Lithium
Lithium | |||||||||||||||||||||
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Pronunciation | /ˈlɪθiəm/ | ||||||||||||||||||||
Appearance | silvery-white | ||||||||||||||||||||
Standard atomic weight Ar°(Li) | |||||||||||||||||||||
Lithium in the periodic table | |||||||||||||||||||||
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kJ/mol | |||||||||||||||||||||
Heat of vaporization | 136 kJ/mol | ||||||||||||||||||||
Molar heat capacity | 24.860 J/(mol·K) | ||||||||||||||||||||
Vapor pressure
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Atomic properties | |||||||||||||||||||||
Discovery | Johan August Arfwedson (1817) | ||||||||||||||||||||
First isolation | William Thomas Brande (1821) | ||||||||||||||||||||
Isotopes of lithium | |||||||||||||||||||||
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Lithium (from
The
Lithium and its compounds have several industrial applications, including heat-resistant glass and
Lithium is present in biological systems in trace amounts. It has no established metabolic function. Lithium-based drugs are useful as a mood stabilizer and antidepressant in the treatment of mental illness such as bipolar disorder.
Properties
Atomic and physical
The
Lithium metal is soft enough to be cut with a knife. It is silvery-white. In air it oxidizes to lithium oxide.[9] Its melting point of 180.50 °C (453.65 K; 356.90 °F)[12] and its boiling point of 1,342 °C (1,615 K; 2,448 °F)[12] 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
Lithium's
Lithium has a mass specific heat capacity of 3.58 kilojoules per kilogram-kelvin, the highest of all solids.[20][21] Because of this, lithium metal is often used in coolants for heat transfer applications.[20]
Isotopes
Naturally occurring lithium is composed of two stable
7Li is one of the
Lithium isotopes fractionate substantially during a wide variety of natural processes,[30] 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.[31]
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
Both stable isotopes of lithium can be laser cooled and were used to produce the first quantum degenerate Bose-Fermi mixture.[33]
Occurrence
Astronomical
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.[34]
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.[35] 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.[36] The lack of lithium in older stars is apparently caused by the "mixing" of lithium into the interior of stars, where it is destroyed,[37] 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.[38]
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.[38][40][41] 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.[38]
On 27 May 2020, astronomers reported that
Terrestrial
Although lithium is widely distributed on Earth, it does not naturally occur in elemental form due to its high reactivity.
Estimates for the Earth's crustal content range from 20 to 70 ppm by weight.[47] Lithium constitutes about 0.002 percent of Earth's crust.[48] 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.[47] Another significant mineral of lithium is lepidolite which is now an obsolete name for a series formed by polylithionite and trilithionite.[49][50] Another source for lithium is hectorite clay, the only active development of which is through the Western Lithium Corporation in the United States.[51] At 20 mg lithium per kg of Earth's crust,[52] lithium is the 25th most abundant element.
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."[53]
Chile is estimated (2020) to have the largest reserves by far (9.2 million tonnes),[54] and Australia the highest annual production (40,000 tonnes).[54] 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 Australia, Argentina and China.[55][56] 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 is considered as a potentially economical deposit, with 160 000 tonnes of lithium.[57] 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.[58]
In June 2010,
Biological
Lithium is found in trace amount in numerous plants, plankton, and invertebrates, at concentrations of 69 to 5,760
Lithium is easily absorbed by
Many of lithium's major biological effects can be explained by its competition with other ions.[67] The
competes with other ions such as sodium (immediately below lithium on the periodic table), which like lithium is also a monovalent alkali metal
History
Arfwedson later showed that this same element was present in the minerals
Australian psychiatrist John Cade is credited with reintroducing and popularizing the use of lithium to treat mania in 1949.[89] 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
The demand for lithium increased dramatically during the
Lithium is used to decrease the melting temperature of glass and to improve the melting behavior of
The development of lithium ion batteries increased the demand for lithium and became the dominant use in 2007.[93] With the surge of lithium demand in batteries in the 2000s, new companies have expanded brine isolation efforts to meet the rising demand.[94][95]
It has been argued that lithium will be one of the main objects of geopolitical competition in a world running on renewable energy and dependent on batteries, but this perspective has also been criticised for underestimating the power of economic incentives for expanded production.[96]
Chemistry
Of lithium metal
Lithium reacts with water easily, but with noticeably less vigor than other alkali metals. The reaction forms hydrogen gas and lithium hydroxide.[9] 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).[47] Lithium is one of the few metals that react with nitrogen gas.[97][98]
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.[38]
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
2O) and peroxide (Li
2O
2) when burnt in O2, salts with similar solubilities, and thermal instability of the carbonates and nitrides.[47][99] The metal reacts with hydrogen gas at high temperatures to produce lithium hydride (LiH).[100]
Lithium forms a variety of binary and ternary materials by direct reaction with the main group elements. These
It dissolves in ammonia (and amines) to give [Li(NH3)4]+ and the solvated electron.[99]
Inorganic compounds
Lithium forms salt-like derivatives with all
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
Like its inorganic compounds, almost all organic compounds of lithium formally follow the
Production
Country | Production | Reserves[note 1] | Resources |
---|---|---|---|
Argentina | 6,590 | 3,600,000 | 22,000,000 |
Australia | 74,700 | 6,200,000 | 8,700,000 |
Austria | - | - | 60,000 |
Bolivia | - | - | 23,000,000 |
Brazil | 2,630 | 390,000 | 800,000 |
Canada | 520 | 930,000 | 3,000,000 |
Chile | 38,000 | 9,300,000 | 11,000,000 |
China | 22,600 | 3,000,000 | 6,800,000 |
Czech Republic | - | - | 1,300,000 |
DR Congo
|
- | - | 3,000,000 |
Finland | - | - | 68,000 |
Germany | - | - | 3,800,000 |
Ghana | - | - | 200,000 |
India | - | - | 5,900,000[104][105] |
Kazakhstan | - | - | 50,000 |
Mali | - | - | 890,000 |
Mexico | - | - | 1,700,000 |
Namibia | - | - | 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] | 1,100,000 | 14,000,000 |
Zimbabwe | 1,030 | 310,000 | 690,000 |
Other countries | - | 2,800,000 | - |
World total | 146,000[note 3] | 28,000,000 | 105,000,000+ |
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.[106]
Reserves and occurrence
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
The
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).[111]
Lithium triangle and other brine sources
The world's top four lithium-producing countries from 2019, as reported by the US Geological Survey, are Australia, Chile, China and Argentina.[55]
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. The Lithium Triangle is believed to contain over 75% of existing known lithium reserves.[112] Deposits are also found in South America throughout the Andes mountain chain. Chile is 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.[113][114] Half the world's known reserves are located in Bolivia along the central eastern slope of the Andes. The Bolivian government has invested US$900 million in lithium production and in 2021 successfully produced 540 tons.[115][113] The brines in the salt pans of the Lithium Triangle vary widely in lithium content.[116] Concentrations can also vary in time as brines are fluids that are changeable and mobile.[116]
In the US, lithium is recovered from brine pools in Nevada.[20] Projects are also under development in Lithium Valley in California.[117]
Hard-rock deposits
Since 2018 the Democratic Republic of Congo is known to have the largest lithium spodumene hard-rock deposit in the world.[118] 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.[119] 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.[120][121] Operational mining began in 2022.[122]
A deposit discovered in 2013 in Wyoming's Rock Springs Uplift is estimated to contain 228,000 tons.[clarification needed] Additional deposits in the same formation were estimated to be as much as 18 million tons.[123] Similarly in Nevada, the McDermitt Caldera hosts lithium-bearing volcanic muds that consist of the largest known deposits of lithium within the United States.[124]
The
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 45,000 tonnes of lithium carbonate and hydroxide per year and plans to reach full design capacity by 2030.[126]
Sources
Another potential source of lithium as of 2012[update] was identified as the leachates of
Pricing
In 1998, the price of lithium metal was about 95 USD/kg (or US$43/
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.[132]
Extraction
Lithium and its compounds were historically isolated and extracted from hard rock but by the 1990s
By early 2021, much of the lithium mined globally comes from either "spodumene, the mineral contained in hard rocks found in places such as Australia and North Carolina"[134] or from the salty brine pumped directly out of the ground, as it is in locations in Chile.[134][116] In Chile's Salar de Atacama, the lithium concentration in the brine is raised by solar evaporation in a system of ponds.[116] The enrichment by evaporation process may require up to one-and-a-half years, when the brine reaches a lithium content of 6%.[116] The final processing in this example is done near the city of Antofagasta on the coast where pure lithium carbonate, lithium hydroxide, and lithium chloride are produced from the brine.[116]
Low-cobalt cathodes for lithium batteries are expected to require lithium hydroxide rather than lithium carbonate as a feedstock, and this trend favors rock as a source.[135][136][137]
One method for lithium extraction, as well as other valuable minerals, is to process geothermal brine water through an electrolytic cell, located within a membrane.[138]
The use of
Environmental issues
The manufacturing processes of lithium, including the solvent and
Lithium extraction can be fatal to aquatic life due to water pollution.[146] It is known to cause surface water contamination, drinking water contamination, respiratory problems, ecosystem degradation and landscape damage.[143] It also leads to unsustainable water consumption in arid regions (1.9 million liters per ton of lithium).[143] Massive byproduct generation of lithium extraction also presents unsolved problems, such as large amounts of magnesium and lime waste.[147]In the United States,
Human rights issues
A study of relationships between lithium extraction companies and indigenous peoples in Argentina indicated that the state may not have protected 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.[149]
Development of the
Applications
Batteries
In 2021, most lithium is used to make
Ceramics and glass
Lithium oxide is widely used as a
Electrical and electronic
This section needs expansion with: beyond concerns about only lithium carbonate in the second paragraph. Lithium carbonate is simply not close to the most economically interesting lithium++ battery chemistry by late in the 2010s. You can help by adding to it. (March 2021) |
Late in the 20th century, lithium became an important component of battery electrolytes and electrodes, because of its high
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
Lubricating greases
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.[20][159][160]
Metallurgy
Lithium (e.g. as lithium carbonate) is used as an additive to
Lithium (as lithium fluoride) is used as an additive to aluminium smelters (Hall–Héroult process), reducing melting temperature and increasing electrical resistance,[164] a use which accounts for 3% of production (2011).[55]
When used as a
Silicon nano-welding
Lithium has been found effective in assisting the perfection of silicon nano-welds in electronic components for electric batteries and other devices.[168]
Pyrotechnics
Lithium compounds are used as
Air purification
Lithium peroxide (Li2O2) in presence of moisture not only reacts with carbon dioxide to form lithium carbonate, but also releases oxygen.[171][172] 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.[173]
Optics
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.[177]
Organic and polymer chemistry
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.
Military
Metallic lithium and its complex hydrides, such as lithium aluminium hydride (LiAlH4), are used as high-energy additives to rocket propellants.[38] LiAlH4 can also be used by itself as a solid fuel.[183]
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.[184]
Lithium hydride containing lithium-6 is used in thermonuclear weapons, where it serves as fuel for the fusion stage of the bomb.[185]
Nuclear
Lithium-6 is valued as a source material for
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
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.". Castle Bravo first used lithium-7 in the Shrimp, its first device, which weighed only 10 tons, and generated massive nuclear atmospheric contamination of Bikini Atoll. This perhaps accounts for the decline of US nuclear infrastructure.[194] 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.[195]
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.[195]
Medicine
Lithium is useful in the treatment of
Precautions
Hazards | |
---|---|
GHS labelling: | |
Danger | |
H260, H314 | |
P223, P231+P232, P280, P305+P351+P338, P370+P378, P422[198] | |
NFPA 704 (fire diamond) |
Lithium metal is
See also
- Cosmological lithium problem
- Dilithium
- Halo nucleus
- Isotopes of lithium
- List of countries by lithium production
- Lithia water
- Lithium–air battery
- Lithium burning
- Lithium compounds (category)
- Lithium-ion battery
- Lithium Tokamak Experiment
Notes
- ^ a b Appendixes Archived 6 November 2011 at the Wayback Machine. By USGS definitions, the reserve base "may encompass those parts of the resources that have a reasonable potential for becoming economically available within planning horizons beyond those that assume proven technology and current economics. The reserve base includes those resources that are currently economic (reserves), marginally economic (marginal reserves), and some of those that are currently subeconomic (subeconomic resources)."
- ^ In 2013
- ^ Excludes U.S. production
- ^ Beryllium and fluorine occur only as one isotope, 9Be and 19F respectively. These two, together with 7Li, as well as 2H, 11B, 15N, 209Bi, and the stable isotopes of C, and O, are the only nuclides with low enough thermal neutron capture cross sections aside from actinides to serve as major constituents of a molten salt breeder reactor fuel.
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External links
- McKinsey review of 2018 (PDF)
- Lithium at The Periodic Table of Videos(University of Nottingham)
- International Lithium Alliance (archived, August 2009)
- USGS: Lithium Statistics and Information
- Lithium Supply & Markets 2009 IM Conference 2009 Sustainable lithium supplies through 2020 in the face of sustainable market growth
- University of Southampton, Mountbatten Centre for International Studies, Nuclear History Working Paper No5. (PDF) (archived February 26 February 2008)
- Lithium preserves by Country at investingnews.com