping Zheng a,b,⇑, Suping Peng a, Yuhan Lin a, Xuefei Zhang b, Mingming Li a
a
College of Geoscience and Surveying Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China
b
MNR Key Laboratory of Saline Lake Resources and Environments, Institute of Mineral Resources, Chinese Academy of Geological Sciences, Beijing 100037, China

a r t i c l e i n f o a b s t r a c t

Article history: The demand for lithium resources is increasing sharply with the rapid development of electric vehicles. It
Received 6 April 2022 is of great economic significance to expand the geological resources of lithium and improve the utiliza-
Revised 5 September 2022 tion rate of lithium-containing salt lakes. In this paper, the hydrochemical types of the lithium-containing
Accepted 30 September 2022
salt lakes in the Tibet Plateau were classified according to a large amount of hydrochemical data obtained
Available online 04 October 2022
Handing Editor: M. Santosh
from a recent investigation on the Tibet Plateau. In addition, the lithium extraction methods used in the
salt lakes within each hydrochemical type area were analyzed and summarized, which provided a refer-
ence for the selection of lithium extraction processes in the same hydrochemical type of lithium-
Keywords:
containing salt lakes in the future. The binding energies of Li(Ι) and anions in salt lakes with different
Tibet Plateau hydrochemical types were calculated by density functional theory, which provides the theoretical basis
Lithium-containing salt lake for selecting the best lithium extraction technology in different salt lakes. We emphasize that the process
Hydrochemical type with the combined characteristics of high efficiency, economy and environmental protection should be
Lithium extraction process selected according to the hydrochemical type of different salt lakes. In the future, different salt lakes
should focus on direct lithium extraction technology from the original brine.
Ó 2022 China University of Geosciences (Beijing) and Peking University. Published by Elsevier B.V. on
behalf of China University of Geosciences (Beijing). This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Lithium, as a rare metal, is the lightest alkali metal in nature
(density 0.534 g/cm3) (Tarascon, 2010; Liu et al., 2020). With a ser-
ies of advantages, such as high charge per unit mass, high energy
density, and the lowest activity in alkali metal elements
(Tarascon and Armand, 2001; Berecibar, 2019), lithium is known
as an important strategic resource in the 21st century (Qian
et al., 2015; Wiśniewska et al., 2018; Li et al., 2019a). Lithium is
widely used in the military (Cyburt et al., 2010; Schulz et al.,
2017), geology, materials, medicine, nuclear industry, and aero-
space fields (Wu and Huang, 2006; Zhao et al., 2014; Wu et al.,
2019; Zhang et al., 2019b; Clara and Martins, 2020; Lu et al.,
2021). In recent years, new energy vehicles with lithium batteries
as the main power source have rapidly developed with the contin-
uous consumption of global petroleum energy (Mika et al., 2018;
Jiménez-De-La-Cuesta and Mauritsen, 2019; Johnson and Lyman,
2020; Bandh et al., 2021; Ye et al., 2021). It is predicted that the
global demand for lithium resources will continue to increase at
⇑ Corresponding author at: College of Geoscience and Surveying Engineering,
China University of Mining and Technology (Beijing), Beijing 100083, China.
E-mail address: zhengmp2010@126.com (M. Zheng).
an annual rate of 10% (Martin et al., 2017; Liu et al., 2019). There-
fore, the separation and recovery of lithium from lithium-
containing mineral resources are of great climatic and economic
significance.
The main lithium resources in the world are distributed in sea-
water, solid-phase ore, and salt-lake brine. Among them, the total
amount of lithium resources in seawater is the largest, approxi-
mately 230 billion tons of lithium (lithium metal), which is thou-
sands of times the total amount of lithium ore and brine lithium
resources. The grade of the lithium resources in seawater is too
low (0.1–0.2 ppm) to have economic utilization value at present,
and the cost of extracting lithium from seawater will be dozens
of times higher than that from salt-lake brine and solid-phase
ore even after decades of scientific and technological progress
(Kesler et al., 2012; Ogawa et al., 2014). At present, the main
sources of lithium in the world are derived from salt-lake brine
(62.6%) and lithium-containing hard rock minerals (37.4%), and
salt-lake lithium resources account for 71.9% of lithium resources
in China. The lithium extraction process of lithium-containing hard
rock minerals (spodumene, lepidolite, etc.) is mature and includes
the processes of hard rock crushing, high-temperature crystalliza-
tion, and acid leaching flotation, which consume much energy and
chemical reagents, resulting in great pollution and high cost (the

https://doi.org/10.1016/j.gsf.2022.101485
1674-9871/Ó 2022 China University of Geosciences (Beijing) and Peking University. Published by Elsevier B.V. on behalf of China University of Geosciences (Beijing).
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
T. Ding, M. Zheng, S. Peng et al.
cost of producing lithium carbonate products per ton is 30% – 50%
higher than that of extracting lithium from the salt lake) (Kesler
et al., 2012; Yan et al., 2012; Xing et al., 2019; Salakjani et al.,
2021; Rioyo et al., 2022). Therefore, the development of an efficient
salt-lake lithium extraction process is of great significance to
developing lithium resources.
The factors affecting the selection of lithium extraction technol-
ogy in different salt lakes mainly include the hydrochemical prop-
erties of brine (Zheng and Liu, 2010; Yu et al., 2015a), salinity,
supporting power equipment of lakes, and environmental protec-
tion requirements (Zheng and Qi, 2006; Gao et al., 2012; Yu
et al., 2013; Zheng et al., 2016; Li et al., 2019a; Zhang et al.,
2019a; Meng et al., 2021; Sun et al., 2021). Among them, the
hydrochemical properties and types of salt lakes are the key factors
that determine the selection of the extraction process of salt lake
lithium ore. Recently, some studies have reviewed lithium extrac-
tion technologies from salt lakes on the Tibet Plateau (Xu et al.,
2016, 2017b; Wang et al., 2018a; Liu et al., 2019; Zhang et al.,
2019b, 2021; Weng et al., 2020). Liu et al. (2017) summarized
the technologies of lithium extraction from high-magnesium salt
lakes on the Tibet Plateau; Zhao et al. (2017) pointed out the char-
acteristics of critical lithium extraction technologies and the influ-
ence of high magnesium to lithium ratio conditions on the
separation effect. Some scientists have reported many certain
types of techniques used in salt lakes, such as the membrane
method (Li et al., 2019b; Razmjou et al., 2019; Zhang et al., 2020;
Hou et al., 2021; Butt et al., 2022), solvent extraction method (Ji
et al., 2016; Shi et al., 2018; Li et al., 2019c; Su et al., 2019;
Wang et al., 2019b), adsorption method (Wang et al., 2018b; Li
et al., 2020; Weng et al., 2020; Luo et al., 2021; Yang et al., 2022)
and evaporative crystallization method (Wu et al., 2012a; Yu
et al., 2013, 2014,2015c,2016; Han et al., 2021). Herein, the spatial
zoning regularity was revealed by reasonably dividing the hydro-
chemical characteristics and types of lithium-containing salt lakes
in the Tibet Plateau. The lithium extraction process used in the
hydrochemical belt of the salt lakes was explored, and the prob-
lems that existed in the production and technical improvement
were analyzed, aiming to provide a reference for selecting suitable
lithium extraction technology for lithium-containing salt lakes
with relevant hydrochemical types in the world.
2. Hydrochemical classification of salt lakes
The hydrochemical properties and classification of salt lakes are
the key factors in selecting the extraction process of lithium
extraction technology from salt lakes. The concentration of the
main ions in salt lakes is used as the basis for dividing the hydro-
chemical types of salt lakes, including cations such as Na+, K+, Ca2+,
Mg2+, and Li+ and anions such as Cl-, SO2- 2– –
4 , CO3 , and HCO3 (Wu
et al., 2005; Zheng and Qi, 2006; Zheng and Liu, 2010; Ye and
Zheng, 2016). In this paper, the corrected Kurnakov-Valyashko
method was used to classify lithium-containing salt lakes in the
Tibet Plateau, which were divided into chloride type, magnesium
sulfate subtype, sodium sulfate subtype, and carbonate type.
According to the total alkalinity ratio and the different saline min-
eral assemblages, the carbonate type was divided into three sub-
types (strong carbonate subtype, moderate carbonate subtype,
and weak carbonate subtype). The distribution of the hydrochem-
ical type of the salt lakes in the Tibet Plateau exhibits the charac-
teristics of areas in the east–west direction and belts in the
north–south direction, which are roughly divided into 5 belts
(Fig. 1). They are from the south to north Belt I (carbonate belt),
Belt II (sodium sulfate subtype belt), Belt III (magnesium sulfate
subtype belt), Belt IV (chloride-sulfate type belt), and Belt V
(sodium sulfate subtype leakage belt).
2
Geoscience Frontiers 14 (2023) 101485
2.1. Carbonate belt (Belt I)
Belt I is mainly carbonate-type and is located in southern Tibet.
Belt I is divided into two sub-belts by taking the Mountain-
Nyenchen Tanglha Range as the boundary, including the South
sub-belt (low-mineralized carbonate-type sub-belt in southern
Tibet, I1) and the North sub-belt (high-mineralized carbonate-
type sub-belt in northern Tibet, I2). The south sub-belt is domi-
nated by generalized salt lakes (x(NaCleq)
0.30%) and freshwater
lakes. In addition, some small lakes are salt lakes (x(NaCleq) > 3.5%);
for example, the mineralization of Cuochuolong Salt Lake reaches
154.1 g/L. There are high concentrations of Li+ in saltwater lakes
and salt lakes in hydrochemical belts (Nie et al., 2011; Wu et al.,
2012a; Yu et al., 2015b; Zheng et al., 2016).
Among them, the hydrochemical type of Gongzhucuo Salt Lake
belongs to the weak carbonate type. The salinity of Gongzhucuo
Salt Lake is 5.4 g/L, its Li+ concentration reaches 37.53 mg/L, and
the Li  103/TDS is 6.95, which is consistent with the anomalous
center of high Li+ concentrations in the plateau geothermal water
reported in the literature (Zheng, 2019; Wang et al., 2020a), indi-
cating that the source of lithium in the plateau salt lake is closely
related to geothermal water (Fig. 2) (Wang et al., 2021a). The lakes
in the North sub-belt are mainly salt lakes and saltwater lakes, and
the salinity of the saltwater lakes is also higher than that in the
south sub-belt. The sub-belt salt lake is characterized by high con-
centrations of alkali metals (such as lithium, cesium, and rubid-
ium) and low concentrations of magnesium. The brine
compositions of Zabuye Salt Lake and Dangxiongcuo Salt Lake
serve as the typical representatives, and the specific hydrochemical
coefficients are shown in Table 1.
2.2. Sodium sulfate subtype belt (Belt II)
The sodium sulfate subtype belt (Belt II) is located in the north
of the carbonate belt (Belt I) and extends in an east–west direction.
The subtype belt includes salt lakes and some saltwater lakes,
which are mainly the sodium sulfate type, a small part of magne-
sium sulfate- and carbonate-type salt lakes, and a small amount
of freshwater lakes. The value of Li  103/TDS in the salt lakes
decreases gradually from south to north, and the Mg/Li value of
the hydrochemical belt is slightly higher than that of the carbonate
belt (Belt I). The Mg/Li value is basically less than 30, and a few salt
lakes have high Mg/Li values (Table 2).
2.3. Magnesium sulfate subtype belt (Belt III)
The magnesium sulfate subtype belt (Belt III) is located in the
north of the sodium sulfate subtype belt (Belt III), which is dis-
tributed in an east--west direction. The subtype belt is dominated
by magnesium sulfate subtype salt lakes and a small number of
sodium sulfate subtypes and chloride types. There are many salt
lakes and saltwater lakes in the sub belt, and some small freshwa-
ter lakes are distributed close to modern glaciers. The lake water is
characterized by a high Mg/Li value, which is generally 12–85.
Among them, the Mg/Li value of Ruolacuo Salt Lake is the highest
(approximately 172), and the Mg/Li value of Akesaiqin Lake is the
lowest (approximately 5.91). The lithium content and Li  103/TDS
of the whole distribution belt (Belt III) are lower than those of belts
I and II (Table 3). The contents of boron and potassium in Belt III
are generally low, and only some lakes are high. For example, the
B2O3 content of Yongbocuo is up to 17,000 mg/L, and the potas-
sium content is up to 5380 mg/L. Recently, an abnormal accumula-
tion area of chloride type appeared near Duogecuoren Salt Lake in
the south of the hydrochemical belt (Fig. 3), which is associated
with the occurrence of a large range of Jurassic gypsum mounds.
In addition, an anomaly of the bromine chloride coefficient was
T. Ding, M. Zheng, S. Peng et al. Geoscience Frontiers 14 (2023) 101485

Fig. 1. Hydrochemical belt distribution of lithium-containing salt lakes in the Tibet Plateau in China (I, Carbonate belt; II, Sodium sulfate subtype belt; III, Magnesium sulfate
subtype belt; IV, Chloride sulfate type belt; V, Sulfate type leakage belt).

Fig. 2. Lithium trend surface analysis of geothermal water in Tibet Plateau.

found in the Duogecuoren Lake area (Wu et al., 2012b; Niu et al.,
2013). Therefore, it is speculated that the deep part of the
chloride-type accumulation area may contain a Jurassic sodium
potassium salt body similar to its western Turkmen.
2.4. Chloride sulfate type belt (Belt IV belt) and sulfate type leakage
belt (Belt V)
The chloride-sulfate belt (Belt IV) is located in the northeast of
the magnesium sulfate subtype belt (Belt III), extending from east
to the west in a long diamond shape, including the Kumukuli mag-
nesium sulfate subtype substabel (IV1), the Qaidam perimeter
sodium sulfate substrane (IV2), the Qaidam magnesium sulfate
subtype subsist (IV3), and the two chloride subsist (IV4) at the Qai-
dam Drought Center.
The lakes in the Kumukuli magnesium sulfate subtype belt (IV1)
are distributed in the Kumukuli Basin, which is characterized by an
extremely high Mg/Li value (473–2781), while Li  103/TDS of
0.02–0.08 is the lowest (Table 4). The sodium sulfate subtype
(IV2) around Qaidam is distributed in the vast area around the
north and south of Qaidam, scattered in the north foot of East Kun-
lun Mountain, the south foot of South Qilian Mountain and Qilian
Mountain, which includes salt lakes and freshwater lakes. The
freshwater lake replenished by glacier-melt water is a carbonate

3
T. Ding, M. Zheng, S. Peng et al. Geoscience Frontiers 14 (2023) 101485

Table 1
Hydrochemical coefficients of the carbonate-type hydrochemical belt (I1/I2) containing lithium salt lake.
P
Salt lake Hydrochemical type Salt lake belt TDS Li(Ι) Mg/Li Li 103/ salt
(g/L) (mg/L)
Gongzhucuo Strength carbonate type I1 5.40 37.48 2.19 6.95
Aguocuo Strength carbonate type Ⅰ2 300.00 101.00 0.10 0.34
Daduocuo Strength carbonate type Ⅰ2 135.45 196.30 2.02 1.45
Dabicuo Strength carbonate type Ⅰ2 63.83 33.20 5.28 0.52
Zabuye North Medium carbonate type Ⅰ2 396.00 1848.00 0.01 4.67
Zabuye South Medium carbonate type Ⅰ2 243.00 1085.00 0.02 4.47
Chalicuo Medium carbonate type Ⅰ2 39.42 34.00 2.80 0.86
BangeⅠ Medium carbonate type Ⅰ2 68.50 104.00 0.64 1.52
BangeⅡ Medium carbonate type Ⅰ2 401.91 267.30 0.07 0.67
Bange III Medium carbonate type Ⅰ2 187.33 121.00 0.99 0.65
Dangqiongcuo Strength carbonate type Ⅰ2 205.94 404.51 0.26 1.96
Yagedongcuo Weak carbonate type Ⅰ2 68.02 126.00 1.92 1.85
Chalaka Medium carbonate type Ⅰ2 68.72 185.04 0.15 2.69
Dujiali Medium carbonate type Ⅰ2 219.73 462.50 0.43 2.10
DubukeⅡ Weak carbonate type Ⅰ2 302.05 950.73 0.02 3.15
Zhaxicuo Strength carbonate type Ⅰ2 21.60 26.90 9.29 1.25
Jiongmocuo Medium carbonate type Ⅰ2 17.14 26.20 10.24 1.53
Gegengcuo Medium carbonate type Ⅰ2 85.97 25.00 3.22 0.29
Awengcuo Medium carbonate type Ⅰ2 27.28 51.30 6.10 1.88
Angdaer Weak carbonate type Ⅰ2 180.87 64.00 3.36 0.35
Pengyancuo Weak carbonate type Ⅰ2 208.08 74.50 0.77 0.36
Beileicuo Weak carbonate type Ⅰ2 204.04 120.03 0.96 0.59
Rebangcuo Weak carbonate type Ⅰ2 75.91 15.96 22.83 0.21

Table 2
Hydrochemistry coefficient of lithium in a lake of the sodium sulfate subtype belt.
P
Salt lake Hydrochemical type Salt lake belt TDS Li(Ι) Mg/Li Li 103/ salt
(g/L) (mg/L)
Laguocuo Sodium sulfate subtype Ⅱ 43.99 317.30 3.04 7.21
Jibuchaka Magnesium sulfate subtype Ⅱ 82.20 466.00 3.07 5.67
Mamicuo Sodium sulfate subtype Ⅱ 153.41 995.25 3.64 6.49
Dongcuo Sodium sulfate subtype Ⅱ 67.61 86.20 19.37 1.28
Nieercuo Sodium sulfate subtype Ⅱ 248.58 630.10 2.49 2.53
Zacangchaka I Magnesium sulfate subtype Ⅱ 73.35 120.00 15.79 1.64
Zacangchaka Ⅱ Sodium sulfate subtype Ⅱ 384.78 999.88 14.70 2.60
Zacangchaka III Magnesium sulfate subtype Ⅱ 57.28 489.60 2.45 8.55
Duomacuo Magnesium sulfate subtype Ⅱ 203.31 80.50 264.59 0.40
Bilongcuo Sodium sulfate subtype Ⅱ 257.90 205.00 24.98 0.79
Timaerchaka Chloride type Ⅱ 311.49 357.00 33.33 1.15
Kongkongchaka Magnesium sulfate subtype Ⅱ 164.25 305.00 7.54 1.86
Eyacuo Magnesium sulfate subtype Ⅱ 205.63 273.50 67.93 1.33
Jialecuo Sodium sulfate subtype Ⅱ 328.25 312.00 7.24 0.95
Chanacuo Magnesium sulfate subtype Ⅱ 349.87 299.50 67.10 0.86
Chabocuo Sodium sulfate subtype Ⅱ 251.48 243.40 19.91 0.97
Amucuo Sodium sulfate subtype Ⅱ 218.84 135.03 94.26 0.62
Maguochaka Sodium sulfate subtype Ⅱ 321.59 311.00 20.63 0.97
Riwanchaka Ⅱ Magnesium sulfate subtype Ⅱ 321.65 168.02 19.51 0.52
Gangmacuo Weak carbonate type Ⅱ 369.07 205.05 0.46 0.56
Jiezechaka Weak carbonate type Ⅱ 143.12 135.50 1.68 0.95

Table 3
Hydrochemistry coefficient of lithium in the lake of the magnesium sulfate subtype belt.
P
Salt lake Hydrochemical type Salt lake belt TDS Li(Ι) Mg/Li Li 103/ salt
(g/L) (mg/L)
Bandao Chloride type III 247.90 97.70 13.51 0.39
Longmucuo Magnesium sulfate subtype III 172.50 169.80 88.10 0.98
Yakecuo Magnesium sulfate subtype III 236.78 107.00 55.79 0.45
Duogecuoren Chloride type III 284.48 167.79 12.16 0.59
Yupanhu Magnesium sulfate subtype III 324.74 74.40 73.12 0.23
Shuangjuhu Magnesium sulfate subtype III 317.34 271.00 65.68 0.85
Yongbohu Magnesium sulfate subtype III 330.10 166.40 29.84 0.50
Maergaichaka Magnesium sulfate subtype III 78.72 30.15 25.44 0.38
Ruolacuo Magnesium sulfate subtype III 103.91 24.05 172.14 0.23
Akesaiqin Magnesium sulfate subtype III 28.09 94.00 5.91 3.35
Lexiewudan Chloride type III 136.62 171.00 12.81 1.25
Kushui Magnesium sulfate subtype III 113.85 68.00 49.32 0.60

4
T. Ding, M. Zheng, S. Peng et al. Geoscience Frontiers 14 (2023) 101485

low, ranging from 0.05 to 0.11, while Mg/Li is the highest, reaching
1145–4215.
The sulfate-type leakage area (V) is east of the above four
hydrochemical belts and is roughly bounded by the northeast-
trending large fault of Yangbajing, including Sanjiang in the eastern
Tibetan Plateau and the vast areas in the middle and lower reaches
of Yarlung Zangbo. Belt V is dominated by large-scale saltwater
lakes and freshwater lakes (outflow lakes), and some are salt lakes.
From northeast to southeast, Qinghai Lake has the largest plateau
area (4320.31 km, August 2009) and belongs to the magnesium
sulfate subtype, and Yangzhuoyongcuo (magnesium sulfate sub-
type) and Pumoyongcuo (sodium sulfate subtype) are brackish
water lakes in Southeast Tibet. The lithium content of the leakage
area is generally low (Table 5). Qinghai Lake Li  103/TDS is 0.057,
which is 11 times higher than that of modern seawater.

3. Extracting lithium technology

3.1. Belt I

Fig. 3. Abnormal accumulation area of chloride salt lake and bromo-chlorine
coefficient of salt spring.
type with a high Mg/Li ratio (approximately 105), while the
lithium content and Li  103/TDS are 0.01–0.24. The magnesium
sulfate subtype (IV3) in the Qaidam region is distributed in most
areas of the Qaidam Basin. Most lakes are mostly salt lakes with
a high salinity, which belong to the magnesium sulfate subtype.
The Mg/Li of the salt lakes is generally 40–114, of which the high-
est is 1190.82 (Gaskule Lake).
The lithium content of the salt lakes in eastern and western Tai-
jinar to Yiliping is high, up to 0.42–0.80. The chloride sub belt (IV4)
is the concentration center of the late Quaternary salt lake evolu-
tion in the Qaidam Basin, which is located in Qarhan Salt Lake,
Kunteyi Lake, potassium Lake, and Niulang Zhinv Lake on the
northern margin. The salinity of IV4 is as high as 617.2 g/L, which
is rare worldwide. Due to the long-range northward stress from
land-land collision, the residual ultraconcentrated brine of the
Kunteyi Lake gathered to the lake edge. The lithium content of Niu-
lang Zhinv Lake is 100 mg/L, while that of Potassium Lake is
2.2 mg/L. The reason for the difference needs to be studied in detail
in the future. The Li  103/TDS of the salt lakes in belt IV4 is very
Zabuye Salt Lake is the only salt lake used for lithium extraction
in the carbonate hydrochemical belt of the Tibet Plateau. It is
located in the territory of Zhongba County, Ngari Prefecture, Tibet,
and belongs to the arid high prototype climate (Wang et al.,
2019a). Zabuye Salt Lake, with an area of 247 km2, is divided into
2 lakes from north and south, which is in the late stage of salt lake
evolution (Zheng et al., 2007; Wang et al., 2016; Ling et al., 2017).
The south of Zabuye Salt Lake became a semidry salt lake, making
the lake a solid–liquid coexistence of salt lake deposits. The lake is
rich in lithium, potassium, boron, rubidium, cesium, bromine, and
other mineral elements, in which lithium carbonate reserves reach
1.84 million tons. The lithium mine development process of
Zabuye Salt Lake is divided into halogen production and crystal-
lization steps. In the halogen production stage, the salt field is used
to rapidly enrich lithium in the brine to prepare a high-
concentration lithium-containing brine. Salt gradient solar pond
technology is mainly used in the crystallization stage, and the pro-
duction process route is shown in Fig. 4 (Sang et al., 2003; Nie et al.,
2010; Deng et al., 2016; Xu et al., 2017a). The salt gradient solar
ponds consist of 3 functional regions, in which the uppermost
region is the upper troposphere (a layer of freshwater), the middle
region is the concentration gradient layer, and the lower layer is
the energy storage area. In the concentration gradient layer, the
specific gravity of the salt solution gradually increases with the
depth of the pool, and there is no convective movement in this
layer. Therefore, the concentration gradient layer prevents the heat
in the lower layer from dissipating upward, which ensures that the
solar energy is stored in the energy storage area at the bottom of

Table 4
Hydrochemistry coefficient of chloride-sulfate type lacustrine lithium.
P
Salt lake Hydrochemical type Salt lake belt TDS Li(Ι) Mg/Li Li 103/ salt
(g/L) (mg/L)
Aqikekule Magnesium sulfate subtype Ⅳ1 82.70 6.79 473.00 0.08
Ayakekumu Magnesium sulfate subtype Ⅳ1 157.40 2.97 2781.00 0.02
Mangya Sodium sulfate subtype Ⅳ2 41.40 10.00 105.20 0.24
Xiligou Sodium sulfate subtype Ⅳ2 259.90 215.00 51.68 0.82
Yiliping Magnesium sulfate subtype Ⅳ3 328.00 262.00 92.29 0.80
West Taijinar Magnesium sulfate subtype Ⅳ3 338.00 201.53 67.74 0.60
East Taijinar Magnesium sulfate subtype Ⅳ3 332.00 141.00 40.33 0.42
Da Qaidam Magnesium sulfate subtype Ⅳ3 276.00 84.91 114.22 0.31
Gasikule Magnesium sulfate subtype Ⅳ3 333.51 24.85 1190.82 0.07
Qarhan Chloride type Ⅳ4 413.81 126.00 508.00 0.30
Kunteyi Chloride type Ⅳ4 329.40 26.84 1414.81 0.08
Potassium Lake Chloride type Ⅳ4 404.40 2.20 4215.56 0.05
Niulang Zhinv lake Chloride type Ⅳ4 617.20 100.00 1145.00 0.11

5
T. Ding, M. Zheng, S. Peng et al.
Table 5
Some related hydrochemical data of lakes in the Leaked area.
Salt lake Hydrochemical type
Qinghai Lake Sodium sulfate subtype
Pumoyongcuo Magnesium sulfate subtype
Yangzhuoyongcuo Sodium sulfate subtype
Fig. 4. Production process of lithium extraction in Zabuye Salt Lake.
the pool (Sang et al., 2006). The brine in the solar ponds is heated
to 40–60 ℃ to meet the conditions of high-temperature crystalliza-
tion of lithium carbonate. Lithium carbonate is concentrated and
precipitated to directly obtain a grade of approximately 75%
lithium carbonate products, and then the obtained lithium carbon-
ate is purified by the carbonation method (Huang et al., 2009; Ding
et al., 2022a).
China Tibet Mining Development Co. ltd started the construc-
tion of the first phase of Li2CO3 in Zabuye Salt Lake in March
2003, and Li2CO3 was successfully produced in August 2005. How-
ever, there are some problems in the process, such as large brine
process loss, cold and hypoxia in areas above 4000 m above sea
level, and poor basic conditions, resulting in limited production
capacity. Based on Zabuye Salt Lake brine hydrochemical charac-
teristics, a series of technical improvements were made to enhance
the output of Li2CO3 production.
The PAN-Li/Al-LDH composite adsorbent was directly synthe-
sized by modification of kaolin using the high-voltage electrostatic
spinning method. The synthesis process is shown in Fig. 5. The
adsorption capacity of PAN-Li/Al-LDHs for Li+ in salt lakes was
revealed by adsorption kinetics experiments, isothermal adsorp-
tion models, fixed bed adsorption experiments, and 60 cycles of
adsorption. The results showed that the adsorption capacity of
PAN-Li/Al-LDHs for Li+ in brine reached 5.2 mg/g at a pH of 3.
The adsorption kinetics were in line with the pseudosecond-
Geoscience Frontiers 14 (2023) 101485
P
Salt lake belt TDS Li(Ι) Mg/Li Li 103/ salt
(g/L) (mg/L)
Ⅴ 14.12 0.808 982 0.057
Ⅴ 0.38 0.01 3631 0.026
Ⅴ 1.87 0.53 356 0.284
order adsorption kinetics model, and the isothermal adsorption
model conformed to the Langmuir model. The adsorption capacity
of PAN-Li/Al-LDHs remained at 4.9 mg/g after 60 cycles of adsorp-
tion experiments. Based on quantum chemical calculations com-
bined with X-ray diffraction (XRD), Fourier transform infrared
(FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray
photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller
(BET) methods, the Al-O- and Al-Al structures of PAN-Li/Al-LDHs
exhibited the largest adsorption energy and served as the main
adsorption sites for Li+ in the brine (Fig. 6). PAN-Li/Al-LDHs were
used without any chemical reagents, and only water in the desorp-
tion process was employed to elute the adsorbed Li+, which did not
cause any damage to the fragile ecological environment in Tibet
(Ding et al., 2022a).
The adsorption technology was further optimized to improve
the adsorption capacity of the adsorbents for Li+ in the salt lake.
The functional groups of crown ether with special adsorption
effects on Li+ were intercepted, and a new type of mineral carrier
adsorption material was synthesized by chemical grafting technol-
ogy and bulk blending technology with silica gel and zeolite with
rich reserves in Zabuye Salt Lake as the carrier (Fig. 7) (Ding
et al., 2021; Ding et al., 2022b). The quantum chemical calculation
was used to improve the adsorption site in this kind of technical
route. The adsorption mechanism of the adsorbents for Li+ was
explained by density functional theory (DFT) combined with a ser-
6
T. Ding, M. Zheng, S. Peng et al. Geoscience Frontiers 14 (2023) 101485

Fig. 5. Synthesis roadmap of modified kaolin.

Fig. 6. The adsorption mechanism of modified kaolin.

Fig. 7. (a) Natural zeolite and (b) silica gel-coated zeolite nanoparticles.

7
T. Ding, M. Zheng, S. Peng et al.
ies of characterization methods (Shang et al., 2014; Mahammedi
et al., 2017). Due to the reliability of the B3LYP hybrid functional
in processing electron exchange and correlation in extensive
molecular systems, the 6–31 + G (d, p) basis sets of the B3LYP
hybrid functional (Lee et al., 1988; Raghavachari, 2000) were uti-
lized to optimize the initial structures of the complexes and Li(Ι)
(Fig. 8). In addition, the 6–311 + G (d, p) basis sets of the B3LYP
hybrid functional were employed to calculate the natural bond
orbit (NBO) of the complex and further analyze the interaction
mechanism between the functional groups and Li(Ι) (Fig. 9)
(Ramos-Sanchez et al., 2014; Wang et al., 2020b). According to
density functional theory and a series of characterization methods,
C-O in the functional groups of the natural mineral grafted crown
ether participated in the coordination of Li(I) as an electron donor,
and the natural electron configuration of Li+ is 2 s0.093p0.183d0.01.
The results showed that the electrons were mainly transferred
from the functional group to the 3P orbital of Li+, realizing the
selective adsorption of Li+ in the salt-lake brine. Among them, 4-
Fig. 8. Initial structure diagram of functional groups in mineral grafted 18 crown 6 ether: (a) HOMO and (b) LUMO.
Fig. 9. Mineral grafting before and after adsorption of functional groups in 18 crown 6 ethers: (a) HOMO and (b) LUMO.
8
Geoscience Frontiers 14 (2023) 101485
formyl benzo 15-crown-5(4-FB15C5) was grafted onto zeolite
through an acetal reaction to synthesize a nanofiber containing
crown ether, which reached adsorption equilibrium within 2.5 h
with a maximum adsorption capacity of 8.6 mg/g, exhibiting the
prospect of industrial application.
3.2. Belt II
Only Jiezechaka Salt Lake is currently conducting pilot tests in
the belt II. Due to the low Mg/Li value in salt lakes, the extraction
method is adopted as the main technology to extract lithium. The
lithium extraction process is shown in Fig. 10.
The extraction method for lithium extraction was first reported
in a patent published by the American lithium company in 1968,
which used 20% and 80% tributyl phosphate (TBP) and diisobuty-
rone (DIBK), respectively. However, the lithium extraction process
is cumbersome and expensive, and the extraction rate of lithium
reached 80% after seven extractions (Zhou et al., 2020). Although
T. Ding, M. Zheng, S. Peng et al.
Fig. 10. Lithium extraction process.
the extraction method has not been industrialized, it laid a theoret-
ical foundation for the subsequent extraction of lithium from high-
magnesium salt lakes by the TBP-DIBK system. The Shanghai Insti-
tute of Organic Chemistry, Chinese Academy of Sciences, improved
the TBP extraction system in 1975. TBP, N-503, and 200 kerosene
with system proportions of 20%, 20%, and 60% were added to
extract lithium from the saturated magnesium chloride solution
(Shi et al., 2019). The total recovery rate of lithium in the pilot test
was more than 96%, and the production cost of lithium carbonate
per ton was approximately 40,000 yuan. However, the TBP used
in this method has certain toxicity (Chen et al., 2019, 2021; Cui
et al., 2021; Sun et al., 2022). In 1979, the Qinghai Salt Lake
Research Institute of the Chinese Academy of Sciences evaporated
salt lake brine, precipitated a mixed salt of magnesium and potas-
sium, and acidified the brine to remove boron. FeCl3 was added to
the lithium-rich brine, and then the self-invented 80% TBP-200 sul-
fonated kerosene extraction system was added to form the extract
LiFeCl42TBP in the organic phase of the brine. HCl (6–9 mol/L)
served as the stripping solution to release lithium from the LiFeCl4-
2TBP extract, and the obtained product was dried to obtain the
anhydrous LiCl product. The extraction rate of lithium was 99.1%,
and the separation coefficient of lithium and magnesium was
1.87  105. Among them, TBP is a neutral extractant with a long
service life, easy preparation and purification, low price, no com-
bustion at room temperature, low solubility in water, and stable
chemical properties. However, TBP has a slight inhibitory effect
on cholinesterase in human erythrocytes and plasma. TBP is neces-
sary to recycle and reuse to avoid environmental pollution and
human harm and save costs (Sharma et al., 2016; Swain, 2017).
Su et al. (2020a), Su et al. (2020b), Su et al. (2020c) conducted a
series of in-depth studies on the lithium extraction process of a
salt-lake extraction system. The influence of the pH value of the
solution on the extraction system was determined, and the extrac-
tion complexes formed by Li+ and H+ in the TBP-FeCl3 system were
[Li(TBP)2] [FeCl4] and [H(TBP)2] [FeCl4], respectively. The extraction
experiments were carried out at 25 ℃. The equilibrium constant K
of TBP for H+ was 6.63 times that of Li+, and the competition
between Li+ and H+ in the extraction system was quantitatively
studied. On this basis, P507 was added to the original extraction
system to form a TBP/P507-FeCl3 extraction system. In the system,
the extractant was still TBP, and the lithium-containing extract
was [Li(TBP)2] [FeCl4]. When stripping with water, Li+ in the extract
[Li(TBP)2] [FeCl4] was released to achieve the stripping effect. Com-
9
Geoscience Frontiers 14 (2023) 101485
pared with the traditional TBP-FeCl3 extraction system, the strip-
ping process reduced the use of concentrated acid and promoted
the green process of lithium extraction to a certain extent.
3.3. Belt III
Only Longmuco Salt Lake has carried out pilot production of
lithium extraction in belt III. The aluminum-based adsorbent was
used to adsorb lithium ions in the original brine, and then a
nanofiltration membrane was used to produce battery-grade
lithium carbonate products. The production process is shown in
Fig. 11. In the industrialization of lithium salt lakes, the extraction
method is a lithium extraction technology with broad application
prospects, which has the advantages of simple operation, easy
recycling, and environmental protection. The separation and selec-
tive capture of metal ions in the liquid phase by adsorption is also a
current metallurgy chemical research hotspot in the field of envi-
ronmental and energy recovery.
At present, the adsorbents used for lithium extraction in salt
lakes mainly include manganese-based ion sieve adsorbents,
titanium-based ion sieve adsorbents, surface-ion imprinting adsor-
bents, and aluminum-base adsorbents (Choubey et al., 2017).
Among them, the ion sieve-type adsorption material is a kind of
adsorbent with the highest adsorption capacity in the current
report, which possesses the maximum adsorption capacity of
49.6 mg/g (Sun et al., 2011). The precursor of the lithium-ion sieve
was formed by the reaction of manganese oxide and lithium salt,
and the ion sieve was obtained by eluting Li+ with acid (Kamran
and Park, 2020). The ion sieve was placed in the brine containing
lithium to adsorb Li+ in the brine to form lithium manganese com-
posite oxides, and the newly formed lithium manganese composite
oxide was pickled to extract Li+ (Fig. 12). Common manganese-
based precursors include LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4
with a spinel structure, which selectively adsorb Li+ after acid elu-
tion. However, due to the Jahn teller effect produced by the 3,4
valent disproportionation reaction of Mn, manganese-based adsor-
bents are dissolved and damaged in the adsorption process, result-
ing in the unstable structure of the adsorbent, which is difficult for
industrial application (Chitrakar et al., 2001; Zhang et al., 2007;
Wang et al., 2009; Ryu et al., 2015; Xiao et al., 2015). Therefore,
researchers have tried to prepare a new type of ion sieve with more
stable oxides. In 1971, Desckanvers and others synthesized a Li4-
Ti5O12 titanium ion sieve with a spinel structure, and the structural
T. Ding, M. Zheng, S. Peng et al. Geoscience Frontiers 14 (2023) 101485

formula was [Li]8a[Li1/3Ti5/3]16d[O4]32e with a lattice constant

of 0.836 nm. The titanium lithium-ion sieve usually takes TiO2 or
Ti(OC4H9)4 as the titanium source and LiOH, Li2CO3, or CH3COOLi
as the lithium source. The precursors are generated by the high-
temperature solid phase reaction or hydrothermal/solvothermal
reaction, and then they are replaced with acid washing to remove
Li+, finally obtaining a titanium ion sieve adsorbent. Titanium
lithium-ion sieves exhibit stable properties, low dissolution loss,
good acid resistance, large adsorption capacity (15–25 mg/g), and
high lithium elution rate (Jeong et al., 2015; Moazeni et al., 2015;
Zhang et al., 2016; Xu et al., 2017b; Li et al., 2020). However, the
problems of titanium as the raw material, the poor permeability
of the powdered titanium in the synthesis process, the easy consol-
idation, and the low effective product rate of the adsorbent result
in the high cost of the titanium adsorbent, slow adsorption rate,
and long adsorption cycle. The adsorption capacity of the titanium
ion sieve is greatly reduced after molding and granulation, which
hinders its further development. Ion imprinting technology is an
effective method to prepare adsorption materials with specific
selectivity to target ions, which is due to the high matching of its
adsorption vacancy with the charge number, radius, and spatial
structure of the template ions. However, the ion imprinting tech-
nologies reported in the literature take expensive crown ether as
functional carriers, and their elution process requires a strong acid,
which is difficult to use on a large scale at present.
Aluminum-based adsorbents developed from the aluminum
salt precipitation method are currently the only adsorbents for
industrial lithium extraction from salt lakes (Wang et al., 2013).
The core of the adsorbents is the synthesis of LiX2Al(OH)3nH2O
with selective adsorption on Li+, where X stands for anion, usually
Cl. The adsorption and desorption mechanism is as follows
(Sileika et al., 2011; Qu et al., 2016; Cai et al., 2018):
LiCl(1X)2Al(OH)3 nH2 O + xLiCl ! LiCl2Al(OH)3nH2 O (Adsorption).

Fig. 11. Production process of lithium extraction by the adsorption method.

Fig. 12. Lithium-ion adsorption process of the ion sieve adsorbent.

10
T. Ding, M. Zheng, S. Peng et al.
LiCl2Al(OH)3 nH2 O + H2 O ! LiCl(1X)2Al(OH)3nH2 O + xLiCl (Desorption).
However, the adsorption capacity of aluminum-based adsorp-
tion materials is low (usually approximately 1–3 mg/g). The effec-
tive adsorption sites are reduced after traditional binder molding
and granulation, which leads to a further decrease in the adsorp-
tion capacity. A large number of adsorption towers are built for
industrial use, resulting in a low lithium recovery rate of brine,
an increase in production cost, and a decrease in production effi-
ciency. These defects seriously hinder the large-scale use of
aluminum-based adsorbents for the selective separation of lithium
ions from brine. In conclusion, the design and development of a
new aluminum-based adsorption material without any chemical
reagent in the lithium extraction process has high selectivity for
lithium ions and completely protects the fragile ecological environ-
ment of the plateau to realize the efficient extraction of lithium
from brine resources, which has important theoretical and applica-
tion value.
3.4. Belt IV and V
Qarhan Salt Lake, western Taijinar Salt Lake, and Yiliping Salt
Lake in this hydrochemical belt were subjected to lithium extrac-
tion and production (Gu et al., 2018). Qarhan salt lake is located
in the mid-eastern Qaidam Basin. It is 168 km long in an east–west
direction and 20–40 km wide in a north–south direction, covering
an area of 5856 km2 and 2680 m above sea level. The LiCl resources
of Qarhan Salt Lake are 1.2  107 tons, which is the salt lake with
the highest total lithium resource found in China. The brine of the
Qarhan salt lake is the chloride type, and the ratio of magnesium to
lithium is high, so it is not suitable for the precipitation method. In
2011, the Qarhan salt lake adopted aluminum adsorbents for
industrial production, and the production cost of Li2CO3 was RMB
6000 yuan/ton. The small adsorption capacity per unit mass of
the aluminum adsorbent and a large number of adsorption towers
were built in the presence of the molding and granulation problem
of the adsorbents, resulting in high costs. In 2014, the combination
of nanofiltration membrane separation technology with
aluminum-based adsorbents was applied in the lithium extraction
of the Qarhan salt lake. Lithium extraction by nanofiltration sepa-
rates Mg(II) and Li(I) from salt lakes based on the specificity of the
interception molecular weight and the membrane pore size of the
nanofiltration membrane to the isolation effect of monovalent
inorganic salts. The separation effect can be expressed by the
apparent interception rate Robs and the separation factor SF:
Robs ¼ ðC F  C P Þ=C F  100%
 
C MgðIIÞ =C LiðIÞ P
SF ¼   ð2Þ
C MgðIIÞ =C LiðIÞ F
where CP and CF are the original brine concentration and nanofiltra-
tion concentration, mol/L. CMg(II) and CLi(I) are the concentrations of
Mg(II) and Li(I) in the osmotic solution and the feedstock liquid,
mol/L. When the SF value is close to 1. The higher the SF value is,
the better the separation effect.
Sun et al. (2015) studied the nanofiltration separation of mag-
nesium and lithium in simulated brine with a DL-2540 nanofiltra-
tion membrane, and the study showed that the nanofiltration
separation of Mg(II) and Li(I) was related to pressure and temper-
ature. The separation rate of Mg(II) and Li(I) decreased when the
temperature increased. When the brine flow increased and the
pH decreased, the retention rate of magnesium increased, and
the retention rate of lithium decreased, which was conducive to
the separation of magnesium and lithium. The retention rate of
Mg(II) by the DL-2540 membrane was approximately 60%, and
Geoscience Frontiers 14 (2023) 101485
the separation factor (SF) of magnesium and lithium was approxi-
mately 0.35. Wen et al. (2006) used the DL 2540C membrane pro-
vided by GE Osmonics for nanofiltration separation under the
experimental conditions of 1.1 MPa. The results showed that the
DL 2540C membrane had a high retention rate of sulfate and the
excellent separation effect of the SO2- 4 -type brine. The separation
effect was worse when the salt concentration of the brine
increased, and the DL 2540C membrane was not suitable for
extracting lithium from this type of brine. Kang et al. (2014) veri-
fied the feasibility of the nanofiltration method for lithium extrac-
tion from salt lakes with a DK nanofiltration membrane, in which
three different brines served as the raw materials for the single-
stage operation. The magnesium-lithium ratio in the original solu-
tion was reduced from 48.5, 42.31, and 28.3 to 4.04, 3.21, and 1.86,
respectively. All Ca(II) and SO2-
4 in the raw brine were intercepted,
and the boron interception rate was greater than 73.81%, which
proved that the nanofiltration method can be used for lithium
extraction from salt lakes. Ji et al. (2014) analyzed the separation
effect of magnesium and lithium using a DK nanofiltration mem-
brane. The experimental results showed that the interception rate
of magnesium was significantly reduced with increasing tempera-
ture, while the retention rate of magnesium increased with
decreasing pH. Monovalent metal ions such as Na(I) and K(I)
reduced the separation effect of magnesium and lithium, and the
relationship between magnesium and lithium retention rate was
obtained:
7:26
RMgðIIÞ ¼ RLiðIÞ ð1:06 þ Þ ð3Þ
x  0:77
In summary, nanofiltration membrane separation technology
has high requirements for the total salinity of brine, and brine
can be separated only after dilution. At present, the existing exper-
imental research was carried out in low-concentration simulated
brine, and Mg/Li was generally less than 30. The lithium salt eluted
by the aluminum adsorbents has relatively high purity and low
mineralization, which is suitable for further treatment with the
nanofiltration membrane; therefore, nanofiltration technology
can be combined with adsorption technology to improve the
lithium extraction of salt lakes. Qarhan Salt Lake used the combi-
nation of the adsorption method and nanofiltration membrane
separation technology to reduce the production cost of Li2CO3 to
35,000 yuan/ton, and the output of Li2CO3 in 2020 was approxi-
mately 15,000 tons.
West Taijinar Salt Lake has an altitude of 2680 m, which belongs
to a typical inland arid climate with an average annual tempera-
ture of 4.47 ℃, annual evaporation of 2505.9 mm, and annual pre-
ð1Þ cipitation of 17.8 mm. The concentration of Li(I) in the brine is
201.5 mg/L, Mg/Li is 67.74, the LiCl resource is 3.08 million tons,
and the recoverable reserve is approximately 1.3 million tons,
which is a sulfate-type high-magnesium-lithium-specific salt lake.
The lithium extraction process production line of the calcina-
tion method was built in West Taijinar Salt Lake from 2007 to
2011. In the lithium extraction process, the brine is evaporated
in the salt field to precipitate potassium magnesium mixed salt,
and then most of the boron in the brine is removed by adding acid
to the brine. After boron removal, the brine was evaporated and
crystallized again to remove magnesium and then filtered, washed,
and dried. The main components of the precipitated solid mixed
salt are bischofite and lithium sulfate. The solid mixed salt is
decomposed at high temperatures, and MgO and HCl gas are used
to leach the calcined sinter. The lithium salt is easily soluble in
water and enters the solution, MgO is almost insoluble in water
and remains in the slag, and impurities such as SO2- 4 , magnesium,
and a small amount of boron are in the leaching liquid. Li2CO3
products can be obtained by evaporation, alkali precipitation, and
drying. However, due to the problems of equipment material selec-
11
T. Ding, M. Zheng, S. Peng et al.
tion, HCl recycling, and magnesium slag recovery, the production
could not be continuous at the beginning of the project, and the
cost was as high as more than 8000 yuan. In 2015, West Taijinar
salt lake carried out technical upgrading. The brine of the salt lake
was calcined first and then combined with nanofiltration (Fig. 13).
The Li2CO3 output in 2020 was approximately 0.6 million tons, the
production costs dropped to 40,000 yuan/ton, and the quality of
Li2CO3 was improved, which can be directly used as a raw material
for lithium battery production.
The Yiliping salt lake is located in the middle of the Tsaidam
Basin, and the area is 360 km2. The lake is located in a semiclosed
basin with flat terrain and an altitude of 2683 m. It belongs to a
typical inland arid climate, and the annual evaporation is 150
times the annual rainfall. The Li(I) concentration of the brine is
262 mg/L, Mg/Li is 92.29, LiCl resources are 1.78 million tons,
and the recoverable reserves are approximately 410,000 tons,
which is a sulfate-type high-magnesium-lithium specific salt lake.
The lithium extraction process of Yiliping Salt Lake summarized
the production experience of other similar salt lakes and adopted
the combined process of electrodialysis and nanofiltration
(Fig. 14). In electrodialysis technology, charged particles in solution
migrate through the membrane under the action of an electric
field. The Mg(II) and Li(I) in the brine can be separated using a
monovalent selective ion exchange membrane. The technology
was first applied to desalination and began to be applied to the
separation of Mg(II) and Li(I) in salt lake brine in the early 2000s.
Van der Bruggen et al. (2004) evaluated the monovalent and diva-
lent cation separations of ED (AMV/CMV Selemion membranes and
ACS/CMS Tokuyama membranes) and NF (NTR 7450 and UTC-60)
using electrodialysis techniques, and the results revealed that the
UTC-60 membranes were the most suitable for electrodialysis to
Fig. 13. Process flow chart of the preparation of lithium carbonate by calcination.
12
Geoscience Frontiers 14 (2023) 101485
separate monovalent and divalent cations. Jiang et al. (2014) tried
to extract LiOH from the brine of a salt lake with bipolar membrane
electrodialysis (EEDBM) technology and evaluated the lithium
extraction process with parameters such as current density and
feed concentration. The process cost of EEDBM was approximately
2.59 $/kg, and the density was 30 mA/cm2.
However, H2 and OH– were produced under the electric field
action in the actual production of Yiliping Salt Lake, and the Mg
(OH)2 precipitation generated after a period of use covered the
ion exchange membrane to reduce the efficiency of the membrane.
Therefore, the production of this method requires the frequent dis-
assembly and washing of the membrane, which increases the high
maintenance cost and various production and maintenance pro-
cesses. In 2020, the output of Li2CO3 was approximately 4000 tons,
and the production technology still needs to be improved. Accord-
ing to the hydrochemical characteristics of the brine, Yiliping salt
lake attempted to directly use the adsorption method to extract
lithium. Combined with the early process, lithium is directly sepa-
rated from sodium, potassium, magnesium, boron, and other ele-
ments through adsorption. At the same time, it is seamlessly
connected with the existing 10,000-ton lithium carbonate techni-
cal transformation device to improve the efficiency of lithium
extraction technology and reduce the production cost of lithium
products. At present, the project is in the pilot stage.
4. Discussion
To further reveal the effect of different hydrochemical types on
the lithium extraction process, density functional theory (DFT) was
used to calculate the binding energy between different anions and
T. Ding, M. Zheng, S. Peng et al.
Fig. 14. Lithium extraction process route of Yiliping Salt Lake.
Li(Ι) in brine. The geometries of the isolated lithium cation (Li+),
chloride ion (Cl), sulfate (SO2 2–
4 ), carbonate (CO3 ) and the complex
structures of LiCl, Li+-(CO2– 3 ) and Li +
-(SO2
4 ) were all optimized
under the framework of density functional theory (DFT) with the
B3LYP functional (Becke, 1988; Lee et al., 1988; Raghavachari,
2000) and Pople basis set of 6–31 g(d,p) (Petersson et al., 1988;
Petersson and Laham, 1991). To describe the dispersion interac-
tion, the DFT-D3 dispersion correction method was used in all cal-
culations. The implicit solvent model of SMD (Solvation Model
Based on Density) (Marenich et al., 2009) was applied in all calcu-
lations to correct the solvation effect of water. All calculations were
performed using the Gaussian 16 program. Fig. 15 shows the elec-
tron electrostatic potential analysis of functional groups and the
adsorption energy potential diagrams of anions in different water
chemical types and Li(Ι) in solution. According to the calculation
results of the anion system in salt lakes, the adsorption energies
of Li(Ι) - (Cl), Li(Ι) - (SO2 2–
4 ) and Li(Ι) - (CO3 ) are 1.26 kcalmol
1
, the periodic table. In particular, the radii of Mg2+ and Li+ are simi-
1 1
2.10 kcalmol and 2.63 kcalmol , respectively. Anion adsorp-
tion energy in three hydrochemical types of salt lake Li(Ι) -

(CO2– 2
3 ) > Li(Ι) - (SO4 ) > Li(Ι) - (Cl ). According to Eq. (4), when
lithium is extracted by the adsorption method, the adsorption
energy and capacity of the adsorbed material for Li(Ι) is the highest
in the chloride-type salt lake, and the adsorption capacity is the
lowest in the carbonate-type brine. The binding energy of Li(Ι)
Fig. 15. Optimized geometry and electronic static potential analysis of (a) Cl--ESP, (b) SO2-
13
Geoscience Frontiers 14 (2023) 101485
and CO2–3 in the carbonate brine is the largest, and Li2CO3 has the
property of thermal crystallization. According to the calculation
results, chloride brine is the most suitable for lithium extraction
by adsorption, and carbonate brine is the best for lithium extrac-
tion by the solar pool.
 þ   þ
EðadsorbÞ ¼ E Li  Mol  E Li  EðMolÞ þ EðBSSEÞ ð4Þ
where E(Li+) and E(Mol) are the energies of the isolated lithium
cation and lithium adsorbent (adsorbent and anions), respectively.
E(Li+Mol) is the energy of the complex structure, and E(BSSE) is
the basis set superposition error.
There is a large amount of Mg2+ in the lithium-containing salt
lakes in the magnesium sulfate subtype zone (belt III) and chloride
sulfate type zone (belt IV). The physical and chemical properties of
lithium and magnesium are similar in the diagonal relationship in
lar, which are 72 and 76 pm, respectively, and increase the diffi-
culty of lithium extraction. Nanofiltration (NF) is a pressure-
driven separation process between ultrafiltration and reverse
osmosis that has the advantages of low operating pressure, high
flux, no phase transition, and green environmental protection (Bi
et al., 2014; Sun et al., 2015; Park et al., 2020; Wang et al.,
2021b). Due to its special nanoscale pore size and the charged
2–
4 -ESP, and (c) CO3 -ESP.
T. Ding, M. Zheng, S. Peng et al.
property of the membrane surface, it has a high rejection rate of
divalent and multivalent ions (Peng and Zhao, 2021; Li et al.,
2022; Luo et al., 2022; Soyekwo et al., 2022), which can realize
the relative separation of monovalent and divalent ions. Therefore,
in salt lakes with high magnesium concentrations, nanofiltration
can be used to separate magnesium from lithium and then carry
out lithium extraction.
5. Conclusions and prospects
In the past 20 years, China has made progress in the research of
lithium extraction from salt lakes. However, the storage conditions
of lithium-containing salt lakes are quite different, resulting in no
reference standard for the selection of the production process. The
production cost of salt lakes in China is still higher than that of salt
lakes with a low magnesium-lithium ratio in South America. In the
future, the market price will fluctuate with the acceleration of the
development process of lithium resources, the release of produc-
tion capacity, and other factors. The lithium extraction industry
will face various pressures, such as production costs and environ-
mental protection. To achieve sustainable development in the
fierce market competition, it is necessary to formulate reasonable
extraction process standards for different hydrochemical types of
lithium-containing salt lakes, improve and optimize the lithium
extraction process, improve the product quality, and reduce the
production costs. In addition, we further improve and enhance in
the following aspects:
(1) The lithium-containing salt lake in the carbonate belt (Belt I)
is not suitable for lithium extraction by adsorption. The
adsorption energies of Li(Ι)-(Cl), Li(Ι)-(SO2 4 ), and Li(Ι)-
(CO2–3 ) are 1.26 kcalmol1, 2.10 kcalmol1, and
2.63 kcalmol1, respectively. The adsorption energy of the
CO2–3 brine on Li(Ι) is greater when the adsorption energy
of the adsorbent is constant, resulting in a decrease in the
effective adsorption energy of the adsorbents and the
adsorption capacity. Therefore, the lithium extraction
method is more suitable for chloride-sulfate type salt lakes
(Belt I), which corresponds to the lithium extraction process
adopted in the existing salt lakes.
(2) The binding energy of CO2– +
3 to Li is high in the lithium-
containing salt lakes of the carbonate belt (Belt I), and Li2CO3
undergoes thermal crystallization. Therefore, the precipita-
tion method for extracting lithium in this hydrochemical
zone saves energy and improves mining efficiency. Salt gra-
dient solar pool technology is an improved precipitation
technology for Li2CO3. In the future, salt gradient solar pool
technology can be further improved to shorten the produc-
tion cycle.
(3) There is more Mg2+ in the lithium salt lakes of the magne-
sium sulfate subtype zone (Belt III) and chloride sulfate type
zone (IV belt), which used the combination of the adsorption
method and nanofiltration membrane method to extract
lithium. Nanofiltration membrane technology can effectively
separate metal ions with different valence states, but it has
strict requirements on the mineralization of brine. The rich
lithium solution after the adsorption concentration has low
mineralization and high lithium concentration, which meets
the production standard of the nanofiltration membrane and
directly produces battery-level Li2CO3 products.
(4) Currently, none of the industrial lithium extraction tech-
nologies can adapt to all types of salt-lake brines. The appli-
cability of lithium extraction technology is singular.
Industrialized salt lakes are a combination of two or more
technologies. Therefore, the development of industrial
14
Geoscience Frontiers 14 (2023) 101485
lithium extraction can take the comprehensive method as
a research hotspot in the future, aiming to achieve a more
efficient recovery of lithium resources in salt lakes.
(5) Direct lithium extraction technology for the original brine
must be developed. The traditional technology of extracting
lithium from salt lakes is based on the raw material of pre-
liminarily processed brine obtained after sodium and
potassium removal by salt field spreading and drying pro-
cesses. Generally, some lithium resources will be lost in
the process of salt field drying, mining, and brine trans-
portation, which is mainly reflected in the leakage of salt
pans and the loss of sodium salts and potassium salts.
The original brine adsorption of lithium directly uses the
original brine as raw material, which effectively avoids
the loss in the salt pan process, improves the yield of
lithium resources, extends the service life of resources,
enhances the scale of production, reduces the production
costs, and reduces the area of the salt pans, which is more
conducive to environmental protection and the life of local
residents.
(6) The comprehensive development and utilization of salt lake
resources must be carried out. Salt lake resources mainly
contain sodium, magnesium, potassium, lithium, boron,
and other elements. The development and utilization of
magnesium and boron resources is the bottleneck in the
development and utilization of salt lake resources. The solu-
tion to the development of magnesium and boron resources
greatly reduces the difficulty of lithium development and
utilization. Magnesium products have many types, a wide
application range, and high added value and exhibit greater
economic development and utilization value. The develop-
ment and utilization of magnesium-boron resources are
expected to transfer the cost of separation of magnesium-
lithium with a high magnesium-to-lithium ratio and the cost
of boron removal to magnesium products and boron prod-
ucts. At that time, the production cost of the lithium prod-
ucts will be greatly reduced, having the ability to compete
with the salt lakes in South America.
(7) The product standards must be updated. The industry stan-
dard of China’s battery-grade lithium carbonate (YS/T582)
originates from the extraction of lithium by the ore method,
in which the boron and chlorine contents of the lithium-
containing ores are very low, and the requirements for
boron, chlorine, and other impurity indicators are higher
(30 ppm) than those of the battery-grade lithium carbon-
ate needed. At present, salt lake brine lithium extraction
technology has difficulty meeting the requirements of boron
and chlorine in the YS/T 582–2013 standard, which would
require secondary purification, increasing the production
costs again. On this basis, it is necessary to explore the
impact of boron and chlorine on battery-grade lithium car-
bonate, update the current product industry standards, and
formulate scientific product quality standards.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors gratefully thank the National Natural Science Foun-
dation of China for financial support (No. 91962219).
T. Ding, M. Zheng, S. Peng et al. Geoscience Frontiers 14 (2023) 101485

References Jiménez-De-La-Cuesta, D., Mauritsen, T., 2019. Emergent constraints on Earth’s

transient and equilibrium response to doubled CO2 from post-1970s global
warming. Nat. Geosci. 12 (11), 902–905.
Bandh, S.A., Shafi, S., Peerzada, M., Rehman, T., Bashir, S., Wani, S.A., Dar, R., 2021.
Johnson, G.C., Lyman, J.M., 2020. Warming trends increasingly dominate global
Multidimensional analysis of global climate change: a review. Environ. Sci.
ocean. Nat. Clim. Chang. 10 (8), 757–761.
Pollut. Res. 28 (20), 24872–24888.
Kamran, U., Park, S.J., 2020. MnO2-decorated biochar composites of coconut shell
Becke, A.D., 1988. Density-functional exchange-energy approximation with correct
and rice husk: An efficient lithium ions adsorption-desorption performance in
asymptotic behavior. Phys. Rev. A. 38 (6), 3098–3100.
aqueous media, Chemosphere. 260, 127500. https://doi.org10.1016/j.
Berecibar, M., 2019. Accurate predictions of lithium-ion battery life. Nature 568
chemosphere.2020.127500.
(7752), 325–326.
Kang, W., Shi, L., Zhao, Y., Zhang, D., Zhang, H., Wang, M., 2014. Preliminary test of
Bi, Q., Zhang, Z., Zhao, C., Tao, Z., 2014. Study on the recovery of lithium from
separation of Mg2+/Li+ in salt lake brine by nanofiltration. Inorgan. Chem.
high Mg2+/Li+ ratio brine by nanofiltration. Water Sci. Technol. 70 (10), 1690–
Indust. 46 (12), 22–24 (in Chinese).
1694.
Kesler, S.E., Gruber, P.W., Medina, P.A., Keoleian, G.A., Everson, M.P., Wallington, T.J.,
Butt, F.S., Lewis, A., Chen, T., Mazlan, N.A., Wei, X., Hayer, J., Chen, S., Han, J., Yang, Y.,
2012. Global lithium resources: Relative importance of pegmatite, brine and
Yang, S., Huang, Y., 2022. Lithium harvesting from the most abundant primary
other deposits. Ore Geol. Rev. 48, 55–69.
and secondary sources: A comparative study on conventional and membrane
Lee, C., Yang, W., Parr, R.G., 1988. Development of the Colle-Salvetti correlation-
technologies. Membranes 12 (4), 373.
energy formula into a functional of the electron density. Phys. Rev. B. 37 (2),
Cai, J., Zhao, X., Zhang, Y., Zhang, Q., Pan, B., 2018. Enhanced fluoride removal by La-
785–789.
doped Li/Al layered double hydroxides. J. Colloid Interface Sci. 509, 353–359.
Li, X.W., Chao, Y.H., Chen, L.L., Chen, W., Luo, J., Wang, C., Wu, P.W., Li, H.M., Zhu, W.
Chen, W., Li, X.W., Chen, L.L., Zhou, G.L., Lu, Q.Q., Huang, Y., Chao, Y.H., Zhu, W.S.,
S., 2020. Taming wettability of lithium ion sieve via different TiO2 precursors for
2021. Tailoring hydrophobic deep eutectic solvent for selective lithium recovery
effective Li recovery from aqueous lithium resources. Chem. Eng. J. 392, 123731.
from the mother liquor of Li2CO3. Chem. Eng. J. 420, 127648.
https://doi.org/10.1016/j.cej.2019.123731.
Chen, S., Nan, X., Zhang, N., Li, L., Yu, X., Guo, Y., Deng, T., 2019. Solvent extraction
Li, H., Eksteen, J., Kuang, G., 2019a. Recovery of lithium from mineral resources:
process and extraction mechanism for lithium recovery from high Mg/Li-ratio
State-of-the-art and perspectives–A review. Hydrometallurgy 189, 105129.
brine. J. Chem. Eng. Jpn. 52 (6), 508–513.
Li, Z., Mercken, J., Li, X., Riaño, S., Binnemans, K., 2019c. Efficient and sustainable
Chitrakar, R., Kanoh, H., Miyai, Y., Ooi, K., 2001. Recovery of lithium from seawater
removal of magnesium from brines for lithium/magnesium separation using
using manganese oxide adsorbent (H1.6Mn1.6O4) derived from Li1.6Mn1.6O4. Ind.
binary extractants. ACS Sustain. Chem. Eng. 7 (23), 19225–19234.
Eng. Chem. Res. 40 (9), 2054–2058.
Li, X., Mo, Y., Qing, W., Shao, S., Tang, C.Y., Li, J., 2019b. Membrane-based
Choubey, P.K., Chung, K.S., Kim, M.S., Lee, J.C., Srivastava, R.R., 2017. Advance review
technologies for lithium recovery from water lithium resources: A review. J.
on the exploitation of the prominent energy-storage element Lithium. Part II:
Membr. Sci. 591, 117317. https://doi.org/10.1016/j.memsci.2019.117317.
From sea water and spent lithium-ion batteries (LIBs). Miner. Eng. 110, 104–
Li, H., Wang, Y., Li, T., Ren, X.-K., Wang, J., Wang, Z., Zhao, S., 2022. Nanofiltration
121.
membrane with crown ether as exclusive Li+ transport channels achieving
Clara, M.T., Martins, C.J.A.P., 2020. Primordial nucleosynthesis with varying
efficient extraction of lithium from salt lake brine. Chem. Eng. J. 438, 135658.
fundamental constants-Improved constraints and a possible solution to the
Ling, Y., Zheng, M., Sun, Q., Dai, X., 2017. Last deglacial climatic variability in Tibetan
lithium problem. Astron Astrophys. 633, L11. https://doi.org/10.1051/0004-
Plateau as inferred from n-alkanes in a sediment core from Lake Zabuye. Quat.
6361/201937211.
Int. 454, 15–24.
Cui, L., Wang, L., Feng, M., Fang, L., Guo, Y.X., Cheng, F.Q., 2021. Ion-pair induced
Liu, D., Sun, S., Yu, J., 2017. Research and development on technique of lithium
solvent extraction of lithium (I) from acidic chloride solutions with tributyl
recovery from salt lake brine. CIESC J. 69 (1), 141–155 (in Chinese with English
phosphate. Green Energy Environ. 6 (4), 607–616.
abstract).
Cyburt, R.H., Ellis, J., Fields, B.D., Luo, F., Olive, K.A., Spanos, V.C., 2010. Nuclear
Liu, G., Zhao, Z., Ghahreman, A., 2019. Novel approaches for lithium extraction from
reaction uncertainties, massive gravitino decays and the cosmological lithium
salt-lake brines: A review. Hydrometallurgy 187, 81–100.
problem. J. Cosmol. Astropart. P. 10, 032. https://doi.org/10.1088/1475-7516/
Liu, X., Zhong, M., Chen, X., Li, J., He, L., Zhao, Z., 2020. Enriching lithium and
2010/10/032.
separating lithium to magnesium from sulfate type salt lake brine.
Deng, S.H., Yang, Z.X., Yang, J.Y., Yang, X., Yin, C., Han, J., Yi, D.Q., 2016. New process
Hydrometallurgy 192, 105247. https://doi.org/10.1016/j.
for preparation of high purity lithium carbonate from coarse salt in Zabuye Salt
hydromet.2020.105247.
Lake. Inorgan. Chem. Indust. 48 (4), 26–30 (in Chinese with English abstract).
Lu, G., Dong, Z., Liu, W., Jiang, X., Yang, Z., Liu, Q., 2021. Universal lithiophilic
Ding, T., Wu, Q., Zheng, M., Nie, Z., Li, M., Peng, S., Wang, Y., Yu, X., Qian, C., Tang, S.,
interfacial layers toward dendrite-free lithium anodes for solid-state lithium-
Wang, M., 2021. Polyacrylonitrile/Crown ether composite nanofibers with high
metal batteries. Sci. Bull. 66, 1746–1753.
efficiency for adsorbing Li(I): Experiments and theoretical calculations. Front.
Luo, Q., Dong, M., Nie, G., Liu, Z., Wu, Z., Li, J., 2021. Extraction of lithium from salt
Energy Res. 9, 765612. https://doi.org/10.3389/fenrg.2021.765612.
lake brines by granulated adsorbents. Colloids Surf. A Physicochem. Eng. Asp.
Ding, T., Zheng, M., Lin, Y., 2022a. Adsorption of Li(I) ions through new high-
628, 127256.
performance electrospun PAN/Kaolin nanofibers: A combined experimental and
Luo, H., Peng, H., Zhao, Q., 2022. High flux Mg2+/Li+ nanofiltration membranes
theoretical calculation. ACS Omega 7 (13), 11430–11439. https://doi.org/
prepared by surface modification of polyethylenimine thin film composite
10.1021/acsomega.2c00658.
membranes. Appl. Surf. Sci. 579, 152161.
Ding, T., Zheng, M., Nie, Z., Ma, L., Ye, C., Wu, Q., Zhao, Y., Yang, D., Wang, K., 2022b.
Mahammedi, N.A., Ferhat, M., Tsumuraya, T., Chikyow, T., 2017. Prediction of
Impact of regional climate change on the development of lithium resources in
optically active transitions in type-VIII guest-free silicon clathrate Si46: a
Zabuye Salt Lake. Tibet. Front. Earth Sci. 10, 865158 https://doi:10.3389/feart.
comparative study of its physical properties with type-I counterpart through
2022.865158.
first-principles. J. Phys. D. 122 (20), 205103. https://doi.org/10.1063/1.4999985.
Gao, F., Zheng, M.P., Song, P., Bu, L.Z., Wang, Y.S., 2012. The 273.15-K-isothermal
Marenich, A.V., Cramer, C.J., Truhlar, D.G., 2009. Universal solvation model based on
evaporation experiment of lithium brine from the Zhabei Salt Lake, Tibet, and
solute electron density and on a continuum model of the solvent defined by the
its geochemical significance. Aquat. Geochem. 18 (4), 343–356.
bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B. 113 (18),
Gu, D., Sun, W., Han, G., Cui, Q., Wang, H., 2018. Lithium ion sieve synthesized via an
6378–6396.
improved solid-state method and adsorption performance for West Taijinar Salt
Martin, G., Rentsch, L., Höck, M., Bertau, M., 2017. Lithium market research–global
Lake brine. Chem. Eng. J. 350, 474–483.
supply, future demand and price development. Energy Stor. Mater. 6, 171–179.
Han, J.H., Nie, Z., Fang, C.H., Wu, Q., Cao, Q., Wang, Y.S., Bu, L.Z., Yu, J.J., 2021.
Meng, F., McNeice, J., Zadeh, S.S., Ghahreman, A., 2021. Review of lithium
Analysis of existing circumstance of supply and demand on China0 s lithium
production and recovery from minerals, brines, and lithium-ion batteries.
resources. Inorgan. Chem. Industry 53(12), 61-11 (in Chinese with English
Miner Process Extr M. 42 (2), 123–141.
abstract).
Mika, J., Forgo, P., Lakatos, L., Olah, A.B., Rapi, S., Utasi, Z., 2018. Impact of 1.5 K
Hou, J., Zhang, H., Thornton, A.W., Hill, A.J., Wang, H.T., Konstas, K., 2021. Lithium
global warming on urban air pollution and heat island with outlook on human
extraction by emerging metal–organic framework-based membranes. Adv.
health effects. Curr. Opin. Env. Sust. 30, 151–159.
Funct. Mater. 31 (46), 2105991.
Moazeni, M., Hajipour, H., Askari, M., Nusheh, M., 2015. Hydrothermal synthesis
Huang, W., Wang, X., Sun, Z., Nie, Z., Sha, Z.L., 2009. Zabuye Salt Lake solar pond in
and characterization of titanium dioxide nanotubes as novel lithium
Tibet, China: Construction and operational experience. Natural Resour. Environ.
adsorbents. Mater. Res. Bull. 61, 70–75.
Issues 15 (1), 39.
Nie, Z., Bu, L.Z., Zheng, M.P., Zhang, Y.S., 2010. Phase chemistry study on brine from
Jeong, J.M., Rhee, K.Y., Park, S.J., 2015. Effect of chemical treatments on lithium
the Zabuye carbonate-type salt lake in Tibet. Acta Geol. Sin. 84 (4), 587–592 (in
recovery process of activated carbons. J. Ind. Eng. Chem. 27, 329–333.
Chinese with English abstract).
Ji, L.M., Hu, Y.H., Li, L.J., Shi, D., Li, J.F., Nie, F., Song, F.G., Zeng, Z.M., Sun, W., Liu, Z.Q.,
Nie, Z., Bu, L.Z., Zheng, M.P., Huang, W.N., 2011. Experimental study of natural brine
2016. Lithium extraction with a synergistic system of dioctyl phthalate and
solar ponds in Tibet. Sol. Energy 85 (7), 1537–1542.
tributyl phosphate in kerosene and FeCl3. Hydrometallurgy 162, 71–78.
Niu, X., Chen, W., Liu, X., 2013. Geochemical characteristics on salt springs and
Ji, C., Zhang, J., Zhang, Z., Sun, S., Li, P., Yu, J., 2014. Separation properties of
potash perspective in Dogai Coring Area of Qiangtang Basin. Geoscience 27 (3),
magnesium and lithium from brine with high Mg(2+)/Li+ ratio by DK
621–628 (in Chinese with English abstract).
nanofiltration membrane. J. Membr. Sci. Technol. 34 (03), 79–85 (in Chinese
Ogawa, Y., Koibuchi, H., Suto, K., Inoue, C., 2014. Effects of the chemical
with English abstract).
compositions of Salars de Uyuni and Atacama brines on lithium concentration
Jiang, C., Wang, Y., Wang, Q., Feng, H., Xu, T., 2014. Production of lithium hydroxide
during evaporation. Resour. Geol. 64 (2), 91–101.
from lake brines through electro–electrodialysis with bipolar membranes
Park, S.H., Kim, J.H., Moon, S.J., Jung, J.T., Wang, H.H., Ali, A., Quist-Jensen, C.A.,
(EEDBM). Ind. Eng. Chem. Res. 53 (14), 6103–6112.
Macedonio, F., Drioli, E., Lee, Y.M., 2020. Lithium recovery from artificial brine

15
T. Ding, M. Zheng, S. Peng et al.
using energy-efficient membrane distillation and nanofiltration. J. Membr. Sci.
598, 117683.
Peng, H., Zhao, Q., 2021. A nano-heterogeneous membrane for efficient separation
of lithium from high magnesium/lithium ratio brine. Adv. Funct. Mater. 31 (14),
2009430.
Petersson, G.A., Bennett, A., Tensfeldt, T.G., Laham, M.A., Shirley, W.A., Mantzaris, J.,
1988. A complete basis set model chemistry. I. The total energies of closed-shell
atoms and hydrides of the first-row elements. J. Chem. Phys. 89 (4), 2193–2218.
Petersson, G.A., Laham, M.A., 1991. A complete basis set model chemistry. II. Open-
shell systems and the total energies of the first-row atoms. J. Chem. Phys. 94 (9),
6081–6090.
Qian, J., Henderson, W.A., Xu, W., Bhattacharya, P., Engelhard, M., Borodin, O., Zhang,
J.G., 2015. High rate and stable cycling of lithium metal anode. Nat. Commun. 6
(1), 1–9.
Qu, J., He, X., Wang, B., Zhong, L., Wan, L., Li, X., Song, S., Zhang, Q., 2016. Synthesis of
Li–Al layered double hydroxides via a mechanochemical route. Appl. Clay Sci.
120, 24–27.
Raghavachari, K., 2000. Perspective on ‘‘Density functional thermochemistry. III. The
role of exact exchange”. Theor. Chem. Acc. 103 (3), 361–363.
Ramos-Sanchez, G., Callejas-Tovar, A., Scanlon, L.G., 2014. DFT analysis of Li
intercalation mechanisms in the Fe-phthalocyanine cathode of Li-ion batteries.
Phys. Chem. Chem. Phys. 16 (2), 743–752.
Razmjou, A., Asadnia, M., Hosseini, E., Korayem, H.A., Vicki Chen, V., 2019. Design
principles of ion selective nanostructured membranes for the extraction of
lithium ions. Nat. Commun. 10 (1), 1–15.
Rioyo, J., Tuset, S., Grau, R., 2022. Lithium extraction from spodumene by the
traditional sulfuric acid process: A review. Miner. Process. Extr. M. 43,
97–106.
Ryu, T., Shin, J., Lee, D.H., Ryu, J., Park, I., Hong, H., Huh, Y.S., Kim, B.-G., Chung, K.-S.,
2015. Development of multistage column for lithium recovery from an aqueous
solution. Hydrometallurgy. 157, 39–43.
Salakjani, N.K., Singh, P., Nikoloski, A.N., 2021. Production of lithium–A literature
review. Part 2. Extraction from spodumene. Miner. Process. Extr. M. 42 (4), 268–
283.
Sang, S.H., Yin, H.A., Tang, M.L., Zhang, Y.X., 2003. (Liquid+ solid) metastable
equilibria in quinary system Li2CO3 + Na2CO3 + K2CO3+ Li2B4O7 + Na2B4O7 +
K2B4O7 + H2O at T= 288 K for Zhabuye salt lake. J. Chem. Thermody. 35 (9),
1513–1520.
Sang, S.H., Yin, H.A., Xing, W.Z., 2006. (Solid+ liquid) metastable equilibria in
quaternary system (Li2SO4 + K2SO4 + Li2B4O7 + K2B4O7 + H2O) at T= 288 K. J.
Chem. Thermody. 38 (2), 173–178.
Schulz, A., Bakhru, H., DeRosa, D., Higashiya, S., Rane-Fondacaro, M., Haldar, P.,
2017. Quantifying lithium in the solid electrolyte interphase layer and beyond
using Lithium-Nuclear Reaction Analysis technique. J. Power Sources 360, 129–
135.
Shang, S.L., Wang, W.Y., Zhou, B.C., Wang, Y., Darling, K.A., Kecskes, L.J., Mathaudhu,
S.N., Liu, Z.K., 2014. Generalized stacking fault energy, ideal strength and
twinnability of dilute Mg-based alloys: A first-principles study of shear
deformation. Acta Mater. 67, 168–180.
Sharma, A.D., Patil, N.D., Patwardhan, A.W., Moorthy, R.K., Ghosh, P.K., 2016.
Synergistic interplay between D2EHPA and TBP toward the extraction of
lithium using hollow fiber supported liquid membrane. Sep. Purif. Technol. 51
(13), 2242–2254.
Shi, D., Zhang, L., Peng, X., Li, L.J., Song, F., Nie, F., Ji, L., Zhang, Y., 2018. Extraction of
lithium from salt lake brine containing boron using multistage centrifuge
extractors. Desalination 441, 44–51.
Shi, D., Cui, B., Li, L., Peng, X., Zhang, L., Zhang, Y., 2019. Lithium extraction from low-
grade salt lake brine with ultrahigh Mg/Li ratio using TBP–kerosene–FeCl3
system. Sep. Purif. Technol. 211, 303–309.
Sileika, T.S., Kim, H.D., Maniak, P., Messersmith, P.B., 2011. Antibacterial
performance of polydopamine-modified polymer surfaces containing passive
and active components. ACS Appl. Mater. Interfaces. 3 (12), 4602–4610.
Soyekwo, F., Wen, H., Liao, D., Liu, C.K., 2022. Nanofiltration membranes modified
with a clustered multiquaternary ammonium-based ionic liquid for
improved magnesium/lithium separation. ACS Appl. Mater. Inter. 14 (28),
32420–32432. https://doi.org/10.1021/acsami.2c03650.
Su, H., Zhu, Z., Wang, L., Qi, T., 2019. Advances and prospects of extracting and
recovering lithium from salt lake brines. Materials Reviews 33 (13), 2119–2126
(in Chinese with English abstract).
Su, H., Ju, J., Zhang, J., Yi, A., Lei, Z., Wang, L., Qi, T., 2020a. Lithium recovery from
lepidolite roasted with potassium compounds. Miner. Eng. 145, 106087. https://
doi.org/10.1016/j.mineng.2019.106087.
Su, H., Li, Z., Zhang, J., Liu, W., Zhu, Z., Wang, L., Qi, T., 2020b. Combining selective
extraction and easy stripping of lithium using a ternary synergistic solvent
extraction system through regulation of Fe3+ coordination. ACS Sustain. Chem.
Eng. 8 (4), 1971–1979. https://doi.org/10.1021/acssuschemeng.9b06432.
Su, H., Li, Z., Zhang, J., Zhu, Z., Wang, L., Qi, T., 2020c. Recovery of lithium from salt
lake brine using a mixed ternary solvent extraction system consisting of TBP,
FeCl3 and P507. Hydrometallurgy 197, 105487. https://doi.org/10.1016/j.
hydromet.2020.105487.
Sun, S.Y., Cai, L.J., Nie, X.Y., Song, X., Yu, J.G., 2015. Separation of magnesium and
lithium from brine using a Desal nanofiltration membrane. J. Water Process.
Eng. 7, 210–217.
Sun, Q., Chen, H., Yu, J.G., 2022. Investigation on the lithium extraction process with
the TBP–FeCl3 solvent system using experimental and DFT methods. Ind. Eng.
Chem. Res. 61 (13), 4672–4682.
16
Geoscience Frontiers 14 (2023) 101485
Sun, S.Y., Song, X., Zhang, Q.H., Wang, J., Yu, J.G., 2011. Lithium extraction/insertion
process on cubic Li-Mn-O precursors with different Li/Mn ratio and
morphology. Adsorption 17 (5), 881–887.
Sun, Y., Wang, Q., Wang, Y., Yun, R., Xiang, X., 2021. Recent advances in magnesium/
lithium separation and lithium extraction technologies from salt lake brine. Sep.
Purif. Technol. 256, 117807.
Swain, B., 2017. Recovery and recycling of lithium: A review. Sep. Purif. Technol.
172, 388–403.
Tarascon, J.M., Armand, M., 2001. Issues and challenges facing rechargeable lithium
batteries. Nature 414, 359–367.
Tarascon, J.M., 2010. Is lithium the new gold? Nat. Chem. 2(6), 510-510.
Van der Bruggen, B., Koninckx, A., Vandecasteele, C., 2004. Separation of
monovalent and divalent ions from aqueous solution by electrodialysis and
nanofiltration. Water Res. 38 (5), 1347–1353.
Wang, S., Chen, X., Zhang, Y., Zhang, Y., Zheng, S., 2018a. Lithium adsorption from
brine by iron-doped titanium lithium ion sieves. Particuology 41, 40–47.
Wang, S.L., Lin, C.H., Yan, Y.Y., Wang, M.K., 2013. Synthesis of Li/Al LDH using
aluminum and LiOH. Appl. Clay Sci. 72, 191–195.
Wang, L., Meng, C.G., Ma, W., 2009. Study on Li+ uptake by lithium ion-sieve via the
pH technique. Colloid Surface A. 334 (1–3), 34–39.
Wang, L., Rehman, D., Sun, P.F., Deshmukh, A., Zhang, L.Y., Han, Q., Yang, Z., Wang, Z.
Y., Park, H.D., Lienhard, J.H., Tang, C.Y., 2021b. Novel positively charged metal-
coordinated nanofiltration membrane for lithium recovery. ACS Appl. Mater.
Inter. 13 (14), 16906–16915.
Wang, H., Zheng, M., Yuan, H., 2016. Highstands in the interior of the Qinghai-
Tibetan Plateau since the last interglacial: evidence from grain-size analysis of
lacustrine core sediments in Zabuye Salt Lake. Geol. J. 51 (5), 737–747.
Wang, H., Wang, Z., Yue, R., Gao, F., Ren, R., Wei, J., Wang, X., Kong, Z., 2020b.
Functional group-rich hyperbranched magnetic material for simultaneous
efficient removal of heavy metal ions from aqueous solution. J. Hazard. Mater.
384, 121288. https://doi.org/10.1016/j.jhazmat.2019.121288.
Wang, S., Zheng, S., Wang, Z., Cui, W., Zhang, H., Yang, L., Zhang, Y., Li, P., 2018b.
Superior lithium adsorption and required magnetic separation behavior of iron-
doped lithium ion-sieves. Chem. Eng. J. 332, 160–168.
Wang, Y., Zheng, M., Yan, L., Bu, L., Qi, W., 2019a. Influence of the regional climate
variations on lake changes of Zabuye, Dangqiong Co and Bankog Co salt lakes in
Tibet. J. Geogr. Sci. 29 (11), 1895–1907.
Wang, Y., Liu, H., Fan, J., Liu, X., Hu, Y., Hu, Y., Zhou, Z., Ren, Z., 2019b. Recovery of
lithium ions from salt lake brine with a high magnesium/lithium ratio using
heteropolyacid ionic liquid. ACS Sustain. Chem. Eng. 7 (3), 3062–3072.
Wang, C., Zheng, M., Zhang, X., Xing, E., Zhang, J., Ren, J., Ling, Y., 2020a. O, H, and Sr
isotope evidence for origin and mixing processes of the Gudui geothermal
system, Himalayas. China Geosci Front. 11 (4), 1175–1187.
Wang, C., Zheng, M., Zhang, X., Wu, Q., Liu, X., Ren, J., Chen, S., 2021a. Geothermal-
type lithium resources in Southern Xizang. China Acta Geol. Sin-Engl. 95 (3),
860–872.
Wen, X., Ma, P., Zhu, C., He, Q., Deng, X., 2006. Preliminary study on recovering
lithium chloride from lithium-containing waters by nanofiltration. Sep. Purif.
Technol. 49 (3), 230–236.
Weng, D., Duan, H., Hou, Y., Huo, J., Chen, L., Zhang, F., Wang, J., 2020. Introduction of
manganese based lithium-ion Sieve-A review. Prog. Nat. Sci. 30 (2), 139–152.
Wiśniewska, M., Fijałkowska, G., Ostolska, I., Franus, W., Nosal-Wiercińska, A.,
Tomaszewska, B., Wójcik, G., 2018. Investigations of the possibility of lithium
acquisition from geothermal water using natural and synthetic zeolites
applying poly (acrylic acid). J. Clean. Prod. 195, 821–830.
Wu, J., Chen, J., Huang, Y., Feng, K., Deng, J., Huang, W., Li, Y., 2019. Cobalt atoms
dispersed on hierarchical carbon nitride support as the cathode electrocatalyst
for high-performance lithium-polysulfide batteries. Sci. Bull. 64 (24), 1875–
1880.
Wu, G., Huang, M., 2006. Organolithium reagents in pharmaceutical asymmetric
processes. Chem. Rev. 106 (7), 2596–2616.
Wu, Q., Li, L., An, Y., 2005. Artificial neural network (ANN) method for predicting of
hydrochemical types of salt lakes. Anal. Sci. 21 (3), 271–273 (in Chinese with
English abstract).
Wu, Q., Zheng, M.P., Nie, Z., Bu, L.Z., 2012a. Natural evaporation and crystallization
regularity of Dangxiongcuo carbonate-type salt lake brine in Tibet. Chin. J.
Inorgan. Chem. 28 (9), 1895–1903 (in Chinese with English abstract).
Wu, Z.M., Zheng, M.P., Liu, X.F., Nie, Z., 2012b. Concentration of brines from the
Dogai Coring Lake, Northern Tibet, by using the two-step process: freezing and
solar evaporation. Chin. J. Inorgan. Chem. 28 (5), 995–1000 (in Chinese with
English abstract).
Xiao, J., Nie, X., Sun, S., Song, X., Li, P., Yu, J., 2015. Lithium ion adsorption–
desorption properties on spinel Li4Mn5O12 and pH-dependent ion-exchange
model. Adv. Powder Technol. 26 (2), 589–594.
Xing, P., Wang, C., Zeng, L., Ma, B., Wang, L., Chen, Y., Yang, C., 2019. Lithium
extraction and hydroxysodalite zeolite synthesis by hydrothermal conversion of
a-spodumene. ACS Sustain. Chem. Eng. 7 (10), 9498–9505.
Xu, W.N., Bu, L.Z., Kong, W.G., Zheng, M.P., Nie, Z., 2017a. Monitoring of the dynamic
change of Zabuye Salt Lake: A remote sensing approach. Sci. Technol. Rev. 35
(6), 89–96 (in Chinese).
Xu, X., Chen, Y., Wan, P., Gasem, K., Wang, K., He, T., Adidharma, H., Fan, M., 2016.
Extraction of lithium with functionalized lithium ion-sieves. Prog. Mater. Sci.
84, 276–313.
Xu, X., Zhou, Y., Fan, M., Lv, Z., Tang, Y., Sun, Y., 2017b. Lithium adsorption
performance of a three-dimensional porous H2TiO3-type lithium ion-sieve in
strong alkaline Bayer liquor. Rsc. Adv. 7 (31), 18883–18891.
T. Ding, M. Zheng, S. Peng et al.
Yan, Q., Li, X., Yin, Z., Wang, Z., Guo, H., Peng, W., Hu, Q., 2012. A novel process for
extracting lithium from lepidolite. Hydrometallurgy 121, 54–59.
Yang, J., Qu, G., Liu, C., Zhou, S., Li, B., 2022. An effective lithium ion-imprinted
membrane containing 12-crown ether-4 for selective recovery of lithium.
Chem. Eng. Res. Des. 184, 639–650.
Ye, B., Jiang, J., Liu, J., Zheng, Y., Zhou, N., 2021. Research on quantitative assessment
of climate change risk at an urban scale: Review of recent progress and outlook
of future direction. Renew. Sust. Energ. Rev. 135, 110415. https://doi.org/
10.1016/j.rser.2020.110415.
Ye, C.Y., Zheng, M.P., 2016. Study on the existence forms of chemical components
and saturation index of waters from Gasikule Salt Lake. Qinghai Province.
Science & Technology Review. 34 (21), 101–111 (in Chinese with English
abstract).
Yu, X.D., Jiang, D.B., Tan, Q., Zeng, Y., 2014. Solid-liquid equilibrium in the aqueous
system containing the chlorides of lithium, rubidium and magnesium at 323 K.
Fluid Phase Equilib. 367, 63–68.
Yu, X.D., Luo, Y.L., Wu, L.T., Cheng, X.L., Zeng, Y., 2016. Solid-liquid equilibrium on
the reciprocal aqueous Quaternary system Li+, Mg2+//Cl, and borate-H2O at 323
K. J. Chem. Eng. Data. 61 (9), 3311–3316.
Yu, X., Zeng, Y., Mu, P., Tan, Q., Jiang, D., 2015c. Solid-liquid equilibrium in the
quinary system LiCl-KCl-RbCl-MgCl2-H2O at T=323 K. Fluid Phase Equilib. 387,
88–94.
Yu, J.J., Zheng, M.P., Wu, Q., 2013. Research progress of lithium extraction process in
lithium-containing salt lake. Chem. Indust. Eng. Progr. 32 (1), 13–21 (in Chinese
with English abstract).
Yu, J.J., Zheng, M.P., Wu, Q., Nie, Z., Bu, L., 2015a. Extracting lithium from Tibetan
Dangxiong Tso Salt Lake of carbonate type by using geothermal salinity-
gradient solar pond. Sol. Energy 115, 133–144.
Yu, J.J., Zheng, M.P., Wu, Q., Wang, Y.S., Nie, Z., Bu, L.Z., 2015b. Natural evaporation
and s crystallization of Dujiali salt lake water in Tibet. Chem. Indust. Eng. Progr.
34 (12), 4172–4178 (in Chinese with English abstract).
Zhang, Y., Hu, Y., Wang, L., Sun, W., 2019a. Systematic review of lithium extraction
from salt-lake brines via precipitation approaches. Miner. Eng. 139, 105868.
Zhang, Y., Lv, W., Huang, Z., Zhou, G., Deng, Y., Zhang, J., Yang, Q.H., 2019b. An air-
stable and waterproof lithium metal anode enabled by wax composite
17
Geoscience Frontiers 14 (2023) 101485
packaging. Sci. Bull. 64 (13), 910–917. https://doi.org/10.1016/j.
scib.2019.05.025.
Zhang, Q.H., Sun, S., Li, S., Jiang, H., Yu, J.G., 2007. Adsorption of lithium ions on novel
nanocrystal MnO2. Chem. Eng. Sci. 62 (18–20), 4869–4874.
Zhang, Y., Wang, L., Sun, W., Hu, Y., Tang, H., 2020. Membrane technologies for Li+/
Mg2+ separation from salt-lake brines and seawater: A comprehensive review. J.
Ind. Eng. Chem. 81, 7–23.
Zhang, Y., Sun, W., Xu, R., Wang, L., Tang, H., 2021. Lithium extraction from water
lithium resources through green electrochemical-battery approaches: A
comprehensive review. J. Clean. Prod. 285, 124905. https://doi.org/10.1016/j.
jclepro.2020.124905.
Zhang, L., Zhou, D., Yao, Q., Zhou, J., 2016. Preparation of H2TiO3-lithium adsorbent
by the solgel process and its adsorption performance. Appl. Surf. Sci. 368, 82–
87.
Zhao, T., Qin, Y., Zhang, P., Wang, B., Yang, J.F., 2014. High-performance, reaction
sintered lithium disilicate glass–ceramics. Ceram. Int. 40 (8), 12449–12457.
Zhao, X., Zhang, Q., Wu, H., Hao, X., Wang, L., Huang, X., 2017. Extraction of lithium
from salt lake brine. Progr. Chem. 29 (7), 796–808 (in Chinese).
Zheng, M.P., 2019. Hydrochemical characteristics and evolution of hot fluids in the
Gudui geothermal field in Comei County, Himalayas. Geothermics 81, 243–258.
Zheng, M.P., Liu, X.F., 2010. Hydrochemistry and mineral assemblages of salt lakes
in Qinghai-Tibet Plateau. Acta Geol. Sin. 84 (11), 1585–1600 (in Chinese with
English abstract).
Zheng, M.P., Qi, W., 2006. Saline resources and its development in China. Conservat.
Utilizat. Miner. Resour. 5, 45–50 (in Chinese with English abstract).
Zheng, M.P., Yuan, H.R., Liu, J.Y., Li, Y.H., Ma, Z.B., Sun, Q., 2007. Sedimentary
characteristics and paleoenvironmental records of Zabuye Salt Lake, Tibetan
Plateau, since 128 ka BP. Acta Geol. Sin-Engl. 81 (5), 861–879.
Zheng, M.P., Zhang, Y.S., Liu, X.F., Nie, Z., Kong, F.J., Qi, W., Jia, Q.X., Pu, L.Z., Hou, X.H.,
Wang, H.L., Zhang, Z., Kong, W.G., Lin, Y.J., 2016. Progress and prospects of salt
lake research in China. Acta Geol. Sin-Eng. 90 (4), 1195–1235.
Zhou, Z., Fan, J., Liu, X., Hu, Y., Wei, X., Hu, Y., Wang, W., Ren, Z., 2020. Recovery of
lithium from salt-lake brines using solvent extraction with TBP as extractant
and FeCl3 as coextraction agent. Hydrometallurgy 191, 105244. https://doi.org/
10.1016/j.hydromet.2019.105244.