**Abstract**

Demand to lithium rising swiftly as increasing due to its diverse applications such as rechargeable batteries, light aircraft alloys, air purification, medicine and nuclear fusion. Lithium demand is expected to triple by 2025 through the use of batteries, particularly electric vehicles. The lithium market is expected to grow from 184,000 TPA of lithium carbonate to 534,000 TPA by 2025. To ensure the growing consumption of lithium, it is necessary to increase the production of lithium from different resources. Natural lithium resources mainly associate within granite pegmatite type deposit (spodumene and petalite ores), salt lake brines, seawater and geothermal water. Among them, the reserves of lithium resource in salt lake brine, seawater and geothermal water are in 70–80% of the total, which are excellent raw materials for lithium extraction. Compared with the minerals, the extraction of lithium from water resources is promising because this aqueous lithium recovery is more abundant, more environmentally friendly and cost-effective.

**Keywords:** thermodynamics, lithium energy, lithium recovery, adsorption, precipitation, membrane process

### **1. Introduction**

Lithium and its compounds are widely used in manufactured glass, ceramics, greases, batteries, refrigerants, chemical reagents and other industries. World lithium reserves are about 14 million tons, mostly 70–80% is stored in salt lake brine, geothermal water and solid lithium contained in lithium ore. Currently, many researchers are turning their attention to 2600 billion tons of lithium-containing seawater, which is about 15,000 times more than solid lithium ores [1].

Figures for lithium resources and reserves differ considerably accordingly to the source, although there is a unanimous agreement that lithium resources in brine are much larger than those in hard rock [2–6]. The most recent figures from the US Geological Survey indicate total lithium resources (brine + hard rock) to be 54.1 million tons [5]. Approximate minimum and maximum hard rock lithium resources were reported at 12.8 and 30.7 million tons, respectively; while brine field data were reported as 21.3 and 65.3 million tons, respectively, for minimum and maximum estimates [3].

Lithium has various uses, but its abundance in nature is only 0.0018% [7]. The use of lithium on ceramics enriched with Li6 is up to 15% for use in the production of tritium [8, 9]. In addition, enriched Li6 is very expensive, what is commensurate with the value of gold. Consequently, it is necessary to extract and recycle lithium from the waste of solid breeding materials. Hence widespread use of lithium in various spheres, many studies have been conducted to extract lithium from various sources.

Lithium demand is expected to grow continuously and dramatically in the coming years as different types of lithium batteries are the most promising candidates for powering electric or hybrid vehicles [10, 11]. Lithium batteries include both current technologies such as lithium-ion and growing battery technologies such as lithium-sulfur or lithium-air [12–15].

Lithium demand is projected to increase by ~60% from 102,000 to 162,000 tonnes of lithium carbonate equivalent in the next 5 years, with battery applications taking a huge percentage of this growth [16, 17]. It was reported that the present lithium resource in continental and Salar brines is roughly 52.3 million tons of lithium equivalent, mainly in Argentina, Chile and Bolivia, from which 23.2 million tons can be extracted [18]. From the other side, lithium from mineral resources is 8.8 million tons, where there are huge deposits in the United States, Russia and China. Evans estimated lithium reserves and recoverable resources at 29.79 million tons [19].

Meanwhile, the general public mainly associates lithium batteries with portable electronics and electric and hybrid vehicles, large storage capacity lithium batteries are also a lead candidate for a possible energy storage solution for the electric grid, intelligent network, etc. Batteries with large capacity are needed to store green energy, wind, that is, sun and waves, all this by their nature intermittent sources of energy [20–30]. Nowadays battling to achieve a greater percentage of green energy, high-capacity batteries or energy banks are mandatory. Basically, if in the near future we want our energy matrix to be highly dependent on renewable energy, energy banks will be needed to provide continuous energy to the grid, during the time these intermittent energy sources are either off or not working completely (no wind, no waves, at night) [20–22]. After all, on its own of the energy source, high-capacity batteries are also an alternative for storing energy during periods of low demand, allowing this excess energy to be re-injected into the grid at high demand peaks [24].

Currently, lithium is relatively not expensive (a ton of Li2CO3 is about 15,000 USD), the market shows that, its price is rising with increasing demand [25].

In China, lithium prices have risen about 300% since 2016, and contract prices for existing manufacturers have risen to more than 16,000 USD per tonne.

Because of the exhaustion of lithium ores, recent studies have shown recovery of lithium from seawater, brine and geothermal water. Production of lithium from water resources has become more important due to its wide availability, ease of process and cost-effectiveness compared with its production from various resources [26].

Many methods for extracting lithium from seawater, brines and geothermal water have been reported [27]: solvent extraction, including precipitation, liquidliquid extraction, selective membrane separation, electrodialysis, ion exchange adsorption, etc. [28–34]. Of these methods, the most attention was paid to ion exchange adsorption methods based on lithium-ion sieves because of their good lithium-ion selectivity and high adsorption properties [35–37]. From the point of view of cost and efficiency, extraction of lithium ions from solutions by ion exchange adsorption is an important method [38].

Various methods of removing lithium from water have been proposed in recent years. In their midst, adsorption has been proven to be a perfect way to extract lithium, offering significant benefits, such as availability, lower cost, profitability, efficiency and easy operation. For lithium removal, various Li adsorbent materials

**189**

*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water…*

have previously been reported, including metal oxides, clay minerals, silicotitanates and zirconium phosphate. The main attention of the researchers was focused on the adsorbents of titanium-lithium ion sieves [39–43] manganese-lithium ion sieves [44–50] and aluminum salts [51, 52]. Adsorbents of aluminum salts [52] showed

Chitrakar et al. [53] nanoscale H2TiO3 was synthesized by solid-phase reaction and

et al. were synthesized H2TiO3 using different raw materials [41, 42]. Wang et al. synthesized lithium-enriched β-Li2TiO3 with a maximum lithium absorption of

adsorbent H2TiO3 from the lithium-enriched solution has reached 76.7 mg

, the high cost of synthesis and loss of dissolution of the titanium ion is still an obstacle. Chitrakar et al. by hydrothermal reaction synthesized Li1.6Mn1.6O4 and

tured hydrogen oxides of manganese, the saturated adsorption capacity of which

the dismutation reaction during etching can lead to distortion of the lattice and

In addition to lithium and magnesium, the treated salt lake brines may contain significant concentrations of potassium, sodium and boron. Zhou et al. compared the competitive sequences for several cations using TBP/FeCl3 in MIBK as the extractant [55–57]. However, quantitative correlations for competing for ion extrac-

The review is devoted to the extraction of lithium from brines, marine and geothermal waters, the collection of different methods of lithium extraction from water resources, which makes it possible to compare different methods that determine the optimal path for further research. Moreover, scientists around the world are challenged to find a way to extract lithium from water resources that are environmentally friendly, highly selective, economical, time-efficient and easy to process.

Lithium is comparatively abundant on the earth's crust, being the affluent 25th more element [58]. More than 150 minerals contain lithium, in solid sediments, in geothermal waters, in many continental brines and in seawater. The concentration of lithium in seawater is very low, with an average of 0.17 ppm [3, 59]. The change in concentration from 1 to 100 ppm shows geothermal waters around the world [2, 4]. Although lithium deposits in all of the above forms are widespread throughout the world, only a very few are large enough and/or concentrated to potentially allow their exploitation. Several high-grade lithium minerals and brines are the only ones cur-

Interest in the recycling of lithium batteries has grown in recent years. However, recycling is still not economically attractive if compared with the mining of the raw materials [60]. Facilities for recycling are now available in the USA, Canada, Belgium, Germany and Japan. However, lithium availability from recycling is

Figures for lithium resources and reserves differ considerably accordingly to the source, although there is unanimously agreement that lithium resources in brine are much larger than those in hard rock [2–4, 6]. The latest data from the U.S. Geological Survey show that total lithium resources (brine + hard rock) are 54.1 million tons. It was reported that the minimum and maximum reserves of lithium

in LiOH alkali solution [43]. Despite the fact the maximum absorption

adsorption capacity [48]. By Xiao et al. synthesized spinel-struc-

[54]. 1-D MnO2 was synthesized with a maximum adsorption

in LiOH solution (C0 = 35 mg L<sup>−</sup><sup>1</sup>

with lithium absorption of only 2–3 mg g<sup>−</sup><sup>1</sup>

. By

) [50]. In this case,

[41]. Tang et al. and Zhang

*DOI: http://dx.doi.org/10.5772/intechopen.90371*

its adsorption capacity with lithium reached 32 mg g<sup>−</sup><sup>1</sup>

dissolution of manganese, which will violate its cyclicality.

tions, which are crucial in industrial design, were not reported.

stable and high selectivity for Li+

Li+

capacity reaching 46.34 mg g<sup>−</sup><sup>1</sup>

76.7 mg g<sup>−</sup><sup>1</sup>

with 52 mg g<sup>−</sup><sup>1</sup>

was up to 42 mg g<sup>−</sup><sup>1</sup>

**2. Lithium extraction**

rently manufacturing at lithium extraction [2–4].

insignificant as compared with mined raw materials [61].

of Li<sup>+</sup>

g<sup>−</sup><sup>1</sup>

*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water… DOI: http://dx.doi.org/10.5772/intechopen.90371*

have previously been reported, including metal oxides, clay minerals, silicotitanates and zirconium phosphate. The main attention of the researchers was focused on the adsorbents of titanium-lithium ion sieves [39–43] manganese-lithium ion sieves [44–50] and aluminum salts [51, 52]. Adsorbents of aluminum salts [52] showed stable and high selectivity for Li+ with lithium absorption of only 2–3 mg g<sup>−</sup><sup>1</sup> . By Chitrakar et al. [53] nanoscale H2TiO3 was synthesized by solid-phase reaction and its adsorption capacity with lithium reached 32 mg g<sup>−</sup><sup>1</sup> [41]. Tang et al. and Zhang et al. were synthesized H2TiO3 using different raw materials [41, 42]. Wang et al. synthesized lithium-enriched β-Li2TiO3 with a maximum lithium absorption of 76.7 mg g<sup>−</sup><sup>1</sup> in LiOH alkali solution [43]. Despite the fact the maximum absorption of Li<sup>+</sup> adsorbent H2TiO3 from the lithium-enriched solution has reached 76.7 mg g<sup>−</sup><sup>1</sup> , the high cost of synthesis and loss of dissolution of the titanium ion is still an obstacle. Chitrakar et al. by hydrothermal reaction synthesized Li1.6Mn1.6O4 and with 52 mg g<sup>−</sup><sup>1</sup> Li+ adsorption capacity [48]. By Xiao et al. synthesized spinel-structured hydrogen oxides of manganese, the saturated adsorption capacity of which was up to 42 mg g<sup>−</sup><sup>1</sup> [54]. 1-D MnO2 was synthesized with a maximum adsorption capacity reaching 46.34 mg g<sup>−</sup><sup>1</sup> in LiOH solution (C0 = 35 mg L<sup>−</sup><sup>1</sup> ) [50]. In this case, the dismutation reaction during etching can lead to distortion of the lattice and dissolution of manganese, which will violate its cyclicality.

In addition to lithium and magnesium, the treated salt lake brines may contain significant concentrations of potassium, sodium and boron. Zhou et al. compared the competitive sequences for several cations using TBP/FeCl3 in MIBK as the extractant [55–57]. However, quantitative correlations for competing for ion extractions, which are crucial in industrial design, were not reported.

The review is devoted to the extraction of lithium from brines, marine and geothermal waters, the collection of different methods of lithium extraction from water resources, which makes it possible to compare different methods that determine the optimal path for further research. Moreover, scientists around the world are challenged to find a way to extract lithium from water resources that are environmentally friendly, highly selective, economical, time-efficient and easy to process.

### **2. Lithium extraction**

*Thermodynamics and Energy Engineering*

sources.

use of lithium on ceramics enriched with Li6

of tritium [8, 9]. In addition, enriched Li6

lithium-sulfur or lithium-air [12–15].

Lithium has various uses, but its abundance in nature is only 0.0018% [7]. The

Lithium demand is expected to grow continuously and dramatically in the coming years as different types of lithium batteries are the most promising candidates for powering electric or hybrid vehicles [10, 11]. Lithium batteries include both current technologies such as lithium-ion and growing battery technologies such as

Lithium demand is projected to increase by ~60% from 102,000 to 162,000 tonnes of lithium carbonate equivalent in the next 5 years, with battery applications taking a huge percentage of this growth [16, 17]. It was reported that the present lithium resource in continental and Salar brines is roughly 52.3 million tons of lithium equivalent, mainly in Argentina, Chile and Bolivia, from which 23.2 million tons can be extracted [18]. From the other side, lithium from mineral resources is 8.8 million tons, where there are huge deposits in the United States, Russia and China. Evans estimated lithium reserves and recoverable resources at 29.79 million tons [19]. Meanwhile, the general public mainly associates lithium batteries with portable electronics and electric and hybrid vehicles, large storage capacity lithium batteries are also a lead candidate for a possible energy storage solution for the electric grid, intelligent network, etc. Batteries with large capacity are needed to store green energy, wind, that is, sun and waves, all this by their nature intermittent sources of energy [20–30]. Nowadays battling to achieve a greater percentage of green energy, high-capacity batteries or energy banks are mandatory. Basically, if in the near future we want our energy matrix to be highly dependent on renewable energy, energy banks will be needed to provide continuous energy to the grid, during the time these intermittent energy sources are either off or not working completely (no wind, no waves, at night) [20–22]. After all, on its own of the energy source, high-capacity batteries are also an alternative for storing energy during periods of low demand, allowing this excess energy to be re-injected into the grid at high demand peaks [24]. Currently, lithium is relatively not expensive (a ton of Li2CO3 is about 15,000 USD), the market shows that, its price is rising with increasing demand [25].

In China, lithium prices have risen about 300% since 2016, and contract prices

Because of the exhaustion of lithium ores, recent studies have shown recovery of lithium from seawater, brine and geothermal water. Production of lithium from water resources has become more important due to its wide availability, ease of process and

Various methods of removing lithium from water have been proposed in recent

years. In their midst, adsorption has been proven to be a perfect way to extract lithium, offering significant benefits, such as availability, lower cost, profitability, efficiency and easy operation. For lithium removal, various Li adsorbent materials

for existing manufacturers have risen to more than 16,000 USD per tonne.

cost-effectiveness compared with its production from various resources [26]. Many methods for extracting lithium from seawater, brines and geothermal water have been reported [27]: solvent extraction, including precipitation, liquidliquid extraction, selective membrane separation, electrodialysis, ion exchange adsorption, etc. [28–34]. Of these methods, the most attention was paid to ion exchange adsorption methods based on lithium-ion sieves because of their good lithium-ion selectivity and high adsorption properties [35–37]. From the point of view of cost and efficiency, extraction of lithium ions from solutions by ion

exchange adsorption is an important method [38].

with the value of gold. Consequently, it is necessary to extract and recycle lithium from the waste of solid breeding materials. Hence widespread use of lithium in various spheres, many studies have been conducted to extract lithium from various

is up to 15% for use in the production

is very expensive, what is commensurate

**188**

Lithium is comparatively abundant on the earth's crust, being the affluent 25th more element [58]. More than 150 minerals contain lithium, in solid sediments, in geothermal waters, in many continental brines and in seawater. The concentration of lithium in seawater is very low, with an average of 0.17 ppm [3, 59]. The change in concentration from 1 to 100 ppm shows geothermal waters around the world [2, 4]. Although lithium deposits in all of the above forms are widespread throughout the world, only a very few are large enough and/or concentrated to potentially allow their exploitation. Several high-grade lithium minerals and brines are the only ones currently manufacturing at lithium extraction [2–4].

Interest in the recycling of lithium batteries has grown in recent years. However, recycling is still not economically attractive if compared with the mining of the raw materials [60]. Facilities for recycling are now available in the USA, Canada, Belgium, Germany and Japan. However, lithium availability from recycling is insignificant as compared with mined raw materials [61].

Figures for lithium resources and reserves differ considerably accordingly to the source, although there is unanimously agreement that lithium resources in brine are much larger than those in hard rock [2–4, 6]. The latest data from the U.S. Geological Survey show that total lithium resources (brine + hard rock) are 54.1 million tons. It was reported that the minimum and maximum reserves of lithium

in hard rocks were 12.8 and 30.7 million tons, respectively; while the brine field data were reported as 21.3 and 65.3 million tons, respectively, for the minimum and maximum evaluation [3].
