======================================================================
= Lithium =
======================================================================
Introduction
======================================================================
{{Redirect|3Li|the isotope of lithium with three
nucleons|Lithium-3{{chem2|^{3}Li}}}}
Lithium (from , , ) 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 or mineral oil. It exhibits a
metallic luster. It corrodes quickly 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. 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.
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.
Lithium is present in biological systems in trace amounts. It has no
established metabolic function in humans. Lithium-based drugs are
useful as a mood stabilizer and antidepressant in the treatment of
mental illness such as bipolar disorder.
Atomic and physical
=====================
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+. 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). Molten lithium is significantly more reactive than its solid
form.
Lithium metal is soft enough to be cut with a knife. It is
silvery-white. In air it oxidizes to lithium oxide. Its melting point
of and its boiling point of 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. 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). 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's coefficient of thermal expansion is twice that of aluminium
and almost four times that of iron. Lithium is superconductive below
400 μK at standard pressure and at higher temperatures (more than 9 K)
at very high pressures (>20 GPa). 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. Multiple
allotropic forms have been identified for lithium at high pressures.
Lithium has a mass specific heat capacity of 3.58 kilojoules per
kilogram-kelvin, the highest of all solids. Because of this, lithium
metal is often used in coolants for heat transfer applications.
Isotopes
==========
Naturally occurring lithium is composed of two stable isotopes, 6Li
and 7Li, the latter being the more abundant (95.15% natural
abundance). 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. 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. 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. 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.
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. 7Li can also be
generated in carbon stars. 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.
Lithium isotopes fractionate substantially during a wide variety of
natural processes, 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.
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.
Both stable isotopes of lithium can be laser cooled and were used to
produce the first quantum degenerate Bose-Fermi mixture.
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.
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. 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. The lack of lithium in older stars is
apparently caused by the "mixing" of lithium into the interior of
stars, where it is destroyed, 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.
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. 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.
On 27 May 2020, astronomers reported that classical nova explosions
are galactic producers of lithium-7.
Terrestrial
=============
Although lithium is widely distributed on Earth, it does not naturally
occur in elemental form due to its high reactivity. 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), or 25
micromolar; higher concentrations approaching 7 ppm are found near
hydrothermal vents.
Estimates for the Earth's crustal content range from 20 to 70 ppm by
weight. 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. Another significant mineral of lithium is lepidolite
which is now an obsolete name for a series formed by polylithionite
and trilithionite. Another source for lithium is hectorite clay, the
only active development of which is through the Western Lithium
Corporation in the United States. At 20 mg lithium per kg of Earth's
crust, lithium is the 31st 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."
Chile is estimated (2020) to have the largest reserves by far (9.2
million tonnes), and Australia the highest annual production (40,000
tonnes). One of the largest 'reserve bases' 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. 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 is considered as a potentially economical deposit, with 160 000
tonnes of lithium. 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.
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. These estimates are "based principally on old data, which was
gathered mainly by the Soviets during their occupation of Afghanistan
from 1979-1989". 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". 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.
Biological
============
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. Marine organisms tend to bioaccumulate lithium more than
terrestrial organisms. Whether lithium has a physiological role in any
of these organisms is unknown.
Lithium concentrations in human tissue averages about 24 ppb (4 ppb in
blood, and 1.3 ppm in bone).
Lithium is easily absorbed by plants and lithium concentration in
plant tissue is typically around 1 ppm. Some plant families
bioaccumulate more lithium than others. 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.
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.
Lithium accumulation does not appear to affect the essential nutrient
composition of plants. 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. 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).
Many of lithium's major biological effects can be explained by its
competition with other ions.
The monovalent lithium ion 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 (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.
Lithium ions can also permeate through ligand-gated ion channels as
well as cross both nuclear and mitochondrial membranes.
Like sodium, lithium can enter and partially block (although not
permeate) potassium channels and calcium channels.
The biological effects of lithium are many and varied but its
mechanisms of action are only partially understood.
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.
Even the exact mechanisms involved in lithium toxicity are not fully
understood.
History
======================================================================
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. 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. This element formed compounds similar to those
of sodium and potassium, though its carbonate and hydroxide were less
soluble in water and less alkaline. 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".
Arfwedson later showed that this same element was present in the
minerals spodumene and lepidolite.See:
* Arfwedson, Aug. (1818) , 'Afhandlingar i Fysik, Kemi och
Mineralogi', 6 : 145-172. (in Swedish)
* Arfwedson, Aug. (1818)
[
https://babel.hathitrust.org/cgi/pt?id=njp.32101076802493;view=1up;seq=105
"Untersuchung einiger bei der Eisen-Grube von Utö vorkommenden
Fossilien und von einem darin gefundenen neuen feuerfesten Alkali"]
(Investigation of some minerals occurring at the iron mines of Utö and
of a new refractory alkali found therein), 'Journal für Chemie und
Physik', 22 (1) : 93-117. (in German) In 1818, Christian Gmelin was
the first to observe that lithium salts give a bright red color to
flame. However, both Arfwedson and Gmelin tried and failed to isolate
the pure element from its salts. 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. 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). In 1855, larger quantities of lithium were
produced through the electrolysis of lithium chloride by Robert Bunsen
and Augustus Matthiessen. 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.
Australian psychiatrist John Cade is credited with reintroducing and
popularizing the use of lithium to treat mania in 1949. 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.
Lithium is used to decrease the melting temperature of glass and to
improve the melting behavior of aluminium oxide in the Hall-Héroult
process. 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. 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. With the surge of lithium
demand in batteries in the 2000s, new companies have expanded brine
isolation efforts to meet the rising demand.
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. 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). Lithium is one
of the few metals that react with nitrogen gas.
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.
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 () and peroxide () when burnt in O2, salts with
similar solubilities, and thermal instability of the carbonates and
nitrides. The metal reacts with hydrogen gas at high temperatures to
produce lithium hydride (LiH).
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.
It dissolves in ammonia (and amines) to give [Li(NH3)4]+ and the
solvated electron.
Inorganic compounds
=====================
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. 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 Lithium borohydride and Lithium aluminium hydride 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
===================
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. 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). 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.
Production
======================================================================
Lithium mine production (2023), reserves and resources in tonnes
according to USGS
Country data-sort-type="number" | Production data-sort-type="number"
| Reserves data-sort-type="number" | 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
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 1,800,000 14,000,000
Zimbabwe 14,900 480,000 860,000
Other countries - 2,800,000 -
| **World total**
| **204,000**
| **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.
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.
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 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.
The US Geological Survey (USGS) estimated worldwide identified lithium
reserves in 2022 and 2023 to be 26 million and 28 million tonnes,
respectively. An accurate estimate of world lithium reserves is
difficult. 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.
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).
Lithium triangle and other brine sources
==========================================
The world's top four lithium-producing countries in 2019, as reported
by the US Geological Survey, were Australia, Chile, China and
Argentina.
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 was estimated to contain over 75% of existing known
lithium reserves. Deposits found in subsurface brines have also been
found in 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. 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. The brines in
the salt pans of the Lithium Triangle vary widely in lithium content.
Concentrations can also vary over time as brines are fluids that are
changeable and mobile.
In the US, lithium is recovered from brine pools in Nevada. Projects
are also under development in Lithium Valley in California and from
brine in southwest Arkansas using a direct lithium extraction process,
drawing on the deep brine resource in the Smackover Formation.
Hard-rock deposits
====================
Since 2018 the Democratic Republic of Congo is known to have the
largest lithium spodumene hard-rock deposit in the world. 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.
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. Operational mining began in 2022.
Extracting lithium from brine deep in Wyoming's Rock Springs Uplift
has been proposed as revenue source to make atmospheric carbon
sequestration economically viable. Additional deposits in the same
formation were estimated to be as much as 18 million tons if economic
means of recovery can be employed. Similarly in Nevada, the McDermitt
Caldera hosts lithium-bearing volcanic muds that consist of the
largest known deposits of lithium within the United States.
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 %.
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.
Sources
=========
Another potential source of lithium was identified as the leachates
of geothermal wells, which are carried to the surface. Recovery of
this type of lithium has been demonstrated in the field; the lithium
is separated by simple filtration. Reserves are more limited than
those of brine reservoirs and hard rock.
Pricing
=========
In 1998, the price of lithium metal was about (or US$43/lb). After
the 2008 financial crisis, major suppliers, such as Sociedad Química y
Minera (SQM), dropped lithium carbonate pricing by 20%. 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. Global consumption may jump to
300,000 metric tons a year by 2020 from about 150,000 tons in 2012, to
match the demand for lithium batteries that has been growing at about
25% a year, outpacing the 4% to 5% overall gain in lithium production.
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.
Extraction
============
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. Most of these were
in Chile, Argentina and Bolivia and the lithium is extracted from the
brine by evaporative processes. Large lithium-clay deposits under
development in the McDermitt caldera (Nevada, United States) require
concentrated sulfuric acid to leach lithium from the clay ore.
By early 2021, much of the lithium mined globally came from either
"spodumene, the mineral contained in hard rocks found in places such
as Australia and North Carolina" or from salty brine pumped directly
out of the ground, as it is in locations in Chile and Argentina. In
Chile's Salar de Atacama, the lithium concentration in the brine is
raised by solar evaporation in a system of ponds. The enrichment by
evaporation process may require up to one-and-a-half years, when the
brine reaches a lithium content of 6%. 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.
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. Some
recent lithium mining projects are attempting to bring DLE into
commercial production by these non-evaporative DLE approaches.
One method direct lithium extraction, as well as other valuable
minerals, is to process geothermal brine water through an electrolytic
cell, located within a membrane.
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). Ion-selective cells within
a membrane in principle could collect lithium either by use of
electric field or a concentration difference. In 2024, a
redox/electrodialysis system was claimed to offer enormous cost
savings, shorter timelines, and less environmental damage than
traditional evaporation-based systems.
Environmental issues
======================
The manufacturing processes of lithium, including the solvent and
mining waste, presents significant environmental and health hazards.
Lithium extraction can be fatal to aquatic life due to water
pollution. It is known to cause surface water contamination, drinking
water contamination, respiratory problems, ecosystem degradation and
landscape damage. It also leads to unsustainable water consumption in
arid regions (1.9 million liters per ton of lithium), such as in
northwestern Argentina. Massive byproduct generation of lithium
extraction also presents unsolved problems, such as large amounts of
magnesium and lime waste.
Although lithium occurs naturally, it is a non-renewable resource 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.
In the United States, open-pit mining and mountaintop removal mining
compete with brine extraction mining. 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.
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. In 2024, an EU backed lithium mining project created
large scale protests in Serbia.
Some animal species associated to salt lakes in the Lithium Triangle
(on the borders of Argentina, Bolivia and Chile) are particularly
threatened by the damages of lithium production to the local
ecosystem, including the Andean flamingo and 'Orestias
parinacotensis', a small fish locally known as "karachi".
Human rights issues
=====================
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.
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.
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. 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.
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. 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. Protestors have been occupying the site
of the proposed mine since January 2021.
Batteries
===========
In 2021, most lithium is used to make lithium-ion batteries for
electric cars and mobile devices.
Ceramics and glass
====================
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. 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.
Electrical and electronic
===========================
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. Other rechargeable batteries that use
lithium include the lithium-ion polymer battery, lithium iron
phosphate battery, and the nanowire battery.
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'".
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.
Metallurgy
============
Lithium (e.g. as lithium carbonate) is used as an additive to
continuous casting mould flux slags where it increases fluidity, a use
which accounts for 5% of global lithium use (2011). Lithium compounds
are also used as additives (fluxes) to foundry sand for iron casting
to reduce veining.
Lithium (as lithium fluoride) is used as an additive to aluminium
smelters (Hall-Héroult process), reducing melting temperature and
increasing electrical resistance, a use which accounts for 3% of
production (2011).
When used as a flux for welding or soldering, metallic lithium
promotes the fusing of metals during the process and eliminates the
formation of oxides by absorbing impurities. 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).
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.
Pyrotechnics
==============
Lithium compounds are used as pyrotechnic colorants and oxidizers in
red fireworks and flares.
Air purification
==================
Lithium chloride and lithium bromide are hygroscopic and are used as
desiccants for gas streams. 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.
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.
Optics
========
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. 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. Lithium fluoride is sometimes used in focal lenses of
telescopes.
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.
Organic and polymer chemistry
===============================
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 in anionic polymerization of unfunctionalized
olefins. 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.
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. LiAlH4 can also be used by itself as a solid fuel.
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.
Lithium hydride containing lithium-6 is used in thermonuclear weapons,
where it serves as fuel for the fusion stage of the bomb.
Nuclear
=========
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. Lithium-7
gained interest for use in nuclear reactor coolants.
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.
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.
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. 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.
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.
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.
Medicine
==========
Lithium is useful in the treatment of bipolar disorder. 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+. 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.
Precautions
======================================================================
{{Chembox
| container_only = yes
|Section7=
}}
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 is
safely stored in non-reactive compounds such as naphtha.
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
External links
======================================================================
*
[
https://www.mckinsey.com/~/media/mckinsey/industries/metals%20and%20mining/our%20insights/lithium%20and%20cobalt%20a%20tale%20of%20two%20commodities/lithium-and-cobalt-a-tale-of-two-commodities.pdf
McKinsey review of 2018] (PDF)
* [
http://www.periodicvideos.com/videos/003.htm Lithium] at 'The
Periodic Table of Videos' (University of Nottingham)
*
[
https://web.archive.org/web/20090817001127/http://www.lithiumalliance.org/
International Lithium Alliance] (archived, August 2009)
* [
http://minerals.usgs.gov/minerals/pubs/commodity/lithium/ USGS:
Lithium Statistics and Information]
* [
http://trugroup.com/whitepapers/TRU-Lithium-Outlook-2020.pdf
Lithium Supply & Markets 2009 IM Conference 2009 Sustainable
lithium supplies through 2020 in the face of sustainable market
growth]
*
[
https://web.archive.org/web/20080226213021/https://www.mcis.soton.ac.uk/Site_Files/pdf/nuclear_history/Working_Paper_No_5.pdf
University of Southampton, Mountbatten Centre for International
Studies, Nuclear History Working Paper No5.] (PDF) (archived February
26 February 2008)
*
[
https://investingnews.com/daily/resource-investing/battery-metals-investing/lithium-investing/lithium-reserves-country/
Lithium reserves by Country] at investingnews.com
License
=========
All content on Gopherpedia comes from Wikipedia, and is licensed under CC-BY-SA
License URL:
http://creativecommons.org/licenses/by-sa/3.0/
Original Article:
http://en.wikipedia.org/wiki/Lithium
