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Lithium
Lithium
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Lithium, 3Li
A block of metal in a gloved hand
Freshly cut sample of lithium, with minimal oxides
Lithium
Pronunciation/ˈlɪθiəm/ (LITH-ee-əm)
Appearancesilvery-white
Standard atomic weight Ar°(Li)
Lithium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
H

Li

Na
heliumlithiumberyllium
Atomic number (Z)3
Groupgroup 1: hydrogen and alkali metals
Periodperiod 2
Block  s-block
Electron configuration[He] 2s1
Electrons per shell2, 1
Physical properties
Phase at STPsolid
Melting point453.65 K ​(180.50 °C, ​356.90 °F)
Boiling point1617 K ​(1344 °C, ​2451 °F)
Density (at 20° C)0.5334 g/cm3[3]
when liquid (at m.p.)0.512 g/cm3
Critical point3220 K, 67 MPa (extrapolated)
Heat of fusion3.00 kJ/mol
Heat of vaporization136 kJ/mol
Molar heat capacity24.860 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 797 885 995 1144 1337 1610
Atomic properties
Oxidation statescommon: +1
−1[4]
ElectronegativityPauling scale: 0.98
Ionization energies
  • 1st: 520.2 kJ/mol
  • 2nd: 7298.1 kJ/mol
  • 3rd: 11815.0 kJ/mol
Atomic radiusempirical: 152 pm
Covalent radius128±7 pm
Van der Waals radius182 pm
Color lines in a spectral range
Spectral lines of lithium
Other properties
Natural occurrenceprimordial
Crystal structurebody-centered cubic (bcc) (cI2)
Lattice constant
Body-centered cubic crystal structure for lithium
a = 350.93 pm (at 20 °C)[3]
Thermal expansion46.56×10−6/K (at 20 °C)[3]
Thermal conductivity84.8 W/(m⋅K)
Electrical resistivity92.8 nΩ⋅m (at 20 °C)
Magnetic orderingparamagnetic
Molar magnetic susceptibility+14.2×10−6 cm3/mol (298 K)[5]
Young's modulus4.9 GPa
Shear modulus4.2 GPa
Bulk modulus11 GPa
Speed of sound thin rod6000 m/s (at 20 °C)
Mohs hardness0.6
Brinell hardness5 MPa
CAS Number7439-93-2
History
Namingfrom the Greek word λιθoς, stone
DiscoveryJohan August Arfwedson (1817)
First isolationWilliam Thomas Brande (1821)
Isotopes of lithium
Main isotopes[6] Decay
Isotope abun­dance half-life (t1/2) mode pro­duct
6Li [1.9%, 7.8%] stable
7Li [92.2%, 98.1%] stable
Significant variation occurs in commercial samples because of the wide distribution of samples depleted in 6Li.
 Category: Lithium
| references

Lithium (from Ancient Greek: λίθος, líthos, 'stone') is a chemical element; it has symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid element. Like all alkali metals, lithium is highly reactive and flammable, and must be stored in vacuum, inert atmosphere, or inert liquid such as purified kerosene[7] or mineral oil. It exhibits a metallic luster when pure, but quickly corrodes in air to a dull silvery gray, then black tarnish. It does not occur freely in nature, but occurs mainly as pegmatitic minerals, which were once the main source of lithium. Due to its solubility as an ion, it is present in ocean water and is commonly obtained from brines. Lithium metal is isolated electrolytically from a mixture of lithium chloride and potassium chloride.

The nucleus of the lithium atom verges on instability, since the two stable lithium isotopes found in nature have among the lowest binding energies per nucleon of all stable nuclides. Because of its relative nuclear instability, lithium is less common in the Solar System than 25 of the first 32 chemical elements even though its nuclei are very light: it is an exception to the trend that heavier nuclei are less common.[8] For related reasons, lithium has important uses in nuclear physics. The transmutation of lithium atoms to helium in 1932 was the first fully human-made nuclear reaction, and lithium deuteride serves as a fusion fuel in staged thermonuclear weapons.[9]

Lithium and its compounds have several industrial applications, including heat-resistant glass and ceramics, lithium grease lubricants, flux additives for iron, steel and aluminium production, lithium metal batteries, and lithium-ion batteries. Batteries alone consume more than three-quarters of lithium production.[10]

Lithium is present in biological systems in trace amounts. Lithium-based drugs are useful as a mood stabilizer and antidepressant in the treatment of mental illness such as bipolar disorder.

Properties

[edit]

Atomic and physical

[edit]
Lithium ingots with a thin layer of black nitride tarnish

The alkali metals are also called the lithium family, after its leading element. Like the other alkali metals (which are sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr)), lithium has a single valence electron that, in the presence of solvents, is easily released to form Li+.[11] Because of this, lithium is a good conductor of heat and electricity as well as a highly reactive element, though it is the least reactive of the alkali metals. Lithium's lower reactivity is due to the proximity of its valence electron to its nucleus (the remaining two electrons are in the 1s orbital, much lower in energy, and do not participate in chemical bonds).[11] Molten lithium is significantly more reactive than its solid form.[12][13]

Lithium metal is soft enough to be cut with a knife. It is silvery-white. In air it oxidizes to lithium oxide.[11] Its melting point of 180.50 °C (453.65 K; 356.90 °F)[14] and its boiling point of 1,342 °C (1,615 K; 2,448 °F)[14] are each the highest of all the alkali metals while its density of 0.534 g/cm3 is the lowest.

Lithium has a very low density (0.534 g/cm3), comparable with pine wood.[15] It is the least dense of all elements that are solids at room temperature; the next lightest solid element (potassium, at 0.862 g/cm3) is more than 60% denser. Apart from helium and hydrogen, as a solid it is less dense than any other element as a liquid, being only two-thirds as dense as liquid nitrogen (0.808 g/cm3).[16] Lithium can float on the lightest hydrocarbon oils and is one of only three metals that can float on water, the other two being sodium and potassium.

Lithium floating in oil

Lithium's coefficient of thermal expansion is twice that of aluminium and almost four times that of iron.[17] Lithium is superconductive below 400 μK at standard pressure[18] and at higher temperatures (more than 9 K) at very high pressures (>20 GPa).[19] At temperatures below 70 K, lithium, like sodium, undergoes diffusionless phase change transformations. At 4.2 K it has a rhombohedral crystal system (with a nine-layer repeat spacing); at higher temperatures it transforms to face-centered cubic and then body-centered cubic. At liquid-helium temperatures (4 K) the rhombohedral structure is prevalent.[20] Multiple allotropic forms have been identified for lithium at high pressures.[21]

Lithium has a mass specific heat capacity of 3.58 kilojoules per kilogram-kelvin, the highest of all solids.[22][23] Because of this, lithium metal is often used in coolants for heat transfer applications.[22]

Isotopes

[edit]

Naturally occurring lithium is composed of two stable isotopes, 6Li and 7Li, the latter being the more abundant (95.15% natural abundance).[24][25] Both natural isotopes have anomalously low nuclear binding energy per nucleon (compared to the neighboring elements on the periodic table, helium and beryllium); lithium is the only low numbered element that can produce net energy through nuclear fission. The two lithium nuclei have lower binding energies per nucleon than any other stable nuclides other than hydrogen-1, deuterium and helium-3.[26] As a result of this, though very light in atomic weight, lithium is less common in the Solar System than 25 of the first 32 chemical elements.[8] Seven radioisotopes have been characterized, the most stable being 8Li with a half-life of 838 ms and 9Li with a half-life of 178 ms. All of the remaining radioactive isotopes have half-lives that are shorter than 8.6 ms. The shortest-lived isotope of lithium is 4Li, which decays through proton emission and has a half-life of 7.6 × 10−23 s.[27] The 6Li isotope is one of only five stable nuclides to have both an odd number of protons and an odd number of neutrons, the other four stable odd-odd nuclides being hydrogen-2, boron-10, nitrogen-14, and tantalum-180m.[28]

7Li is one of the primordial elements (or, more properly, primordial nuclides) produced in Big Bang nucleosynthesis. A small amount of both 6Li and 7Li are produced in stars during stellar nucleosynthesis, but it is further "burned" as fast as produced.[29] 7Li can also be generated in carbon stars.[30] Additional small amounts of both 6Li and 7Li may be generated from solar wind, cosmic rays hitting heavier atoms, and from early solar system 7Be radioactive decay.[31]

Lithium isotopes fractionate substantially during a wide variety of natural processes,[32] including mineral formation (chemical precipitation), metabolism, and ion exchange. Lithium ions substitute for magnesium and iron in octahedral sites in clay minerals, where 6Li is preferred to 7Li, resulting in enrichment of the light isotope in processes of hyperfiltration and rock alteration. The exotic 11Li is known to exhibit a neutron halo, with 2 neutrons orbiting around its nucleus of 3 protons and 6 neutrons. The process known as laser isotope separation can be used to separate lithium isotopes, in particular 7Li from 6Li.[33]

Nuclear weapons manufacture and other nuclear physics applications are a major source of artificial lithium fractionation, with the light isotope 6Li being retained by industry and military stockpiles to such an extent that it has caused slight but measurable change in the 6Li to 7Li ratios in natural sources, such as rivers. This has led to unusual uncertainty in the standardized atomic weight of lithium, since this quantity depends on the natural abundance ratios of these naturally occurring stable lithium isotopes, as they are available in commercial lithium mineral sources.[34]

Both stable isotopes of lithium can be laser cooled and were used to produce the first quantum degenerate BoseFermi mixture.[35]

Occurrence

[edit]
Lithium is about as common as chlorine in the Earth's upper continental crust, on a per-atom basis.

Astronomical

[edit]

Although it was synthesized in the Big Bang, lithium (together with beryllium and boron) is markedly less abundant in the universe than other elements. This is a result of the comparatively low stellar temperatures necessary to destroy lithium, along with a lack of common processes to produce it.[36]

According to modern cosmological theory, lithium—in both stable isotopes (lithium-6 and lithium-7)—was one of the three elements synthesized in the Big Bang.[37] Though the amount of lithium generated in Big Bang nucleosynthesis is dependent upon the number of photons per baryon, for accepted values the lithium abundance can be calculated, and there is a "cosmological lithium discrepancy" in the universe: older stars seem to have less lithium than they should, and some younger stars have much more.[38] The lack of lithium in older stars is apparently caused by the "mixing" of lithium into the interior of stars, where it is destroyed,[39] while lithium is produced in younger stars. Although it transmutes into two atoms of helium due to collision with a proton at temperatures above 2.4 million degrees Celsius (most stars easily attain this temperature in their interiors), lithium is more abundant than computations would predict in later-generation stars.[40]

Nova Centauri 2013 is the first in which evidence of lithium has been found.[41]

Lithium is also found in brown dwarf substellar objects and certain anomalous orange stars. Because lithium is present in cooler, less-massive brown dwarfs, but is destroyed in hotter red dwarf stars, its presence in the stars' spectra can be used in the "lithium test" to differentiate the two, as both are smaller than the Sun.[40][42][43] Certain orange stars can also contain a high concentration of lithium. Those orange stars found to have a higher than usual concentration of lithium (such as Centaurus X-4) orbit massive objects—neutron stars or black holes—whose gravity evidently pulls heavier lithium to the surface of a hydrogen-helium star, causing more lithium to be observed.[40]

On 27 May 2020, astronomers reported that classical nova explosions are galactic producers of lithium-7.[44][45]

Terrestrial

[edit]

Although lithium is widely distributed on Earth, it does not naturally occur in elemental form due to its high reactivity.[11] The total lithium content of seawater is very large and is estimated as 230 billion tonnes, where the element exists at a relatively constant concentration of 0.14 to 0.25 parts per million (ppm),[46][47] or 25 micromolar;[48] higher concentrations approaching 7 ppm are found near hydrothermal vents.[47]

Estimates for the Earth's crustal content range from 20 to 70 ppm by weight.[49][50] In keeping with its name, lithium forms a minor part of igneous rocks, with the largest concentrations in granites. Granitic pegmatites also provide the greatest abundance of lithium-containing minerals, with spodumene and petalite being the most commercially viable sources.[49] Another significant mineral of lithium is lepidolite which is now an obsolete name for a series formed by polylithionite and trilithionite.[51][52] Another source for lithium is hectorite clay, the only active development of which is through the Western Lithium Corporation in the United States.[53] At 20 mg lithium per kg of Earth's crust,[54] lithium is the 31st most abundant element.[55]

According to the Handbook of Lithium and Natural Calcium, "Lithium is a comparatively rare element, although it is found in many rocks and some brines, but always in very low concentrations. There are a fairly large number of both lithium mineral and brine deposits but only comparatively few of them are of actual or potential commercial value. Many are very small, others are too low in grade."[56]

Chile is estimated (2020) to have the largest reserves by far (9.2 million tonnes),[57] and Australia the highest annual production (40,000 tonnes).[57] One of the largest reserve bases[note 1] of lithium is in the Salar de Uyuni area of Bolivia, which has 5.4 million tonnes. Other major suppliers include Argentina and China.[58][59] As of 2015, the Czech Geological Survey considered the entire Ore Mountains in the Czech Republic as lithium province. Five deposits are registered, one near Cínovec [cs] is considered as a potentially economical deposit, with 160 000 tonnes of lithium.[60] In December 2019, Finnish mining company Keliber Oy reported its Rapasaari lithium deposit has estimated proven and probable ore reserves of 5.280 million tonnes.[61]

In June 2010, The New York Times reported that American geologists were conducting ground surveys on dry salt lakes in western Afghanistan believing that large deposits of lithium are located there.[62] These estimates are "based principally on old data, which was gathered mainly by the Soviets during their occupation of Afghanistan from 1979–1989".[63] The Department of Defense estimated the lithium reserves in Afghanistan to amount to the ones in Bolivia and dubbed it as a potential "Saudi-Arabia of lithium".[64] In Cornwall, England, the presence of brine rich in lithium was well known due to the region's historic mining industry, and private investors have conducted tests to investigate potential lithium extraction in this area.[65][66]

Biological

[edit]

Lithium is found in trace amount in numerous plants, plankton, and invertebrates, at concentrations of 69 to 5,760 parts per billion (ppb). In vertebrates the concentration is slightly lower, and nearly all vertebrate tissue and body fluids contain lithium ranging from 21 to 763 ppb.[47] Marine organisms tend to bioaccumulate lithium more than terrestrial organisms.[67] Whether lithium has a physiological role in any of these organisms is unknown.[47] Lithium concentrations in human tissue averages about 24 ppb (4 ppb in blood, and 1.3 ppm in bone).[68]

Lithium is easily absorbed by plants[68] and lithium concentration in plant tissue is typically around 1 ppm.[69] Some plant families bioaccumulate more lithium than others.[69] Dry weight lithium concentrations for members of the family Solanaceae (which includes potatoes and tomatoes), for instance, can be as high as 30 ppm while this can be as low as 0.05 ppb for corn grains.[68] Studies of lithium concentrations in mineral-rich soil give ranges between around 0.1 and 50−100 ppm, with some concentrations as high as 100−400 ppm, although it is unlikely that all of it is available for uptake by plants.[69] Lithium accumulation does not appear to affect the essential nutrient composition of plants.[69] Tolerance to lithium varies by plant species and typically parallels sodium tolerance; maize and Rhodes grass, for example, are highly tolerant to lithium injury while avocado and soybean are very sensitive.[69] Similarly, lithium at concentrations of 5 ppm reduces seed germination in some species (e.g. Asian rice and chickpea) but not in others (e.g. barley and wheat).[69]

Many of lithium's major biological effects can be explained by its competition with other ions.[70] The monovalent lithium ion Li+
competes with other ions such as sodium (immediately below lithium on the periodic table), which like lithium is also a monovalent alkali metal. Lithium also competes with bivalent magnesium ions, whose ionic radius (86 pm) is approximately that of the lithium ion[70] (90 pm). Mechanisms that transport sodium across cellular membranes also transport lithium. For instance, sodium channels (both voltage-gated and epithelial) are particularly major pathways of entry for lithium.[70] Lithium ions can also permeate through ligand-gated ion channels as well as cross both nuclear and mitochondrial membranes.[70] Like sodium, lithium can enter and partially block (although not permeate) potassium channels and calcium channels.[70]

The biological effects of lithium are many and varied but its mechanisms of action are only partially understood.[71] For instance, studies of lithium-treated patients with bipolar disorder show that, among many other effects, lithium partially reverses telomere shortening in these patients and also increases mitochondrial function, although how lithium produces these pharmacological effects is not understood.[71][72]

Even the exact mechanisms involved in lithium toxicity are not fully understood.

One study indicated reduced cortical lithium in the brains of individuals with Mild Cognitive Impairment (MCI) and Alzheimer's Disease. This deficiency, caused in part by lithium's sequestration within amyloid plaques, has been shown to accelerate Alzheimer's pathology in mouse models through the over-activation of the kinase GSK3β. This physiological role is distinct from the use of lithium-based drugs at much higher pharmacological doses as a mood stabilizer in the treatment of mental illness such as bipolar disorder.[73][74]

History

[edit]
Johan August Arfwedson is credited with the discovery of lithium in 1817.

Petalite (LiAlSi4O10) was discovered in 1800 by the Brazilian chemist and statesman José Bonifácio de Andrada e Silva in a mine on the island of Utö, Sweden.[75][76][77][78] However, it was not until 1817 that Johan August Arfwedson, then working in the laboratory of the chemist Jöns Jakob Berzelius, detected the presence of a new element while analyzing petalite ore.[79][80][81][82] This element formed compounds similar to those of sodium and potassium, though its carbonate and hydroxide were less soluble in water and less alkaline.[83] Berzelius gave the alkaline material the name "lithion/lithina", from the Greek word λιθoς (transliterated as lithos, meaning "stone"), to reflect its discovery in a solid mineral, as opposed to potassium, which had been discovered in plant ashes, and sodium, which was known partly for its high abundance in animal blood. He named the new element "lithium".[11][77][82]

Arfwedson later showed that this same element was present in the minerals spodumene and lepidolite.[84][77] In 1818, Christian Gmelin was the first to observe that lithium salts give a bright red color to flame.[77][85] However, both Arfwedson and Gmelin tried and failed to isolate the pure element from its salts.[77][82][86] It was not isolated until 1821, when William Thomas Brande obtained it by electrolysis of lithium oxide, a process that had previously been employed by the chemist Sir Humphry Davy to isolate the alkali metals potassium and sodium.[40][86][87][88][89] Brande also described some pure salts of lithium, such as the chloride, and, estimating that lithia (lithium oxide) contained about 55% metal, estimated the atomic weight of lithium to be around 9.8 g/mol (modern value ~6.94 g/mol).[90] In 1855, larger quantities of lithium were produced through the electrolysis of lithium chloride by Robert Bunsen and Augustus Matthiessen.[77][91] The discovery of this procedure led to commercial production of lithium in 1923 by the German company Metallgesellschaft AG, which performed an electrolysis of a liquid mixture of lithium chloride and potassium chloride.[77][92][93]

Australian psychiatrist John Cade is credited with reintroducing and popularizing the use of lithium to treat mania in 1949.[94] Shortly after, throughout the mid-20th century, lithium's mood stabilizing applicability for mania and depression took off in Europe and the United States.

The production and use of lithium underwent several drastic changes in history. The first major application of lithium was in high-temperature lithium greases for aircraft engines and similar applications in World War II and shortly after. This use was supported by the fact that lithium-based soaps have a higher melting point than other alkali soaps, and are less corrosive than calcium based soaps. The small demand for lithium soaps and lubricating greases was supported by several small mining operations, mostly in the US.

The demand for lithium increased dramatically during the Cold War with the production of nuclear fusion weapons. Both lithium-6 and lithium-7 produce tritium when irradiated by neutrons, and are thus useful for the production of tritium by itself, as well as a form of solid fusion fuel used inside hydrogen bombs in the form of lithium deuteride. The US became the prime producer of lithium between the late 1950s and the mid-1980s. At the end, the stockpile of lithium was roughly 42,000 tonnes of lithium hydroxide. The stockpiled lithium was depleted in lithium-6 by 75%, which was enough to affect the measured atomic weight of lithium in many standardized chemicals, and even the atomic weight of lithium in some "natural sources" of lithium ion which had been "contaminated" by lithium salts discharged from isotope separation facilities, which had found its way into ground water.[34][95]

alt1
alt2
Satellite images of the Salar del Hombre Muerto, Argentina (left), and Uyuni, Bolivia (right), salt flats that are rich in lithium. The lithium-rich brine is concentrated by pumping it into solar evaporation ponds (visible in the left image).

Lithium is used to decrease the melting temperature of glass and to improve the melting behavior of aluminium oxide in the Hall-Héroult process.[96][97] These two uses dominated the market until the middle of the 1990s. After the end of the nuclear arms race, the demand for lithium decreased and the sale of department of energy stockpiles on the open market further reduced prices.[95] In the mid-1990s, several companies started to isolate lithium from brine which proved to be a less expensive option than underground or open-pit mining. Most of the mines closed or shifted their focus to other materials because only the ore from zoned pegmatites could be mined for a competitive price. For example, the US mines near Kings Mountain, North Carolina, closed before the beginning of the 21st century.

The development of lithium-ion batteries increased the demand for lithium and became the dominant use in 2007.[98] With the surge of lithium demand in batteries in the 2000s, new companies have expanded brine isolation efforts to meet the rising demand.[99][100]

Chemistry

[edit]

Of lithium metal

[edit]

Lithium reacts with water easily, but with noticeably less vigor than other alkali metals. The reaction forms hydrogen gas and lithium hydroxide.[11] When placed over a flame, lithium compounds give off a striking crimson color, but when the metal burns strongly, the flame becomes a brilliant silver. Lithium will ignite and burn in oxygen when exposed to water or water vapor. In moist air, lithium rapidly tarnishes to form a black coating of lithium hydroxide (LiOH and LiOH·H2O), lithium nitride (Li3N) and lithium carbonate (Li2CO3, the result of a secondary reaction between LiOH and CO2).[49] Lithium is one of the few metals that react with nitrogen gas.[101][102]

Because of its reactivity with water, and especially nitrogen, lithium metal is usually stored in a hydrocarbon sealant, often petroleum jelly. Although the heavier alkali metals can be stored under mineral oil, lithium is not dense enough to fully submerge itself in these liquids.[40]

Lithium has a diagonal relationship with magnesium, an element of similar atomic and ionic radius. Chemical resemblances between the two metals include the formation of a nitride by reaction with N2, the formation of an oxide (Li
2
O
) and peroxide (Li
2
O
2
) when burnt in O2, salts with similar solubilities, and thermal instability of the carbonates and nitrides.[49][103] The metal reacts with hydrogen gas at high temperatures to produce lithium hydride (LiH).[104]

Lithium forms a variety of binary and ternary materials by direct reaction with the main group elements. These Zintl phases, although highly covalent, can be viewed as salts of polyatomic anions such as Si44-, P73-, and Te52-. With graphite, lithium forms a variety of intercalation compounds.[103]

It dissolves in ammonia (and amines) to give [Li(NH3)4]+ and the solvated electron.[103]

Inorganic compounds

[edit]

Lithium forms salt-like derivatives with all halides and pseudohalides. Some examples include the halides LiF, LiCl, LiBr, LiI, as well as the pseudohalides and related anions. Lithium carbonate has been described as the most important compound of lithium.[103] This white solid is the principal product of beneficiation of lithium ores. It is a precursor to other salts including ceramics and materials for lithium batteries.

The compounds LiBH
4
and LiAlH
4
are useful reagents. These salts and many other lithium salts exhibit distinctively high solubility in ethers, in contrast with salts of heavier alkali metals.

In aqueous solution, the coordination complex [Li(H2O)4]+ predominates for many lithium salts. Related complexes are known with amines and ethers.

Organic chemistry

[edit]
Hexameric structure of the n-butyllithium fragment in a crystal

Organolithium compounds are numerous and useful. They are defined by the presence of a bond between carbon and lithium. They serve as metal-stabilized carbanions, although their solution and solid-state structures are more complex than this simplistic view.[105] Thus, these are extremely powerful bases and nucleophiles. They have also been applied in asymmetric synthesis in the pharmaceutical industry. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric.

Like its inorganic compounds, almost all organic compounds of lithium formally follow the duet rule (e.g., BuLi, MeLi). However, it is important to note that in the absence of coordinating solvents or ligands, organolithium compounds form dimeric, tetrameric, and hexameric clusters (e.g., BuLi is actually [BuLi]6 and MeLi is actually [MeLi]4) which feature multi-center bonding and increase the coordination number around lithium. These clusters are broken down into smaller or monomeric units in the presence of solvents like dimethoxyethane (DME) or ligands like tetramethylethylenediamine (TMEDA).[106] As an exception to the duet rule, a two-coordinate lithate complex with four electrons around lithium, [Li(thf)4]+[((Me3Si)3C)2Li], has been characterized crystallographically.[107]

Production

[edit]
Lithium mine production (2023), reserves and resources in tonnes according to USGS[57]
Country Production Reserves[note 1] Resources
Argentina 8,630 4,000,000 23,000,000
Australia 91,700 7,000,000 8,900,000
Austria - - 60,000
Bolivia - - 23,000,000
Brazil 5,260 390,000 1,300,000
Canada 3,240 1,200,000 5,700,000
Chile 41,400 9,300,000 11,000,000
China 35,700 3,000,000 6,800,000
Czech Republic - - 1,300,000
DR Congo - - 3,000,000
Finland - - 55,000
Germany - - 4,000,000
Ghana - - 200,000
India - - 5,900,000[108][109]
Kazakhstan - - 45,000
Mali - - 1,200,000
Mexico - - 1,700,000
Namibia 2,700 14,000 230,000
Peru - - 1,000,000
Portugal 380 60,000 270,000
Russia - - 1,000,000
Serbia - - 1,200,000
Spain - - 320,000
United States 870[note 2] 1,800,000 14,000,000
Zimbabwe 14,900 480,000 860,000
Other countries - 2,800,000 -
World total 204,000[note 3] 30,000,000 116,000,000+

Lithium production has greatly increased since the end of World War II. The main sources of lithium are brines and ores.

Lithium metal is produced through electrolysis applied to a mixture of fused 55% lithium chloride and 45% potassium chloride at about 450 °C.[110]

Lithium is one of the elements critical in a world running on renewable energy and dependent on batteries. This suggests that lithium will be one of the main objects of geopolitical competition, but this perspective has also been criticised for underestimating the power of economic incentives for expanded production.[111]

Reserves and occurrence

[edit]
Scatter plots of lithium grade and tonnage for selected world deposits, as of 2017

The small ionic size makes it difficult for lithium to be included in early stages of mineral crystallization. As a result, lithium remains in the molten phases, where it gets enriched, until it gets solidified in the final stages. Such lithium enrichment is responsible for all commercially promising lithium ore deposits. Brines (and dry salt) are another important source of Li+. Although the number of known lithium-containing deposits and brines is large, most of them are either small or have too low Li+ concentrations. Thus, only a few appear to be of commercial value.[112]

The US Geological Survey (USGS) estimated worldwide identified lithium reserves in 2022 and 2023 to be 26 million and 28 million tonnes, respectively.[58][57] An accurate estimate of world lithium reserves is difficult.[113][114] One reason for this is that most lithium classification schemes are developed for solid ore deposits, whereas brine is a fluid that is problematic to treat with the same classification scheme due to varying concentrations and pumping effects.[115]

In 2019, world production of lithium from spodumene was around 80,000t per annum, primarily from the Greenbushes pegmatite and from some Chinese and Chilean sources. The Talison mine in Greenbushes is reported to be the largest and to have the highest grade of ore at 2.4% Li2O (2012 figures).[116]

Lithium triangle and other brine sources

[edit]

The world's top four lithium-producing countries in 2019, as reported by the US Geological Survey, were Australia, Chile, China and Argentina.[58]

The three countries of Chile, Bolivia, and Argentina contain a region known as the Lithium Triangle. The Lithium Triangle is known for its high-quality salt flats, which include Bolivia's Salar de Uyuni, Chile's Salar de Atacama, and Argentina's Salar de Arizaro. As of 2018, the Lithium Triangle had been estimated to contain over 75% of then known lithium reserves.[117] Deposits found in subsurface brines have also been found in the United States (southwest Texas and Arkansas)[118] and South America throughout the Andes mountain chain. In 2010, Chile was the leading producer, followed by Argentina. Both countries recover lithium from brine pools. According to USGS, Bolivia's Uyuni Desert has 5.4 million tonnes of lithium.[119][120] Half the world's known reserves as of 2022 were located in Bolivia along the central eastern slope of the Andes. The Bolivian government invested US$900 million in lithium production by 2022, and in 2021 successfully produced 540 tons.[121][119] The brines in the salt pans of the Lithium Triangle vary widely in lithium content.[122] Concentrations can also vary over time as brines are fluids that are changeable and mobile.[122]

Extracting lithium from brine deep in Wyoming's Rock Springs Uplift has been proposed as revenue source to make atmospheric carbon sequestration economically viable.[123] Additional deposits in the same formation were estimated to be as much as 18 million tons if economic means of recovery can be employed.[124] Similarly in Nevada, the McDermitt Caldera hosts lithium-bearing volcanic muds that consist of the largest known deposits of lithium within the United States.[125]

In the US, lithium is recovered from brine pools in Nevada.[22] Projects are also under development in Lithium Valley in California[126] and from brine in southwest Arkansas using the direct lithium extraction process, drawing on the deep brine resource in the Smackover Formation.[127]

Hard-rock deposits

[edit]

Since 2018 the Democratic Republic of Congo is known to have the largest lithium spodumene hard-rock deposit in the world.[128] The deposit located in Manono, DRC, may hold up to 1.5 billion tons of lithium spodumene hard-rock. The two largest pegmatites (known as the Carriere de l'Este Pegmatite and the Roche Dure Pegmatite) are each of similar size or larger than the famous Greenbushes Pegmatite in Western Australia. Thus, the Democratic Republic of Congo is expected to be a significant supplier of lithium to the world with its high grade and low impurities.

On 16 July 2018 2.5 million tonnes of high-grade lithium resources and 124 million pounds of uranium resources were found in the Falchani hard rock deposit in the region Puno, Peru.[129] In 2020, Australia granted Major Project Status (MPS) to the Finniss Lithium Project for a strategically important lithium deposit: an estimated 3.45 million tonnes (Mt) of mineral resource at 1.4 percent lithium oxide.[130][131] Operational mining began in 2022.[132]

The Pampean Pegmatite Province in Argentina is known to have a total of at least 200,000 tons of spodumene with lithium oxide (Li2O) grades varying between 5 and 8 wt %.[133]

In Russia the largest lithium deposit Kolmozerskoye is located in Murmansk region. In 2023, Polar Lithium, a joint venture between Nornickel and Rosatom, has been granted the right to develop the deposit. The project aims to produce 60,000 tonnes of lithium carbonate and hydroxide per year and plans to reach full design capacity by 2030.[134]

Other sources

[edit]

Another potential source of lithium as of 2012 was identified as the leachates of geothermal wells, which are carried to the surface.[135] Recovery of this type of lithium has been demonstrated in the field; the lithium is separated by simple filtration.[136][137] Reserves are more limited than those of brine reservoirs and hard rock.[138]

Pricing

[edit]
Lithium prices

In 1998, the price of lithium metal was about 95 USD/kg (or US$43/lb).[139] After the 2008 financial crisis, major suppliers, such as Sociedad Química y Minera (SQM), dropped lithium carbonate pricing by 20%.[140] Prices rose in 2012. A 2012 Business Week article outlined an oligopoly in the lithium space: "SQM, controlled by billionaire Julio Ponce, is the second-largest, followed by Rockwood, which is backed by Henry Kravis's KKR & Co., and Philadelphia-based FMC", with Talison mentioned as the biggest producer.[141][needs update]

A 2012 Business Week article projected that global lithium consumption could increase to 300,000 metric tons a year by 2020, from about 150,000 tons in 2012, to match the demand for lithium batteries that had then been growing at about 25% a year, outpacing the late-2000s 4% to 5% overall gain in lithium production.[141][needs update]

The price information service ISE – Institute of Rare Earths Elements and Strategic Metals – gives for various lithium substances in the average of March to August 2022 the following kilo prices stable in the course: Lithium carbonate, purity 99.5% min, from various producers between 63 and 72 EUR/kg. Lithium hydroxide monohydrate LiOH 56.5% min, China, at 66 to 72 EUR/kg; delivered South Korea – 73 EUR/kg. Lithium metal 99.9% min, delivered China – 42 EUR/kg.[142]

Extraction

[edit]
Analyses of the extraction of lithium from seawater, published in 1975

Lithium and its compounds were historically isolated and extracted from hard rock. However, by the 1990s mineral springs, brine pools, and brine deposits had become the dominant source.[143] Most of these were in Chile, Argentina and Bolivia and the lithium is extracted from the brine by evaporative processes.[57] Large lithium-clay deposits under development in the McDermitt caldera (Nevada, United States) require concentrated sulfuric acid to leach lithium from the clay ore.[144]

By early 2021, much of the lithium mined globally came from either "spodumene, the mineral contained in hard rock formations found in places such as Australia and North Carolina"[145] or from salty brine pumped directly out of the ground, as it is in locations in Chile, Argentina, and Arkansas.[145][122][127]

In Chile's Salar de Atacama, the lithium concentration in the brine is raised by solar evaporation in a system of ponds.[122] The enrichment by evaporation process may require up to one-and-a-half years, when the brine reaches a lithium content of 6%.[122] The final processing in this example is done in Salar del Carmen and La Negra near the coastal city of Antofagasta where pure lithium carbonate, lithium hydroxide, and lithium chloride are produced from the brine.[122]

Direct Lithium Extraction (DLE) technologies are being developed as alternatives to the evaporitic technology long used to extract lithium salts from brines. The traditional evaporitic technology is a long duration process requiring large amounts of land and intensive water use, and can only be applied to the large continental brines. In contrast, DLE technologies are proposed to tackle the environmental and techno–economic shortcomings by avoiding brine evaporation.[146][147] Some recent lithium mining projects in the United States are attempting to bring DLE into commercial production by these non-evaporative DLE approaches.[127]

One method of direct lithium extraction, as well as other valuable minerals, is to process geothermal brine water through an electrolytic cell, located within a membrane.[148][149]

The use of electrodialysis and electrochemical intercalation was proposed in 2020 to extract lithium compounds from seawater (which contains lithium at 0.2 parts per million).[150][151][152][153] Ion-selective cells within a membrane in principle could collect lithium either by use of electric field or a concentration difference.[153] In 2024, a redox/electrodialysis system was claimed to offer enormous cost savings, shorter timelines, and less environmental damage than traditional evaporation-based systems.[154]

Environmental issues

[edit]
Environmental protests in Belgrade, Serbia, 11 December 2021

The manufacturing processes of lithium, including the solvent and mining waste of particular extraction processes can present environmental and health hazards.[155][156][157] Lithium extraction done poorly can be fatal to aquatic life due to water pollution.[158] The surface brine evaporation process has been known to cause surface water contamination, drinking water contamination, respiratory problems, ecosystem degradation and landscape damage,[155] and could lead to unsustainable water consumption in arid regions (1.9 million liters per ton of lithium), such as in northwestern Argentina.[159][155] Massive byproduct generation of evaporative surface lithium extraction also presents unsolved problems, such as large amounts of magnesium and lime waste.[160]

Although lithium occurs naturally, it is a non-renewable resource[better source needed] yet is seen as crucial in the transition away from fossil fuels, and the extraction process has been criticised for long-term degradation of water resources.[161][162] In the southern reaches of Salar de Atacama lithium-producing company Albemarle Limitada reached a concialiatory agreement in 2024 to make reparations freshwater uptake that would have contributed –along with the uptake of copper mining companies– to dry meadows locatede in the traditional lands of the indigenous Atacameño people.[163][164][165] In its defense Albemarle Limitada have asserted that its use is minimal compared to that of the nearby copper mining companies.[166]

In the United States, open-pit mining and mountaintop removal mining compete with brine extraction mining.[167] Environmental concerns include wildlife habitat degradation, potable water pollution including arsenic and antimony contamination, unsustainable water table reduction, and massive mining waste, including radioactive uranium byproduct and sulfuric acid discharge.[citation needed]

During 2021, a series of mass protests broke out in Serbia against the construction of a lithium mine in Western Serbia by the Rio Tinto corporation.[168] In 2024, an EU backed lithium mining project created large scale protests in Serbia.[169]

Some animal species associated with salt lakes in the Lithium Triangle (in Argentina, Bolivia and Chile) are particularly threatened by the damages of lithium production to the local ecosystem, including the Andean flamingo[170] and Orestias parinacotensis, a small fish locally known as "karachi".[171]

Human rights issues

[edit]

Reporting on lithium extraction companies and indigenous peoples in Argentina found that the state may did not always protect indigenous peoples' right to free prior and informed consent, and that extraction companies generally controlled community access to information and set the terms for discussion of the projects and benefit sharing.[159][172]

In Argentina's Puna region, in 2023, two mining companies (Minera Exar and Sales de Jujuy) extracted over 3.7 billion liters of fresh water, over 31 times the annual water consumption of the local community of Susques department.[159]

Extraction of lithium-rich brines in Salar de Atacama in Chile led to conflict about water use with local communities.[170] The local indigenous population of Likan Antay have a history of both opposing lithium extraction and negotiating for shared benefits with lithium companies.[173] Negotiations occur under the framework of the Indigenous and Tribal Peoples Convention which Chile signed in 2008.[173] It is argued that in Chile "[a]greements between Indigenous organizations and lithium companies have brought significant economic resources for community development, but have also expanded the mining industry's capacity for social control in the area.".[173]

In Zimbabwe, the global increase in lithium prices in the early 2020s triggered a 'lithium fever' that led to displacement of locals and conflicts between small-scale artisanal miners and large-scale mining companies. Some local farmers agreed to relocate and were satisfied with their compensation.[174] Artisanal miners occupied parts of the Sandawana mines and a privately owned lithium claim area in Goromonzi, a rural area close to the capital Harare. The artisanal miners were later evicted after the area was cordoned off and shut down by Zimbabwe's Environmental Management Agency.[175]

Development of the Thacker Pass lithium mine in Nevada, United States, has met with protests and lawsuits from several indigenous tribes who have said they were not provided free prior and informed consent and that the project threatens cultural and sacred sites.[176] They have also expressed concerns that development of the project will create risks to indigenous women, because resource extraction is linked to missing and murdered Indigenous women.[177] Protestors have been occupying the site of the proposed mine since January 2021.[178][167]

Applications

[edit]
Pie chart of how much lithium was used and in what way globally in 2020[179]

Batteries

[edit]

In 2021, most lithium is used to make lithium-ion batteries for electric cars and mobile devices.

Ceramics and glass

[edit]

Lithium oxide is widely used as a flux for processing silica, reducing the melting point and viscosity of the material and leading to glazes with improved physical properties including low coefficients of thermal expansion. Worldwide, this is one of the largest use for lithium compounds.[180][181] Glazes containing lithium oxides are used for ovenware. Lithium carbonate (Li2CO3) is generally used in this application because it converts to the oxide upon heating.[182]

Electrical and electronic

[edit]

Late in the 20th century, lithium became an important component of battery electrolytes and electrodes, because of its high electrode potential. Because of its low atomic mass, it has a high charge- and power-to-weight ratio. A typical lithium-ion battery can generate approximately 3 volts per cell, compared with 2.1 volts for lead-acid and 1.5 volts for zinc-carbon. Lithium-ion batteries, which are rechargeable and have a high energy density, differ from lithium metal batteries, which are disposable (primary) batteries with lithium or its compounds as the anode.[183][184] Other rechargeable batteries that use lithium include the lithium-ion polymer battery, lithium iron phosphate battery, and the nanowire battery.[185]

Over the years opinions have been differing about potential growth. A 2008 study concluded that "realistically achievable lithium carbonate production would be sufficient for only a small fraction of future PHEV and EV global market requirements", that "demand from the portable electronics sector will absorb much of the planned production increases in the next decade", and that "mass production of lithium carbonate is not environmentally sound, it will cause irreparable ecological damage to ecosystems that should be protected and that LiIon propulsion is incompatible with the notion of the 'Green Car'".[59]

Lubricating greases

[edit]

The third most common use of lithium is in greases. Lithium hydroxide is a strong base, and when heated with a fat, it produces a soap, such as lithium stearate from stearic acid. Lithium soap has the ability to thicken oils, and it is used to manufacture all-purpose, high-temperature lubricating greases.[22][186][187]

Metallurgy

[edit]

Lithium (e.g. as lithium carbonate) is used as an additive to continuous casting mould flux slags where it increases fluidity,[188][189] a use which accounts for 5% of global lithium use (2011).[58] Lithium compounds are also used as additives (fluxes) to foundry sand for iron casting to reduce veining.[190]

Lithium (as lithium fluoride) is used as an additive to aluminium smelters (Hall–Héroult process), reducing melting temperature and increasing electrical resistance,[191] a use which accounts for 3% of production (2011).[58]

When used as a flux for welding or soldering, metallic lithium promotes the fusing of metals during the process[192] and eliminates the formation of oxides by absorbing impurities.[193] Alloys of the metal with aluminium, cadmium, copper and manganese are used to make high-performance, low density aircraft parts (see also Lithium-aluminium alloys).[194]

Silicon nano-welding

[edit]

Lithium has been found effective in assisting the perfection of silicon nano-welds in electronic components for electric batteries and other devices.[195]

Lithium is used in flares and pyrotechnics is due to its rose-red flame.[196]

Pyrotechnics

[edit]

Lithium compounds are used as pyrotechnic colorants and oxidizers in red fireworks and flares.[22][197]

Air purification

[edit]

Lithium chloride and lithium bromide are hygroscopic and are used as desiccants for gas streams.[22] Lithium hydroxide and lithium peroxide are the salts most commonly used in confined areas, such as aboard spacecraft and submarines, for carbon dioxide removal and air purification. Lithium hydroxide absorbs carbon dioxide from the air by forming lithium carbonate, and is preferred over other alkaline hydroxides for its low weight.

Lithium peroxide (Li2O2) in presence of moisture not only reacts with carbon dioxide to form lithium carbonate, but also releases oxygen.[198][199] The reaction is as follows:

2 Li2O2 + 2 CO2 → 2 Li2CO3 + O2

Some of the aforementioned compounds, as well as lithium perchlorate, are used in oxygen candles that supply submarines with oxygen. These can also include small amounts of boron, magnesium, aluminium, silicon, titanium, manganese, and iron.[200]

Optics

[edit]

Lithium fluoride, artificially grown as crystal, is clear and transparent and often used in specialist optics for IR, UV and VUV (vacuum UV) applications. It has one of the lowest refractive indices and the furthest transmission range in the deep UV of most common materials.[201] Finely divided lithium fluoride powder has been used for thermoluminescent radiation dosimetry (TLD): when a sample of such is exposed to radiation, it accumulates crystal defects which, when heated, resolve via a release of bluish light whose intensity is proportional to the absorbed dose, thus allowing this to be quantified.[202] Lithium fluoride is sometimes used in focal lenses of telescopes.[22][203]

The high non-linearity of lithium niobate also makes it useful in non-linear optics applications. It is used extensively in telecommunication products such as mobile phones and optical modulators, for such components as resonant crystals. Lithium applications are used in more than 60% of mobile phones.[204]

Organic and polymer chemistry

[edit]

Organolithium compounds are widely used in the production of polymer and fine-chemicals. In the polymer industry, which is the dominant consumer of these reagents, alkyl lithium compounds are catalysts/initiators[205] in anionic polymerization of unfunctionalized olefins.[206][207][208] For the production of fine chemicals, organolithium compounds function as strong bases and as reagents for the formation of carbon-carbon bonds. Organolithium compounds are prepared from lithium metal and alkyl halides.[209]

Many other lithium compounds are used as reagents to prepare organic compounds. Some popular compounds include lithium aluminium hydride (LiAlH4), lithium triethylborohydride, n-butyllithium and tert-butyllithium.

The launch of a torpedo using lithium as fuel

Military

[edit]

Metallic lithium and its complex hydrides, such as lithium aluminium hydride (LiAlH4), are used as high-energy additives to rocket propellants.[40] LiAlH4 can also be used by itself as a solid fuel.[210]

The Mark 50 torpedo stored chemical energy propulsion system (SCEPS) uses a small tank of sulfur hexafluoride, which is sprayed over a block of solid lithium. The reaction generates heat, creating steam to propel the torpedo in a closed Rankine cycle.[211]

Lithium hydride containing lithium-6 is used in thermonuclear weapons, where it serves as fuel for the fusion stage of the bomb.[212]

Nuclear

[edit]

Lithium-6 is valued as a source material for tritium production and as a neutron absorber in nuclear fusion. Natural lithium contains about 7.5% lithium-6 from which large amounts of lithium-6 have been produced by isotope separation for use in nuclear weapons.[213] Lithium-7 gained interest for use in nuclear reactor coolants.[214]

Lithium deuteride was used as fuel in the Castle Bravo nuclear device.

Lithium deuteride was the fusion fuel of choice in early versions of the hydrogen bomb. When bombarded by neutrons, both 6Li and 7Li produce tritium — this reaction, which was not fully understood when hydrogen bombs were first tested, was responsible for the runaway yield of the Castle Bravo nuclear test. Tritium fuses with deuterium in a fusion reaction that is relatively easy to achieve. Although details remain secret, lithium-6 deuteride apparently still plays a role in modern nuclear weapons as a fusion material.[215]

Lithium fluoride, when highly enriched in the lithium-7 isotope, forms the basic constituent of the fluoride salt mixture LiF-BeF2 used in liquid fluoride nuclear reactors. Lithium fluoride is exceptionally chemically stable and LiF-BeF2 mixtures have low melting points. In addition, 7Li, Be, and F are among the few nuclides with low enough thermal neutron capture cross-sections not to poison the fission reactions inside a nuclear fission reactor.[note 4][216]

In conceptualized (hypothetical) nuclear fusion power plants, lithium will be used to produce tritium in magnetically confined reactors using deuterium and tritium as the fuel. Naturally occurring tritium is extremely rare and must be synthetically produced by surrounding the reacting plasma with a 'blanket' containing lithium, where neutrons from the deuterium-tritium reaction in the plasma will fission the lithium to produce more tritium:

6Li + n → 4He + 3H.

Lithium is also used as a source for alpha particles, or helium nuclei. When 7Li is bombarded by accelerated protons 8Be is formed, which almost immediately undergoes fission to form two alpha particles. This feat, called "splitting the atom" at the time, was the first fully human-made nuclear reaction. It was produced by Cockroft and Walton in 1932.[217][218] Injection of lithium powders is used in fusion reactors to manipulate plasma-material interactions and dissipate energy in the hot thermo-nuclear fusion plasma boundary.[219][220]

In 2013, the US Government Accountability Office said a shortage of lithium-7 critical to the operation of 65 out of 100 American nuclear reactors "places their ability to continue to provide electricity at some risk." The problem stems from the decline of US nuclear infrastructure. The equipment needed to separate lithium-6 from lithium-7 is mostly a cold war leftover. The US shut down most of this machinery in 1963, when it had a huge surplus of separated lithium, mostly consumed during the twentieth century. The report said it would take five years and $10 million to $12 million to reestablish the ability to separate lithium-6 from lithium-7.[221]

Reactors that use lithium-7 heat water under high pressure and transfer heat through heat exchangers that are prone to corrosion. The reactors use lithium to counteract the corrosive effects of boric acid, which is added to the water to absorb excess neutrons.[221]

Medicine

[edit]

Lithium is useful in the treatment of bipolar disorder.[222] Lithium salts may also be helpful for related diagnoses, such as schizoaffective disorder and cyclic major depressive disorder. The active part of these salts is the lithium ion Li+.[222] Lithium may increase the risk of developing Ebstein's cardiac anomaly in infants born to women who take lithium during the first trimester of pregnancy.[223]

Precautions

[edit]
Lithium
Hazards
GHS labelling:
GHS02: FlammableGHS05: Corrosive
Danger
H260, H314
P223, P231+P232, P280, P305+P351+P338, P370+P378, P422[224]
NFPA 704 (fire diamond)

Lithium metal is corrosive and requires special handling to avoid skin contact. Breathing lithium dust or lithium compounds (which are often alkaline) initially irritate the nose and throat, while higher exposure can cause a buildup of fluid in the lungs, leading to pulmonary edema. The metal itself is a handling hazard because contact with moisture produces the caustic lithium hydroxide. Lithium metal is safely stored in non-reactive compounds such as naphtha.[226]

See also

[edit]

Notes

[edit]

References

[edit]
[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Lithium is a chemical element with the symbol Li and atomic number 3, classified as a soft, silvery-white under standard conditions. It possesses the lowest density of any solid element at approximately 0.534 g/cm³ and exhibits high reactivity, particularly with water, producing hydrogen gas and lithium hydroxide. Discovered in 1817 by Swedish chemist Johan August Arfwedson during analysis of the mineral petalite, lithium was first isolated in its metallic form in 1821. As one of the few elements synthesized in significant quantities during the , lithium is primordial, yet its observed abundance in old stars falls short of theoretical predictions, a discrepancy known as the . On Earth, it ranks as the 33rd most abundant element in the crust at about 20 parts per million, primarily occurring in minerals like and in brines. Lithium's primary industrial application, accounting for roughly 87% of global consumption, lies in rechargeable lithium-ion batteries essential for electric vehicles, portable electronics, and grid storage due to its high and low . Secondary uses include ceramics and (5%), lubricating greases (2%), and continuous casting of aluminum and magnesium alloys, while in , lithium salts such as serve as a mainstay treatment for by modulating activity. Extraction predominantly from hard-rock mining and evaporative brine operations has raised concerns over water usage and ecosystem disruption in arid regions like South America's , prompting debates on sustainable sourcing amid surging demand.

Physical and Chemical Properties

Atomic and Physical Characteristics

Lithium possesses 3 and Li, positioning it as the first element in group 1 (alkali metals) and period 2 of the periodic table. Its ground-state is [He] 2s¹, consisting of a core with a single in the 2s orbital, which accounts for its chemical reactivity akin to other alkali metals. It exhibits an electronegativity of 0.98 on the Pauling scale and primarily adopts the +1 oxidation state. The first measures 520.2 kJ/mol, the lowest among metals, facilitating easy loss of the to form Li⁺ ions. Elemental lithium manifests as a soft, silvery-white metal at standard conditions, characterized by high and malleability sufficient to be cut with a . It exhibits the lowest among metals at 0.534 g/cm³ near , enabling it to float on despite rapid reaction with it to produce gas and . The stands at 180.5 °C and the at 1342 °C, reflecting relatively weak due to the large and single . Lithium adopts a body-centered cubic at , with a lattice parameter of approximately 350.9 pm, contributing to its low hardness ( 0.6). Key physical properties include moderate thermal conductivity of about 85 W/(m·K) at 300 K and electrical conductivity of 1.1 × 10⁷ S/m, corresponding to a resistivity of 9.4 × 10⁻⁸ Ω·m, values typical for alkali metals but lower than those of transition metals due to fewer free electrons per atom. The empirical atomic radius is 152 pm, while the metallic radius approximates 155 pm, larger than expected for its position owing to poor shielding by the 1s electrons and resulting electron repulsion.
PropertyValueSource Unit
Density (20 °C)0.534 g/cm³
Melting point180.5 °C°C
Boiling point1342 °C°C
Thermal conductivity (300 K)~85 W/(m·K)
Electrical resistivity (20 °C)9.4 × 10⁻⁸ Ω·mΩ·m
These characteristics stem from lithium's position as the least dense and smallest , with bonding dominated by delocalized s-electrons leading to high reactivity and low cohesion.

Isotopes and Nuclear Properties

Lithium, with 3, possesses two stable isotopes: ⁶Li and ⁷Li. The natural isotopic composition consists of approximately 7.5% ⁶Li and 92.5% ⁷Li, yielding a of 6.94 for terrestrial lithium samples. These abundances vary slightly in different geological reservoirs due to processes, but the terrestrial average remains dominated by ⁷Li. ⁶Li has a nuclear spin of 1⁺ and is notable for its high thermal capture cross-section of about 940 barns, facilitating the reaction ⁶Li + n → ⁴He + ³H ( production) with near-100% yield, which underpins applications in thermonuclear weapons and fusion reactor breeding blankets. In contrast, ⁷Li exhibits a nuclear spin of 3/2⁻ and a much lower absorption cross-section (approximately 0.045 barns), making it suitable for pH regulation in (PWR) coolants without significant neutron interference; enriched ⁷Li (depleted in ⁶Li) is specifically used to avoid parasitic generation. Lithium also features several radioactive isotopes, ranging from ³Li to ¹²Li, all of which are short-lived. The longest-lived among them is ⁸Li, with a of 838 milliseconds, decaying primarily via β⁻ emission to ⁸Be (which subsequently alpha-decays). Shorter-lived isotopes include ⁹Li (half-life 178 ms, β⁻ decay) and ¹⁰Li (half-life ~2 μs, ), while the least stable, ⁴Li, undergoes with a half-life of about 7.6 × 10⁻²³ seconds. These isotopes arise in nuclear reactions but have negligible natural occurrence or persistence due to rapid decay.

Occurrence and Distribution

Astronomical and Cosmic Occurrence

Lithium, primarily the isotope ^7Li, originated as a primordial element produced during (BBN) approximately 10-20 seconds after the , when the universe temperature was around 10^9 K, allowing fusion of protons and neutrons into light nuclei. Standard BBN models predict a primordial ^7Li abundance relative to of approximately (4-5) × 10^{-10}, based on baryon-to-photon ratio from measurements. However, spectroscopic observations of lithium in metal-poor halo stars, considered proxies for primordial abundance, yield values around (1-2) × 10^{-10}, presenting the "" unresolved by standard and extensions. In stellar environments, lithium is fragile, destroyed at temperatures above 2.5 × 10^6 K via proton capture reactions like ^7Li(p,α)^4He, leading to depletion in convective zones of main-sequence stars similar to the Sun. Population II stars in the galactic halo retain higher lithium from early cosmic gas, while Population I disk stars show further depletion and enrichment from later galactic evolution. Galactic lithium enrichment occurs primarily through classical novae, recurrent thermonuclear explosions on white dwarfs accreting hydrogen-rich material, producing ^7Li via the Cameron-Fowler mechanism at temperatures of 10^8-10^9 K. Novae contribute significantly, with models estimating they account for much of the observed interstellar medium (ISM) lithium, as ^6Li/^7Li ratios in novae ejecta match galactic observations. Additional cosmic sources include (AGB) stars, where lithium forms via the ^3He(α,γ)^7Be → ^7Li decay in hot bottom burning, and on heavier nuclei in the ISM, producing both ^6Li and ^7Li. Observations of lithium in diffuse ISM clouds, such as toward ζ Persei, reveal abundances consistent with inputs rather than pure primordial gas, with ^7Li/^6Li ratios indicating fresh production. In extragalactic contexts, lithium detections in dwarf galaxies like the show abundances below BBN predictions, suggesting universal depletion mechanisms or alternative production histories. Cosmic rays, accelerated particles interacting with the , contribute to lithium via and fusion reactions, but their role is secondary to novae for ^7Li, as evidenced by isotopic ratios in meteorites and tracing galactic . Overall, while BBN sets the baseline, astrophysical processes dominate the observed cosmic distribution, with lithium abundances varying by factors of 10-100 across stellar populations and ISM phases due to destruction in and episodic enrichment events.

Terrestrial Reserves and Sources

Lithium occurs in the at an average concentration of approximately 20 parts per million, primarily dispersed in , but economic extraction relies on concentrated deposits formed through igneous and evaporitic processes. The element is sourced mainly from two types of deposits: hard-rock pegmatites rich in minerals such as (LiAlSi₂O₆), (K(Li,Al)₃(Al,Si,Rb)₄O₁₀(F,OH)₂), and (LiAlSi₄O₁₀), and lithium-enriched brines in closed-basin salt flats or salars. Hard-rock sources originate from late-stage crystallization in granitic pegmatites, while brines result from the leaching of lithium from surrounding rocks into , followed by in arid environments. Hard-rock deposits dominate current production, with hosting the largest operations, including the , which produced over 1.4 million tons of concentrate in 2023. Other significant hard-rock sites include the Bikita mine in and emerging projects in and , where resources are estimated at 3.2 million tons of equivalent. These deposits require , crushing, and roasting or acid leaching to extract lithium, with global hard-rock resources comprising about 42% of identified totals. Brine deposits, concentrated in the of —encompassing , , and —account for the majority of undeveloped resources, estimated at over 50% of global totals. Key sites include in , which supplies brine-derived lithium for about 40% of world production via solar and precipitation; in , holding 23 million tons of lithium resources but limited by technological and infrastructural challenges; and Argentina's Salar del Hombre Muerto and others, where direct lithium extraction methods are increasingly piloted to reduce times. Brine extraction involves pumping hypersaline water into ponds for concentration, followed by chemical processing, though it raises concerns over water usage in arid regions. Global lithium reserves, defined as economically extractable portions of identified resources, totaled 28 million metric tons of contained lithium as of per U.S. Geological Survey estimates, with resources exceeding 98 million tons including sub-economic and undiscovered amounts. holds the largest reserves at 9.3 million tons, followed by at 6.2 million tons and at 3.6 million tons; Bolivia's 21 million tons in resources remain largely unclassified as reserves due to extraction difficulties. Emerging sources include sedimentary clays like those at in the U.S. and lithium-in-brine from oilfields, such as the in , where a USGS study identified 5 to 19 million tons of potential lithium using analysis of geophysical data.
CountryReserves (million metric tons Li)Primary Source Type
9.3
6.2
3.6
3.0/
1.0/

Biological Roles and Trace Elements

Lithium occurs in trace concentrations within biological systems, typically at levels of 0.1–1 mg/kg in mammalian tissues, with higher accumulation in marine organisms compared to terrestrial ones due to its presence in . In humans, dietary intake averages 0.2–0.6 mg per day from sources such as grains, , and , though this varies by lithium content and regional . Experimental deprivation studies in animals, including rats and , have demonstrated physiological effects such as reduced , impaired growth, and altered activity upon lithium removal from diets, suggesting a potential role at micro-doses. However, these findings do not establish specific deficiency syndromes akin to those for confirmed essential trace elements like or iodine. Lithium is not classified as an essential for humans or higher mammals by standard nutritional criteria, which require demonstrable biochemical functions and overt deficiency symptoms upon deprivation. Proponents of its status cite epidemiological correlations, such as lower rates in populations with higher environmental lithium exposure (e.g., 0.1–0.3 mg/L in ), and its modulation of glycogen synthase kinase-3 (GSK-3), an involved in cellular signaling, , and folate/B12 transport. At physiological concentrations (below 0.1 mM), lithium may enhance DNA replication fidelity and influence activity, potentially contributing to and cognitive preservation, as evidenced by lithium dynamics in aging models. Critics argue these effects are pharmacological rather than nutritional, with no validated recommended daily allowance, and note that lithium's biochemical of magnesium complicates causal attribution. Public and scholarly debate continues about the significance of trace lithium intake for brain health. Some trade-audience books (e.g., Michael Nehls, 2025) argue for a stronger nutritional framing; these views are not a scientific consensus. In non-mammalian organisms, lithium's roles remain unclear; plants exhibit no essentiality, showing toxicity above 10–50 μM, while some and tolerate or bioaccumulate it without defined functions. thresholds in vertebrates occur at serum levels exceeding 1.5 mM, leading to renal, , and neurological impairments, underscoring a narrow therapeutic window that challenges its routine classification as beneficial beyond trace exposure. Ongoing research emphasizes dose-dependent duality: beneficial at ultra-trace levels (e.g., 1 mg/day provisional estimate) for , versus adverse at higher intakes.

Historical Development

Discovery and Early Isolation

Lithium was discovered in 1817 by Swedish chemist Johan August Arfwedson while analyzing samples of the mineral , LiAl(Si₂O₅)₂, obtained from a mine on the island of Utö in . Arfwedson, working in the laboratory of , observed that the atomic weight calculations for petalite and the related mineral did not match known alkali metals like sodium or , leading him to infer the presence of a new element. He isolated its compounds, such as , and named the element "lithium" from word lithos (stone), reflecting its occurrence in minerals rather than plant ashes like other alkalis. Berzelius independently confirmed Arfwedson's findings by detecting lithium in additional minerals including and confirmed its chemical similarity to sodium and through precipitation reactions. Early identification of lithium relied on its distinctive crimson-red coloration when subjected to a blowpipe test, a qualitative method that distinguished it from other elements. Despite these advances, Arfwedson and Berzelius were unable to isolate the pure metal, as chemical reduction methods failed due to lithium's strong affinity for oxygen. The elemental metal was first isolated in impure form in 1821 by William Thomas through of , though yields were minimal and contaminated. Pure lithium metal was not obtained until 1855, when and Augustus Matthiessen in successfully electrolyzed a molten of and , producing sufficient quantities for physical and chemical characterization. This electrolytic process exploited the lower of lithium relative to , allowing selective deposition. These early isolations established lithium as the lightest solid element, with a of 0.534 g/cm³, and highlighted its high reactivity, necessitating inert handling.

Industrial and Scientific Advancements

In the early , lithium compounds were incorporated into ceramics and glass production to enhance resistance and lower melting temperatures, enabling the manufacture of durable enamels and specialty glasses used in industrial applications. By 1935, these uses were documented in U.S. Bureau of Mines reports, reflecting growing recognition of lithium's fluxing properties in metallurgical and glazing processes. The soft drink 7Up was originally marketed as “Bib-Label Lithiated Lemon-Lime Soda” and contained lithium citrate until 1948. A pivotal industrial innovation arrived in 1942 with Clarence Earle's patent for lithium soap-based greases (U.S. Patent 2,274,675), which demonstrated superior stability and load-bearing capacity at elevated temperatures compared to sodium or calcium alternatives, revolutionizing for automotive and machinery components during and postwar expansion. Lithium hydroxystearate greases, refined in subsequent decades, became the dominant type by the , comprising over 50% of the global grease market due to their versatility in multipurpose applications. On the scientific front, lithium enabled groundbreaking nuclear research in 1932 when and bombarded lithium-7 with protons in the first fully artificial , producing two nuclei and confirming quantum tunneling predictions, for which they received the 1951 . This experiment laid foundational principles for particle acceleration and fusion studies. Post-World War II, lithium's isotopes proved critical in thermonuclear weapons; lithium deuteride served as a fusion fuel in staged fission-fusion devices, as demonstrated by the 1954 test, which yielded 15 megatons—over 1,000 times the bomb—highlighting lithium-6's role in tritium production despite unintended lithium-7 contributions. Advancements in accelerated in the amid energy crises, with Stanley Whittingham's development of intercalation cathodes enabling prototype rechargeable lithium batteries based on , though early versions suffered from instability. John Goodenough's 1980 invention of the cathode marked a key milestone, providing higher voltage and capacity, paving the way for commercial lithium-ion batteries introduced by in 1991, which transformed portable electronics with energy densities exceeding 100 Wh/kg. These batteries stemmed from non-aqueous research dating to the late 1960s, prioritizing lithium's high over traditional lead-acid systems.

Chemical Behavior and Compounds

Properties of Elemental Lithium

Elemental lithium is a soft, silvery-white , the lightest solid element, with a of 0.534 g/cm³ at 20 °C. It exhibits a low of 180.5 °C and a of 1342 °C, allowing it to remain solid under standard conditions but liquefy at relatively modest temperatures. In its pure form, lithium adopts a body-centered cubic , contributing to its ductility and malleability despite its low . Lithium demonstrates good electrical conductivity as a metal, with an electrical resistivity of approximately 9.4 × 10⁻⁸ Ω·m at 20 °C and conductivity around 1.1 × 10⁷ S/m. Its thermal properties include moderate conductivity, though specific values vary with temperature; the metal's low and delocalized electrons enable efficient akin to other alkali metals. Mechanically, lithium is highly soft, with a Mohs of 0.6, allowing it to be cut with a knife and deformed easily under pressure. Chemically, elemental lithium is highly reactive due to its low and strong reducing nature. It tarnishes rapidly in moist air, reacting with oxygen to form (Li₂O) and with nitrogen to produce (Li₃N), which forms a protective but imperfect passivation layer. Upon contact with , lithium undergoes a vigorous but less explosive reaction than sodium or , producing and gas via 2Li + 2H₂O → 2LiOH + H₂, accompanied by fizzing and heat evolution sufficient to ignite the hydrogen under certain conditions. This reactivity necessitates storage under inert atmospheres or oils to prevent oxidation or . Due to its flammability and reactivity, elemental lithium poses significant handling hazards; it ignites spontaneously in air above its and reacts exothermically with many substances, earning classifications such as flammable solid under GHS and high ratings on the scale for flammability and reactivity. Pure lithium metal is typically handled in glove boxes or under to mitigate risks of or from trace moisture.

Inorganic Lithium Compounds

Lithium forms a variety of inorganic compounds, predominantly ionic salts due to its +1 oxidation state and high charge density, which imparts polarizing effects leading to deviations from typical alkali metal behavior, such as the thermal decomposition of lithium carbonate unlike more stable heavier analogs. These compounds are synthesized via precipitation from lithium salts, thermal decomposition, or direct reaction of lithium metal with acids or oxides, with industrial production often starting from brine-derived lithium chloride. Lithium carbonate (Li₂CO₃), a white crystalline powder with low solubility (approximately 1.3 g/100 mL at 20°C), decomposes at 723°C to and , reflecting its relative instability compared to sodium or carbonates. It is produced commercially by reacting with or via carbonation of from processing. Key applications include serving as a flux in and to reduce temperatures and , and as a primary precursor for battery-grade materials in lithium-ion cathodes, where purity exceeds 99.5% for technical grades. Medical formulations also employ it for mood stabilization, though this falls under pharmacological uses. Lithium hydroxide (LiOH), typically handled as the monohydrate, is a strong base with high water solubility (12.8 g/100 mL at 20°C) and a melting point of 462°C for the anhydrous form, making it hygroscopic and reactive with CO₂ to form lithium carbonate. Synthesis involves electrolysis of lithium chloride or reaction of lithium carbonate with lime (Ca(OH)₂). It is preferred over carbonate in lithium-ion batteries for high-nickel cathode precursors due to direct incorporation without decarboxylation, comprising over 60% of battery cathode material by weight in nickel-manganese-cobalt formulations. Additional uses include CO₂ scrubbing in submarines and spacecraft via the reaction 2LiOH + CO₂ → Li₂CO₃ + H₂O, and as a thickener in high-temperature lithium greases resistant to water washout. Lithium chloride (LiCl), a , deliquescent solid with 2.068 g/cm³, 605–614°C, and 1382°C, exhibits high in polar solvents (83.05 g/100 mL in at 20°C) and is corrosive in due to its ionic dissociation. It is prepared by neutralizing or carbonate with , or directly from brines. Applications leverage its hygroscopic nature as a in and drying processes, as a flux in and to lower , and in electrolytes for lithium metal production via . It also acts as a catalyst in for reactions like Grignard-type couplings. Lithium oxide (Li₂O), an antit fluorite-structured white powder with 1438°C, forms via direct of lithium metal in oxygen or of / at high temperatures, and sublimes under vacuum to facilitate vapor-phase reactions. It reacts vigorously with to yield (Li₂O + H₂O → 2LiOH) and absorbs CO₂ to form , enabling use in fluxes for control and in components for ionic conductivity. Its high reactivity with metals like at elevated temperatures limits handling in certain alloys. Other notable compounds include (LiF), sparingly soluble with high (845°C), used in pressurized water reactors for control and inhibition via isotopic enrichment in lithium-7 to minimize . These materials generally pose handling risks due to corrosivity and moisture sensitivity, requiring inert atmospheres for storage.
CompoundFormulaMelting Point (°C)Solubility in Water (g/100 mL at 20°C)Primary Industrial Use
Lithium carbonateLi₂CO₃Decomposes at 7231.3Battery precursors, glass flux
Lithium hydroxideLiOH462 (anhydrous)12.8Battery cathodes, CO₂ absorbents
Lithium chlorideLiCl605–61483.05Desiccants, electrolytic fluxes
Lithium oxideLi₂O1438Insoluble (reacts) glazes, CO₂ sorbents

Organic Lithium Chemistry

Organolithium compounds, denoted as RLi where R is an alkyl, aryl, or other organic group, feature a direct carbon-lithium with significant ionic character due to lithium's low . These are among the strongest nucleophiles and bases available in , enabling reactions unattainable with milder organometallics like Grignard reagents. Their development began in , with key contributions from researchers advancing air- and moisture-sensitive handling techniques. Preparation typically involves the reaction of lithium metal with organic halides in an inert solvent such as or , following the general 2Li + RX → RLi + LiX. Commercial production often employs lithium dispersions to enhance reaction rates and yields, particularly for alkyllithiums like . Alternative routes include metal-halogen exchange or with stronger bases, though the direct metallation remains predominant for simple alkyl derivatives. In solution and state, organolithium exhibit oligomeric structures dominated by three-center, two-electron Li-C-Li bridging bonds, leading to aggregation such as tetramers for or hexamers for butyllithium. Aggregation state influences reactivity; monomeric species, stabilized by donor solvents or , display enhanced nucleophilicity compared to clustered forms. These compounds are highly sensitive to air and moisture, igniting spontaneously upon exposure due to rapid exothermic reactions with oxygen or . Reactivity stems from the polarized C-Li bond, facilitating to carbonyls, conjugate additions, and formation of new C-C bonds, often with higher yields than organomagnesium counterparts. As strong bases, they enable directed ortho-metalation for aryl systems and of weak acids, pivotal in synthesizing complex pharmaceuticals and materials. In , alkyllithiums initiate anionic polymerization of dienes and styrenes, yielding controlled stereoregular rubbers like . Functionalized variants, such as those with coordinating groups, allow selective transfers in . Handling requires strict inert atmosphere conditions, using Schlenk techniques or gloveboxes, with personal protective equipment including flame-resistant clothing and goggles to mitigate corrosivity and flammability risks. Quenching procedures involve slow addition to aqueous solvents under nitrogen, followed by extraction, to prevent violent exotherms. Commercial solutions in hydrocarbons are stabilized but remain pyrophoric if concentrated or exposed.

Production Processes

Global Reserves and Resource Assessment

Global lithium reserves, defined by the U.S. Geological Survey (USGS) as lithium content that is economically extractable using current technology and prices, total 30 million metric tons. In contrast, measured and indicated resources, which encompass concentrations not yet proven economically viable but potentially recoverable with future advancements, amount to 115 million metric tons. These assessments, updated annually, reflect identified deposits and are subject to revision based on exploration, technological progress, and market conditions; for instance, the 2025 USGS report revised reserve estimates for , , , the , and using company and government data. The distribution of reserves is concentrated among a few nations, with holding the largest share at 9.3 million metric tons, followed by at 7 million metric tons. possesses 4 million metric tons, 3 million metric tons, the 1.8 million metric tons, and 1.2 million metric tons, with remaining reserves distributed across other countries. Resources show greater concentration in the "" of , where and each hold 23 million metric tons, and 11 million metric tons, primarily in deposits within salt flats. 's resources stand at 8.9 million metric tons, largely from hard-rock pegmatites, while 's are estimated at 6.8 million metric tons. Lithium occurs in diverse geological settings, including continental brines (dominant in ), pegmatite ores (prevalent in and ), and clay deposits (emerging in regions like the and ), each influencing extraction feasibility and reserve classification. resources, while abundant, often face delays in commercialization due to process timelines and environmental factors, whereas hard-rock enables faster scaling but higher energy costs. Overall, current reserves support projected demand growth for decades, assuming no major disruptions, though expanding resources through could mitigate long-term supply risks.
CountryReserves (million metric tons Li)
Chile9.3
Australia7.0
Argentina4.0
China3.0
United States1.8
Canada1.2
Table of major lithium reserves by country, 2025 USGS estimates. Total world reserves: 30 million metric tons.

Extraction Methods from Brines and Ores

Lithium extraction from brines primarily occurs in arid regions like the in , where subsurface salt flats contain concentrated solutions. The conventional method involves pumping into large evaporation ponds, where solar energy evaporates water over 12 to 36 months, progressively concentrating lithium while precipitating impurities such as and . Once lithium reaches sufficient concentration, typically around 6 grams per liter, soda ash () is added to precipitate , which is then filtered, washed, and calcined to battery-grade purity with recovery rates of 50-70%. This process dominates global supply, accounting for over 60% of production from sites like Chile's . Emerging direct lithium extraction (DLE) technologies address evaporation's limitations, including long timelines and water loss, by using adsorbents, ion-exchange resins, or membranes to selectively capture lithium ions from in hours to days, achieving up to 90% recovery before reinjecting depleted . Adsorption with or titanium-based sorbents, followed by with dilute acid, and extraction with organic phases are key variants, though scaling challenges persist due to material durability and impurity co-extraction. Pilot projects in and the demonstrate DLE's potential for lower environmental impact, but as of 2024, it represents less than 1% of commercial output. Hard-rock lithium extraction targets ores, chiefly (LiAlSi2O6), mined via open-pit methods in and emerging African deposits. Ore is crushed, milled to liberate minerals, and concentrated via dense media separation or flotation to 5-6% Li2O grade. The concentrate undergoes thermal treatment at 1,000-1,100°C to convert stable α-spodumene to reactive β-phase, followed by roasting at 240-260°C, converting lithium to water-soluble . Subsequent hot water leaching yields a lithium solution (95-98% recovery), purified via or to remove iron, aluminum, and silica, then processed into or . Alternative ore methods include alkaline roasting with or to avoid strong acids, reducing emissions but requiring higher temperatures, and innovative approaches like flash , which in lab tests extracts 90% lithium from in seconds without acids or roasting. Hard-rock processing consumes more energy than brines—up to 3.5 times higher per ton of lithium carbonate equivalent—but supports faster scaling in geologically diverse regions.

Refining and Processing Techniques

Lithium refining and processing convert raw extracts from brines or ores into commercial products such as lithium carbonate (Li₂CO₃) or lithium hydroxide (LiOH), typically achieving battery-grade purity exceeding 99.5%. These techniques prioritize impurity removal, including sodium, potassium, magnesium, calcium, and boron, through methods like precipitation, ion exchange, and solvent extraction. Brine sources dominate, accounting for approximately 60-70% of global lithium production as of 2023, while hard-rock ores like spodumene contribute the remainder, with processing pathways differing fundamentally due to feedstock chemistry. For brine-based processing, traditional solar evaporation pumps lithium-rich salars into shallow ponds, where solar heat and wind concentrate the solution over 12-18 months, sequentially precipitating impurities like halite and gypsum before lithium enrichment to 4-6% LiCl. The resulting liquor undergoes soda ash (Na₂CO₃) addition at 90-100°C to precipitate Li₂CO₃, followed by filtration, washing, and calcination for purity; recovery rates hover around 50-60%, with significant water loss and land use drawbacks in arid regions. Emerging direct lithium extraction (DLE) bypasses evaporation by selectively adsorbing lithium ions using manganese or titanium-based sorbents, ion-exchange resins, or solvent systems in column or membrane setups, achieving 80-95% recovery in hours to days while reinjecting depleted brine to minimize environmental disruption. DLE elutes lithium as LiCl, which is then converted to hydroxide via lime precipitation or to carbonate, though commercial scaling remains limited by sorbent durability, selectivity against magnesium, and operational costs, with pilot projects demonstrating viability but full plants operational only since 2023 in select sites. Hard-rock refining begins with ore beneficiation via crushing, grinding, and flotation to yield 5-6% Li₂O concentrates from (LiAlSi₂O₆), which is then calcined at 1000-1100°C to form reactive β-spodumene. leaching at 200-250°C solubilizes lithium as Li₂SO₄, followed by impurity removal through of , for calcium and sodium, and ; the purified sulfate solution reacts with NaOH for LiOH or Na₂CO₃ for Li₂CO₃ . This acid-roasting method yields 80-90% recovery but consumes substantial energy (up to 20 GJ/tonne Li₂CO₃ equivalent) and reagents, contrasting with brine processes' lower thermal demands. Alternative alkaline roasting with Na₂CO₃ at 800-900°C has been piloted for reduced emissions, though it generates more waste. Post-extraction purification universally employs multi-stage filtration, carbonation, and recrystallization, often with chelating agents or nanofiltration to meet stringent trace metal limits for battery cathodes. Recycling from spent batteries integrates hydrometallurgical leaching similar to ore processing, recovering 90%+ lithium via treatment, though it represents under 5% of supply as of 2024 due to collection challenges.

Supply Chain Dynamics and Geopolitics

The lithium supply chain begins with extraction primarily from hard-rock spodumene in Australia and brine evaporation in the Lithium Triangle of Argentina, Bolivia, and Chile, which together account for over 60% of global production capacity. In 2024, Australia produced 88,000 metric tons of lithium, representing 48% of the world's total output of approximately 240,000 metric tons, followed by Chile at 49,000 metric tons (24%) and Argentina at 18,000 metric tons. China contributed 41,000 metric tons (18%), but its role extends far beyond mining to dominate downstream processing. This geographic concentration creates vulnerabilities, as raw lithium from Australia and South America is largely shipped to China for conversion into battery-grade chemicals like lithium carbonate and hydroxide. Refining represents a critical bottleneck, with controlling 65% to 72% of global lithium refining capacity as of 2022-2024, despite holding only about 8% of reserves. Chinese firms have expanded influence by investing in overseas mines, such as in and , securing feedstock while maintaining processing hegemony. This dominance exposes Western economies to risks from Chinese export policies, including recent controls on lithium batteries and related technologies imposed in 2025, amid escalating U.S.-China tensions over critical minerals. Geopolitically, lithium's centrality to batteries and has elevated it to a strategic asset, with lithium recognized as a critical mineral essential for lithium-ion batteries in the energy transition, national security, and electric vehicle supply chains. Nations propose national strategic reserves to secure supplies for these applications and mitigate geopolitical risks through domestic production pushes. The , prioritizing reshoring of lithium production and processing to reduce dependence on imports especially from China which dominates refining, via the 2022 , incentivizes domestic refining and mining, including expansions in with government funding for projects such as Thacker Pass, though faces a projected 50 GWh battery undersupply in 2025. The ’s aims to bolster local processing, while seeks non-Chinese offtake partners. These efforts encounter technical and economic hurdles, as Chinese dominance stems from scale, subsidies, and integrated supply chains, potentially slowing global transitions to low-carbon technologies if disruptions occur. Bolivia's vast reserves remain underdeveloped due to political instability and technological challenges in brine extraction, further concentrating supply risks.

Economic and Market Aspects

Lithium prices, benchmarked against (99.5% purity), remained relatively stable at approximately $4,000 to $6,000 per metric from 2010 to 2018, reflecting balanced supply from established and hard-rock operations amid modest demand growth in traditional applications like and ceramics. This period saw minimal volatility, with annual fluctuations under 20%, as global production hovered around 30,000 to 70,000 metric tons of lithium content, insufficiently disrupted by new entrants. A dramatic surge began in , driven by exponential demand for lithium-ion batteries in electric vehicles (EVs), which increased global lithium consumption by over 50% year-on-year by ; the global lithium market was valued at approximately USD 5-8 billion in 2022-2023, with projections for 2030 ranging from USD 15-30 billion at a compound annual growth rate (CAGR) of 15-20%, primarily driven by EVs and energy storage. prices escalated from under $10,000 per metric ton in early to peaks exceeding $80,000 per metric ton by December 2022, representing a volatility spike with intraday swings up to 10% amid futures speculation on exchanges like the Shanghai Metals Market. This boom was exacerbated by supply bottlenecks in key producers such as () and (brines), where weather events and permitting delays constrained output expansions. Post-2022, prices plummeted over 85% to troughs near $9,500 per metric ton by mid-2024, attributable to oversupply from accelerated project ramp-ups—including over 50 new hard-rock mines in —and delayed EV demand realization amid high interest rates curbing auto sales; this correction highlighted the market's sensitivity to capex cycles, where junior miners' aggressive development led to inventories exceeding 100,000 tons globally. Oversupply was further driven by new mines in Africa and expansions in South America, compounded by decelerating EV demand growth from economic pressures and subsidy changes, resulting in revenue declines, margin compression on high-cost assets, inventory buildup, impairment losses, net losses for producers, and negative P/E ratios in this cyclical commodity sector; geopolitical risks and increased competition have intensified these effects. By October 2025, spot prices for Chinese had recovered modestly to 75,400 CNY per metric ton (approximately $10,600 USD), up 5.45% year-to-date, amid production curtailments by Chinese processors and emerging supply deficits projected for 2026. Volatility persists due to structural factors: concentrated supply risks from Australia's 50%+ share of mined lithium and China's dominance in downstream refining (over 60% of global capacity), geopolitical tensions including U.S.-China trade frictions, and demand inelasticity tied to EV mandates despite subsidy fluctuations; for instance, Q3 2025 saw 10-15% price swings from rumors of Australian export curbs and European policy shifts. Empirical models indicate that without diversified sourcing, annual standard deviations in prices could exceed 50%, as observed in 2021-2023, underscoring the need for hedging via long-term contracts that now cover 70% of offtake to mitigate spot market gyrations.
YearAvg. Lithium Carbonate Price (USD/t)Key Driver
2015~5,000Stable industrial demand
2020~8,000Early EV acceleration
2022~45,000 (peak ~80,000)Supply-demand mismatch
2024~12,000Oversupply correction
2025 (Oct)~10,600Production cuts, demand signals

Major Producers and Trade Flows

dominates global lithium mine production, accounting for 48% of the total in the most recent data, primarily through hard-rock mining of ore from operations like Greenbushes and Pilgangoora. follows as the second-largest producer at 24%, extracting lithium from salars such as via evaporation of concentrates. ranks third with 18% of output, sourcing from both and hard-rock deposits including salt lake and pegmatites. contributes 5%, with rapid expansion from projects in the , while smaller producers like , , and each hold under 3%. Global mine production reached 240,000 metric tons of lithium content in 2024, up 18% from 204,000 metric tons in 2023, driven by demand for batteries.
CountryProduction Share (%)Approximate Output (metric tons Li, 2024)
48115,000
2458,000
1843,000
512,000
Others512,000
Trade flows are concentrated in raw concentrates and refined chemicals, with Australia exporting over 90% of its spodumene production—primarily to China for downstream processing into lithium hydroxide and carbonate. Chile and Argentina export lithium carbonate and hydroxide directly to markets in the United States, Europe, and Asia, with the U.S. sourcing 51% of its imports from Argentina and 43% from Chile based on recent patterns. China, Japan, and South Korea emerge as the principal importers of upstream materials, absorbing the bulk of Australian and African exports to fuel their battery manufacturing sectors, while refined products flow back to consumer markets in North America and Europe. Brazil's lithium exports, nearly all spodumene, direct 99% to China amid global market volatility. These flows underscore China's central role in refining, processing over 60% of global lithium despite modest mining output. In the lithium salt market, which includes key intermediates like lithium carbonate and hydroxide, competitors differentiate based on the completeness of vertical integration encompassing resources, processing, and battery production; stringent cost control amid price volatility; technological flexibility in extraction methods, such as adapting between ore-based hard-rock and salt lake brine processes; access to overseas resource bases for supply diversification; and advancements in downstream applications including solid-state battery technologies.

Recent Developments in Supply Expansion

In 2024, lithium supply expansion continued amid low prices that prompted some project delays or cancellations, with notable capacity increases in , , , and . Global mine supply rose by 22 percent that year, driven by ramp-ups at new and existing operations despite market pressures. These developments reflect efforts to meet projected demand growth, with global lithium requirements forecasted to rise from 1.04 million tonnes in 2024 to 3.56 million tonnes by 2035. Argentina emerged as a key growth area, with annual lithium production reaching 18,000 metric tons in , supported by multiple brine-based projects advancing to production. Output is projected to expand 340 percent between and 2035, outpacing regional peers and challenging Chile's position in South American supply. Rio Tinto's Rincon Lithium Project, featuring direct lithium extraction , anticipates construction starting in mid-2025, with first production targeted thereafter and a potential 40-year mine life. Chile's production climbed to 49,000 metric tons in 2024 from 41,000 metric tons in 2023, bolstered by expansions in brine processing and announcements for increased downstream capacity. Government initiatives aim to develop a fuller , including manufacturing, with total announced lithium output capacity set to rise significantly through 2030 via projects incorporating direct lithium extraction methods. In the United States, efforts to onshore supply accelerated with federal support, including $3 billion in Department of Energy funding announced in 2024 for battery materials production. Lithium Americas' Thacker Pass project in , following construction commencement in early 2023, increased its mineral resource estimates and targets a final investment decision in early 2025, positioning it as a major hard-rock development. Refinery projects, such as TerraVolta's in receiving $225 million in DOE grants in 2024, further aim to enhance domestic processing capacity. Australia maintained its status as the top producer, with ongoing expansions at hard-rock mines contributing to global supply stability, though specific 2024-2025 ramp-ups focused on optimizing existing operations amid price volatility. Emerging regions like saw production capacity growth, adding to diversified sourcing options outside traditional brine and hubs. These expansions, however, face challenges from geopolitical tensions, including China's October 2025 export controls on supply chains, which may constrain refined material availability. Competitors in the lithium industry employ strategies such as securing resource monopolies through control over key mines, full supply chain integration with large customers to erect entry barriers, low-cost expansion via new mine developments to undercut rivals, and aggressive capacity builds to launch price wars or capture market share from higher-cost producers. Amid these supply dynamics, the competitive landscape in lithium processing evolves through supply reductions and production halts, which increase market concentration among leading firms. While short-term price wars may occur due to oversupply adjustments, long-term dynamics favor companies with advantages in resources and processing technology, as evidenced by dominant players maintaining profitability amid volatility.

Applications and Uses

Lithium-Ion Batteries and Energy Storage

Lithium-ion batteries (LIBs) operate through the reversible intercalation of lithium ions between a and a metal , such as or lithium nickel manganese cobalt , during charge and discharge cycles. Lithium (atomic number 3) is particularly suited for electrochemical energy storage as the lightest metal (relative atomic mass 6.94) with the most negative standard electrode potential (-3.04 V vs. SHE), providing high open-circuit voltage and theoretical energy density; its small Li+ ion radius (0.076 nm) and low mass facilitate rapid diffusion and reversible intercalation/deintercalation in solid lattices; compared to other alkali metals, its moderate electronegativity (1.0) allows compatibility with organic electrolytes without violent reactions. These properties enable practical specific capacities exceeding 150 mAh/g in cathodes, contributing to densities of 150-250 Wh/kg across common chemistries like NMC and LFP. These properties outperform alternatives like lead-acid or nickel-metal batteries in gravimetric and , with round-trip efficiencies often above 90%. In electric vehicles (EVs), LIBs dominate powertrains, powering over 14 million EVs sold globally in 2023 and accounting for more than 80% of LIB demand in 2024. Battery packs typically range from 40-100 kWh, enabling ranges of 300-500 km per charge, with cycle lives of 1,000-2,000 full equivalents before capacity fades to 80% in NMC variants. For grid-scale , LIBs provide rapid response times under 100 ms for frequency regulation and peak shaving, with deployments exceeding 90 GWh annually by 2024 to integrate variable renewables like solar and . Systems like those in and demonstrate scalability, storing excess daytime generation for evening dispatch, though lithium phosphate (LFP) chemistries are preferred for stationary use due to superior thermal stability and cycle life over 5,000 cycles. Global lithium demand for batteries reached approximately 190,000 tons LCE (lithium carbonate equivalent) in 2024, comprising 87% of total lithium consumption and driving annual LIB production past 1 TWh for the first time. This surge reflects EV adoption and policy incentives, yet supply constraints have caused price volatility, with spot prices falling 80% from 2022 peaks to around $12,000 per ton by mid-2024 amid overcapacity in refining. recovers only 1-5% of lithium currently, limited by economic viability and collection rates below 50% in major markets, underscoring dependence on primary . Despite advances in solid-state electrolytes promising densities over 300 Wh/kg, risks persist, with failure rates under 1 per million cells in controlled testing but higher in field use without advanced battery management systems.

Industrial Materials and Manufacturing

Lithium compounds, particularly (Li₂O) and (Li₂CO₃), are incorporated into and ceramics manufacturing to lower melting points, enhance chemical durability, and improve resistance. In specialty glasses, such as those used for ovenware and stovetops, lithium formulations enable high strength and low coefficients, allowing products like to withstand rapid temperature changes without cracking. Global lithium demand for ceramics and accounted for approximately 7% of total consumption in 2022, reflecting established industrial reliance despite the dominance of battery applications. In metal alloys, elemental lithium is alloyed with aluminum and magnesium to produce , high-strength materials for and structural components. Aluminum-lithium alloys, containing 1-3% lithium by weight, reduce by up to 10% compared to conventional aluminum alloys while increasing and resistance, as demonstrated in applications for fuselages and wings since the . Magnesium-lithium alloys further exploit lithium's low (0.534 g/cm³) for weight-sensitive uses in housings and automotive parts, though challenges necessitate protective coatings. These alloys comprised a minor but specialized segment of lithium use, often processed via or under inert atmospheres to prevent lithium's reactivity with air. Lithium-based greases, formed by reacting (LiOH) or lithium soaps with fatty acids, dominate industrial lubrication due to their water resistance, mechanical stability, and high dropping points exceeding 190°C. These greases, which represented about 4% of global lithium consumption in , are standard in automotive bearings, industrial machinery, and constant velocity joints, outperforming calcium- or sodium-based alternatives in extreme pressure conditions. involves saponification of fats with lithium salts, followed by dispersion in base oils, yielding consistent performance verified through standards like NLGI Grade 2. Additional manufacturing roles include lithium as a flux in iron and production to remove impurities and as an additive in primary aluminum to refine baths, improving current efficiency by 5-10%. In continuous of , lithium compounds facilitate mold formulations that enhance and surface quality. These applications, though niche, underscore lithium's utility in high-temperature where its fluxing properties derive from strong basicity and low .

Medical and Pharmaceutical Applications

Lithium salts, primarily and , are established treatments for , particularly in managing acute manic episodes and providing long-term mood stabilization to prevent relapse. Australian psychiatrist first demonstrated lithium's antimanic effects in 1949 through experiments on guinea pigs and subsequent trials in manic patients, marking a pivotal advancement in psychiatric despite initial regulatory delays due to concerns. Systematic reviews of randomized controlled trials confirm lithium's efficacy in reducing manic relapse rates by up to 40% compared to over periods exceeding one year, with particular benefits in patients exhibiting classic euphoric . The precise mechanism of lithium's mood-stabilizing action remains incompletely understood but involves inhibition of glycogen synthase kinase-3 (GSK-3), modulation of systems including serotonin and glutamate, and enhancement of neuroprotective pathways such as increased (BDNF) expression; more broadly, lithium exerts neuroprotective effects through multiple pathways, including reduction of oxidative stress and inflammation, prevention of apoptosis, and protection against mitochondrial dysfunction. Therapeutic serum concentrations typically range from 0.6 to 1.2 mEq/L, achieved via oral dosing starting at 300-600 mg daily and titrated based on response and tolerance. Lithium also exhibits antisuicidal properties, with meta-analyses showing a 60-80% reduction in risk among bipolar patients on long-term therapy, an effect not fully replicated by alternative mood stabilizers. Administration requires rigorous monitoring to mitigate risks, including renal impairment, , and , which can manifest as , , or seizures at levels above 1.5 mEq/L. Guidelines recommend baseline assessments of renal function (e.g., eGFR), thyroid function (TSH), and electrolytes, followed by serum lithium measurements every 5-7 days during initiation, then every 3-6 months once stable, alongside annual thyroid and renal evaluations. , sodium depletion, or concurrent use of NSAIDs, diuretics, or inhibitors can precipitate toxicity by reducing lithium clearance, necessitating dose adjustments. Beyond , lithium has been investigated for adjunctive roles in and , though evidence is less robust; for instance, while preclinical studies suggest benefits in Alzheimer's models via reduction, clinical trials have yielded inconsistent results without establishing it as standard care. Low-dose lithium (under 300 mg daily) shows preliminary promise in across psychiatric populations and risk reduction in epidemiological data from lithium-rich water sources, but randomized evidence remains limited and requires further validation. Despite superior long-term efficacy data, lithium prescribing has declined since the , attributed to monitoring burdens and the rise of newer agents like and antipsychotics, even as relapse prevention trials affirm its unique prophylactic value.

Nuclear, Military, and Specialized Uses

Lithium-6 deuteride serves as the primary fusion fuel in the secondary stage of thermonuclear weapons, where neutrons from the fission primary react with lithium-6 to produce tritium, enabling deuterium-tritium fusion reactions that amplify the weapon's yield. This design, implemented in devices like the U.S. Castle Bravo test on March 1, 1954, which yielded 15 megatons due to unexpected lithium-7 contributions, relies on enriched lithium-6 to achieve high compression and heating under inertial confinement from the primary's x-rays. The U.S. Department of Energy maintains production of lithium-6 specifically for such applications, highlighting its strategic role in nuclear arsenals. In nuclear reactors, lithium isotopes support advanced technologies: lithium-6 enables tritium breeding for fusion reactors via , while lithium-7 minimizes absorption in pressurized water reactors and systems, reducing corrosion and improving efficiency. Lithium metal has been explored as a in experimental reactors due to its high of 1342°C and thermal conductivity, though safety concerns limit adoption. Military applications of lithium extend beyond batteries to alloys for armor and structural components in aircraft and vehicles, enhancing mobility without sacrificing strength. Lithium-ion batteries power critical systems including submarines for extended , unmanned drones for , and portable soldier equipment, offering high essential for operational endurance. The U.S. Department of Defense's 2023-2030 lithium battery strategy addresses supply vulnerabilities, given integration into weapon systems from to large platforms. Specialized uses include alkyl lithium compounds as initiators in synthesis for high-performance materials and in pharmaceutical intermediates, as well as lithium in ceramics for high-temperature seals and for and applications requiring low . functions in for propulsion and as a in research reactors.

Environmental and Resource Impacts

Empirical Assessment of Extraction Effects

Lithium extraction primarily occurs via two methods: brine evaporation from salt flats in the (, , ) and hard-rock mining of ore, predominantly in . extraction involves pumping hypersaline into evaporation ponds, where solar concentrates lithium over 12-18 months, yielding . This process extracts approximately 0.05-0.1% lithium from , requiring large volumes of for pumping and pond maintenance. Empirical measurements from environmental impact assessments in Argentina's salt flats, such as the Olaroz and Fénix mines, indicate water consumption rates of 1.5 to 2.5 million liters per ton of lithium carbonate equivalent (LCE), primarily from drawdown in endorheic basins with limited recharge. In the , , operational data from major producers like SQM and Albemarle show annual extraction exceeding 40 million cubic meters, correlating with piezometric level declines of 0.5-2 meters per year in monitored wells adjacent to ponds, though basin-wide recharge from remains negligible at under 1% of extraction volumes due to the region's hyper-arid climate. effects include localized salinization of surrounding soils and potential disruption to shallow aquifers supporting microbial mats and flamingo habitats, with surveys documenting reduced depths by up to 30 cm in extraction zones since operations began in the . However, comprehensive hydrologic models suggest that much of the observed drawdown reflects long-term trends predating , with extraction accelerating but not solely causing depletion in fossil aquifers. Hard-rock mining, as assessed in Australian facilities like Greenbushes and Pilgangoora, involves open-pit operations yielding 1-2% lithium-bearing ore, followed by crushing, flotation, and high-temperature roasting. Environmental audits report land clearance of 100-500 hectares per mine, generating 5-10 tons of tailings per ton of LCE, with potential acid mine drainage risks from sulfide minerals contaminating soil and groundwater if unlined. Empirical soil sampling near Pilbara operations detected elevated heavy metals (e.g., arsenic up to 50 mg/kg) in tailings, but groundwater monitoring shows minimal migration beyond containment due to low permeability clays, with pH levels remaining above 7 in downgradient wells. Energy-intensive processing contributes to dust emissions, measured at 1-5 mg/m³ near sites, mitigated by suppression techniques reducing off-site deposition by 80%. Across both methods, from lithium extraction is limited by the element's low inherent , with no widespread of in local biota; boron and magnesium co-extracted in pose greater risks to via alkalization, observed in of 1-2 km from in Argentine salars. Lifecycle analyses indicate that while brine methods have lower direct emissions (5-15 kg CO2e/kg LCE) than hard-rock (20-40 kg CO2e/kg LCE), unmitigated and land effects remain site-specific, often exaggerated in media reports lacking baseline data from pre-mining eras. Independent assessments emphasize that proper pond lining and reinjection trials, as piloted in since 2020, can reduce evaporative losses by 20-30%, underscoring causal links between operational practices and measurable impacts rather than inherent process flaws.

Water Usage, Pollution, and Ecosystem Claims

Claims of excessive usage in lithium extraction often cite figures around 1.9 million liters per metric of lithium, equating to approximately 500,000 gallons, but these typically refer to the volume of evaporated rather than net freshwater consumption. Empirical assessments from environmental impact reports in salt flats indicate actual freshwater consumption for -based lithium carbonate equivalent (LCE) production ranges from 5 to 50 cubic meters per , varying by extraction technology and site-specific hydrology. In the , , major producers like SQM operate under regulated extraction concessions, with monitoring systems tracking and balances to prevent depletion, though the arid region's inherent amplifies local concerns. , predominant in , consumes more —estimated at 170 cubic meters per tonne of lithium hydroxide—due to ore processing and management, but this remains lower than many conventional operations like . Pollution allegations focus on potential from processing chemicals and disposal, yet methods involve minimal reagents, producing primarily hypersaline residues that are managed through reinjection or pond containment rather than widespread toxic releases. In contrast, lithium generates and rock that may leach or acids if not properly neutralized, though site-specific geochemical analyses of legacy operations reveal low levels of common contaminants like or in associated waters. extraction is generally less polluting than due to lower inputs and absence of large-scale excavation, with carbon intensity three times lower per some benchmarks, countering narratives that equate lithium to more chemically intensive sectors. Environmental advocacy groups frequently highlight risks without distinguishing between extraction types or providing comparative , potentially overstating impacts relative to verified monitoring. Ecosystem disruption claims, particularly in Andean salars, emphasize threats to such as flamingo populations, but empirical studies attribute primary declines to climate-driven and reduced rather than direct effects. Lithium operations occupy a fraction of salar areas—pond footprints in cover limited zones with hydrogeological safeguards—yielding no broad evidence of systemic loss or in peer-reviewed analyses. While localized brine pumping can alter subsurface flows, potentially stressing endemic species in fragile altiplano wetlands, integrated assessments incorporating economic valuations of ecosystems suggest extraction paces remain viable with mitigation, challenging alarmist projections of irreversible damage. Socio-ecological research gaps persist, with much criticism rooted in NGO reports that prioritize over longitudinal , underscoring the need for causal attribution beyond in water-stressed basins.

Lifecycle Comparisons to Alternatives

Lifecycle assessments of lithium-ion batteries (LIBs) reveal higher upfront environmental burdens during extraction and compared to lead-acid batteries, primarily due to energy-intensive processing of lithium, , and cathode metals like and . For instance, producing a () battery pack emits approximately 6 times more GHGs than an equivalent lead-acid battery, with LIB contributing 50-100 kg CO₂e per kWh of capacity versus 10-20 kg CO₂e for lead-acid. This disparity stems from lithium evaporation requiring vast water volumes—up to 500,000 liters per metric ton of —and refining steps that consume 15-20 MWh per ton, often powered by fuels in regions like South America's . In contrast, lead-acid batteries rely on abundant lead and , with mining impacts concentrated in smelting emissions and acid runoff, but lower overall energy demands result in reduced cradle-to-gate impacts across categories like acidification and . Nickel-metal (NiMH) batteries, used in hybrids, involve similar cathode processing to LIBs but avoid lithium, yielding comparable GHGs (around 60-80 kg CO₂e/kWh) while facing higher from rare earths in some designs. Sodium-ion batteries (NaIBs), an emerging alternative, leverage sodium's ubiquity to minimize extraction burdens—brine or mineral sources emit 20-50% less than lithium equivalents—but current NaIB prototypes exhibit 10-30% higher lifecycle CO₂ per kWh due to lower (140-160 Wh/kg vs. LIBs' 200-250 Wh/kg) necessitating larger packs for equivalent storage. Full cradle-to-grave analyses, incorporating use and , often favor LIBs in electrified applications over lead-acid or baselines. LIBs' superior efficiency (90-95% round-trip vs. lead-acid's 70-80%) and cycle life (1,000-5,000 vs. 200-500) amortize upfront costs, yielding 20-50% lower lifetime GHGs for EV batteries (61-106 g CO₂e/km over 200,000 km) compared to lead-acid hybrids or internal engines (150-250 g CO₂e/km). recovers 95% of lithium, , and , avoiding 50-70% of mining emissions and surpassing lead-acid rates (95% but with persistent lead leachate risks). and mining for LIB cathodes produces more particulate matter and habitat disruption than lithium operations but higher metal yields per site; overall, LIB supply chains emit 10-15 tons CO₂e per ton of battery material, less than cobalt-dominant alternatives when scaled.
Battery TypeManufacturing GHG (kg CO₂e/kWh)Lifecycle GHG Advantage in EVs (vs. )Key Extraction Concern
Lithium-Ion (LFP)50-10050-70% lower over 200,000 kmWater depletion in brines
Lead-Acid10-2020-40% lower but shorter lifeLead toxicity in waste
Sodium-Ion40-80 (projected)Comparable but density-limitedLower rarity, higher pack mass
These comparisons underscore that while LIBs demand targeted mitigation for mining phases, their systemic efficiency drives net environmental gains absent in less efficient alternatives, contingent on grid decarbonization and recycling infrastructure.

Social, Health, and Safety Considerations

Human Rights and Labor in Mining Regions

In major lithium-producing regions such as Chile's , labor disputes have centered on wage negotiations and working conditions, with unionized workers at Sociedad Química y Minera de Chile (SQM) initiating a strike on , 2021, involving 135 members after failing to agree on pay increases during . Similar organized labor actions reflect established union presence rather than systemic exploitation, contrasting with sectors elsewhere. In , which accounts for over 50% of global hard-rock lithium supply as of 2023, operations adhere to stringent national labor laws under the Fair Work Act, with low reported incidences of rights violations and emphasis on ; for instance, employs over 1,000 workers under regulated shifts and monitoring. Human rights concerns in South America's primarily involve ' claims over land and water access, mandated under national laws like Chile's Consultation Convention (ratified 2008) and Argentina's Law 26.160 on community prior consultation. In Chile's , Atacameño have expressed tensions over extraction's indirect effects on livelihoods, though formal agreements with operators like SQM include benefit funds exceeding $100 million annually by 2022 for local development. In Argentina's , opposition to lithium projects escalated in 2023 amid provincial constitutional reforms easing mining restrictions and protest limitations, prompting widespread demonstrations; police responses included use, resulting in at least 20 injuries including permanent eye damage and allegations of against protesters, as documented by local observers. These events highlight conflicts between provincial governments and , with reforms criticized for prioritizing extraction over , though project approvals still require environmental impact assessments. Emerging lithium operations in , such as in Zimbabwe's Bikita mine (operational since 2022) and Namibia's Karibib project, face governance risks including potential and inadequate , per analyses of transparency; however, no large-scale empirical reports confirm widespread abuses akin to those in . In , illegal artisanal lithium surged by 2024 due to global demand, involving child labor in unregulated sites where children as young as 10 extract ore manually, exposing them to toxic dust and cave-ins, with production estimates reaching 2,000 tons annually from such operations. Major corporate projects, by contrast, implement international standards like the Initiative for Responsible Mining Assurance (IRMA), though adoption remains partial. Worker safety in lithium extraction involves risks from dust inhalation and chemical exposure during brine processing or hard-rock . U.S. data from lithium facilities (2017-2023) show respirable crystalline silica levels below OSHA limits in 90% of samples, but elevated respirable exposures in 15% of cases, prompting enhanced ventilation requirements. In South American brine operations, hyper-arid conditions minimize certain hazards but necessitate protections against evaporative brine splashes, with incident rates comparable to other salt flat at under 2 lost-time injuries per million hours worked in Chilean operations as of 2022. Overall, formalized exhibits better safety records than artisanal alternatives, supported by industry reporting to bodies like the .

Toxicity, Health Risks, and Precautions

Lithium and its compounds exhibit low to moderate in humans, primarily through and corrosive effects rather than high systemic potency, though specific forms like can cause severe burns and neurological symptoms upon exposure. Inhalation of lithium dust or vapors irritates the , leading to symptoms such as coughing and , while dermal contact with reactive compounds like organolithium reagents or results in chemical burns and skin inflammation. Ingestion of soluble lithium salts can produce gastrointestinal distress, , and in high doses, elevated blood lithium levels exceeding 10 mg/L, which correlate with mild manifesting as tremors and ; levels above 15 mg/L risk severe neurological impairment, and 20 mg/L pose lethality risks. Chronic occupational exposure, particularly in mining and battery production, is associated with respiratory irritation and potential systemic effects from dust inhalation, though lithium-specific contributions are often confounded by co-exposures to silica, other metals, or alkaline dusts. Workers handling lithium hydroxide or carbonate report higher incidences of upper respiratory and skin irritations, with studies indicating elevated risks of inflammation and cardiovascular strain from exposure to lithium-containing cathode materials like LiNiCoMnO2 particles. In lithium extraction regions, miners face risks of pneumoconiosis-like conditions from respirable dust, alongside heat-related illnesses and noise-induced hearing loss, but direct causation to lithium ions remains empirically limited compared to physical mining hazards. Therapeutic use of lithium carbonate for psychiatric conditions, while not elemental exposure, informs broader risk profiles, revealing potential for nephrotoxicity and thyroid dysfunction at prolonged serum levels above 1.2 mmol/L, underscoring dose-dependent renal clearance impairments. Precautions for handling elemental lithium emphasize its pyrophoric nature and reactivity with moisture, requiring storage under inert atmospheres like or to prevent spontaneous ignition and evolution. Occupational protocols mandate including chemical-resistant gloves, goggles, and respirators with NIOSH-approved filters for or fumes, alongside local exhaust ventilation to maintain airborne concentrations below permissible exposure limits—such as 25 mg/m³ total for lithium metal per ACGIH guidelines, though tighter controls apply for irritant compounds. In battery and , engineering controls like enclosed processes and mitigate risks from , which can release toxic electrolytes, while workers should avoid contact and use non-sparking tools. For operations, suppression via wet methods and regular health monitoring for renal function and respiratory capacity are recommended, with empirical data from evaluations showing reduced irritation incidents under such measures. Emergency response involves immediate removal from exposure, decontamination with dry methods, and medical evaluation for symptoms like muscle twitching or confusion, avoiding emetics due to corrosive potential.

Regulatory Frameworks and Mitigation

Regulatory frameworks for lithium extraction vary by , with major producers imposing state oversight on operations in the (, , ) and more privatized hard-rock . In , lithium deposits are classified as strategic resources under a 1979 , prohibiting private concessions and requiring joint ventures with the state-owned or ENAMI, as reinforced by 2023 legislation that nationalizes new projects and mandates public-private partnerships to ensure national control over production. This approach aims to capture greater economic value but has deterred foreign investment due to bureaucratic hurdles and profit-sharing requirements, contributing to Chile's lag behind competitors despite holding 40% of global reserves. , by contrast, permits private concessions for lithium under its Mining Code, with incentives like tax stability treaties offering up to 30 years of fiscal predictability, making it the preferred for new developments in the region. regulates lithium primarily through state-level environmental approvals under the Environment Protection and Conservation Act 1999, requiring assessments for water use and impacts in hard-rock mines, which account for over 50% of global supply; these frameworks enforce rehabilitation bonds and monitoring but face criticism for insufficient enforcement in arid regions. Environmental regulations target 's high intensity, which consumes approximately 500,000 liters per ton of lithium produced through solar ponds that can take 12-18 months per cycle. In , the National Lithium Strategy, updated in 2023, mandates environmental impact assessments (EIAs) under the Environmental Evaluation Service, including modeling to limit drawdown, though compliance varies and indigenous communities have challenged approvals in for inadequate consultation. strategies emphasize direct lithium extraction (DLE) technologies, which use adsorption or ion-exchange s to recover lithium from in hours rather than months, reducing loss by up to 90% and minimizing pond footprints; pilot projects in and demonstrate feasibility, though scaling remains constrained by durability and costs. Additional measures include closed-loop , where process is treated and reused, as implemented at sites like Thacker Pass in , cutting freshwater intake by 70%; real-time monitoring of via piezometers and advanced further curbs salinization risks. In , state regulations require zero-discharge policies for mine , with liners and controls to prevent boron and leaching into waterways. Occupational safety standards for handling elemental lithium and lithium compounds fall under general hazardous materials protocols, given its reactivity with water and air, forming hydrogen gas and potential fires. In the United States, the (OSHA) classifies lithium metal as a flammable solid under 29 CFR 1910.106, mandating inert atmospheres for storage, (PPE) like flame-retardant clothing, and emergency eyewash stations within 25 feet of handling areas; for lithium-ion batteries, OSHA's guidelines address risks through ventilation, spill containment, and fire suppression with Class D extinguishers, though no lithium-specific exists, relying instead on the National Institute for Occupational Safety and Health (NIOSH) recommended 25 mg/m³ short-term limit for dust. Transportation regulations by the (DOT) under 49 CFR Parts 171-180 treat lithium batteries as hazardous, requiring UN-tested packaging, labeling with UN3480/UN3481, and state-of-charge limits below 30% for air shipment to mitigate fire propagation. End-of-life mitigation is advanced in the via Regulation (EU) 2023/1542 on batteries, effective from August 2023, which sets efficiency targets of 65% for lithium-based batteries by end-2025, rising to 70% by 2030, and mandates minimum recycled content—6% lithium by 2031, increasing to 12% by 2036—to reduce virgin material demand and associated mining impacts. Producers must declare carbon footprints and provide digital passports for traceability, fostering closed-loop supply chains; however, critics note that current global rates hover below 5% for lithium due to collection inefficiencies and pyrometallurgical process losses, underscoring enforcement gaps. These frameworks collectively aim to balance lithium's strategic role in with abatement, though empirical indicate that regulatory stringency in producing nations often prioritizes over proactive controls, with DLE adoption offering the most causal leverage for .

Future Outlook

Demand Forecasts and Supply Challenges

Global lithium demand is forecasted to expand rapidly, driven predominantly by the proliferation of lithium-ion batteries in electric vehicles (EVs) and stationary . The (IEA) projects that demand could increase nearly fivefold by 2040, exceeding 500,000 metric tons of pure lithium, with the EV sector accounting for the majority of growth under scenarios aligned with net-zero ambitions. Independent analyses, such as from Katusa Research, anticipate demand surging from 1.04 million tonnes of equivalent (LCE) in 2024 to 3.56 million tonnes by 2035, reflecting accelerated EV adoption and grid-scale storage deployment. According to the International Renewable Energy Agency (IRENA) (2024), lithium demand from EV batteries is projected to quadruple by 2030, reaching 2.06–2.47 Mt/year under various scenarios, with total global lithium demand reaching 2.5–3.1 Mt/year primarily from EVs. A China-focused study projects annual EV lithium demand reaching 252 kt by 2035, potentially mitigated by recycling and technological improvements. Lithium faces the largest projected supply deficits among battery and EV minerals, potentially up to 40% by 2035 even with all announced projects proceeding, due to extreme demand multipliers from EV growth. These projections assume continued declines in battery costs and supportive policies, though actual growth may vary with technological substitutions like sodium-ion batteries or slower-than-expected EV penetration in key markets. Lithium supply has scaled with demand in recent years but faces structural challenges that could lead to imbalances. Worldwide production of contained lithium reached approximately 240,000 metric tons in 2024, an 18% increase from 2023, led by expansions in Australia and hard-rock mining operations. Identified resources exceed 98 million metric tons of lithium, sufficient for centuries at current consumption rates, yet extraction bottlenecks persist: brine-based production in the "Lithium Triangle" (Argentina, Bolivia, Chile) requires 18-24 months for evaporation cycles, while hard-rock mining demands high upfront capital and energy inputs. Market forecasts indicate a narrowing surplus—projected at 33,000 metric tons LCE in 2025—potentially shifting to a deficit of 1,500 tons by 2026 as production cuts by high-cost producers take effect amid recovering prices. Geopolitical and processing concentrations exacerbate supply risks. Australia dominates raw output at over 50% of global production, but China controls roughly 60-70% of downstream refining and chemical conversion, creating vulnerabilities to export restrictions or trade tensions. Efforts to diversify, such as U.S. projects under the , encounter economic hurdles, with many initiatives stalling due to volatile prices that fell over 90% to four-year lows of US$610 per tonne LCE by mid-2025 before partial recovery. Permitting delays, in arid extraction regions, and limited —currently under 1% of supply—further constrain near-term scaling, necessitating tripling of production within a decade to meet EV-driven needs without shortages.

Innovations in Extraction and Alternatives

Direct lithium extraction (DLE) technologies have emerged as a key innovation for brine-based production, enabling selective recovery of lithium ions using adsorbents, , or membranes, with reported recovery rates exceeding 90% compared to 40-60% in traditional evaporation ponds. These methods reduce processing times from 12-18 months to days or weeks and can lower usage by up to 70%, though challenges persist in scaling adsorbent and impurity management. , EnergySource Minerals commenced construction of a DLE facility near the in 2025, targeting 5,000 metric tons of equivalent annually by leveraging geothermal brines, with potential expansion to 25,000 tons. Efforts to extract lithium from , which contains approximately 0.17 parts per million, have advanced through adsorption-based systems like lithium-ion sieves and photothermal ion powered by . A 2025 study demonstrated a bionic adsorption-responsive achieving reversible lithium capture with efficiencies improved by solar-driven desorption, potentially slashing needs relative to electrochemical methods. However, economic viability remains limited by low concentrations requiring vast volumes—equivalent to processing 1.5 million tons of for one ton of lithium—necessitating further material innovations to compete with terrestrial sources. In hard-rock mining, primarily from spodumene ores, innovations focus on integrated flowsheets incorporating dense media separation, flotation, and low-emission roasting to boost yields beyond 80% while minimizing acid consumption. FLSmidth's MissionZero designs integrate dry processing and renewable energy to cut Scope 1 and 2 emissions by over 50% compared to conventional wet circuits. Tesla's refinery in Corpus Christi, Texas, employs an acid-free refining route that processes spodumene ore into battery-grade lithium hydroxide, avoiding sulfuric acid through kilns and alkaline leaching. These approaches address the energy-intensive nature of converting spodumene to lithium hydroxide, with pilot-scale pressure leaching achieving 95% extraction rates under optimized conditions. As alternatives to lithium in rechargeable batteries, sodium-ion technologies leverage abundant sodium resources, offering costs 20-30% lower than cells and enhanced safety due to reduced flammability risks. In , prototypes demonstrated cycle lives exceeding 5,000 charges with densities approaching 160 Wh/kg, suitable for stationary storage but trailing lithium-ion's 250+ Wh/kg for vehicles. Commercial deployments, such as those by Seattle-based startups, prioritize grid applications where volume rather than weight is key, though stability issues limit widespread adoption pending further refinements. Other candidates like solid-state batteries with non-lithium anodes remain in early , with no scalable alternatives yet matching lithium's electrochemical performance across applications.

Strategic Importance in Energy Transition

Lithium serves as a critical material in lithium-ion batteries, enabling the high required for electric vehicles (EVs) and stationary systems that support integration into grids. These batteries rely on lithium compounds such as and to facilitate movement between electrodes, providing the electrochemical basis for rechargeable power in applications aimed at reducing dependence. Without scalable lithium supplies, the proliferation of EVs—projected to dominate new vehicle sales in scenarios—and the stabilization of intermittent solar and generation face material constraints, as alternatives like sodium-ion batteries currently lag in performance for high-density needs. Global lithium demand has surged with the , with EVs accounting for nearly 90% of consumption in 2025, up from 64% in 2020. In 2024, EV battery demand exceeded 950 GWh, driving lithium requirements that the (IEA) forecasts to reach levels necessitating 750 kilotons annually by 2040 under baseline scenarios—more than triple 2024 levels. Battery demand alone is expected to grow to over 3 TWh by 2030 in the IEA's Stated Policies Scenario, underscoring lithium's bottleneck role amid policies mandating electrification, such as those in the and . could offset 25-30% of future demand by mid-century if scaled, but primary extraction remains dominant due to insufficient secondary supply volumes. Supply chains exhibit high concentration, amplifying strategic vulnerabilities: , , and dominate raw production, accounting for over 70% of global output, while controls approximately 65% of refining capacity. 's October 2025 export controls on components highlight risks of disruptions, as they target downstream processing and exacerbate dependencies for Western manufacturers. Geopolitical tensions, including U.S. and efforts to diversify via domestic projects and alliances with and , reflect concerns over supply interruptions that could hinder timelines. Emerging producers like and expanded Argentine operations offer growth potential, but environmental permitting delays and capital intensity limit rapid scaling to match demand trajectories.

References

  1. https:///news/2025-10-sodium-ion-battery-breakthrough-power.html
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