Lithium carbonate

Lithium carbonate is an inorganic compound, the lithium salt of carbonate with the formula Li
2CO
3. This white salt is widely used in the processing of metal oxides. It is listed on the World Health Organization's List of Essential Medicines[7] because it can be used as a treatment for mood disorders such as bipolar disorder.[8][7]

Lithium carbonate
Names
IUPAC name
Lithium carbonate
Other names
Dilithium carbonate, Carbolith, Cibalith-S, Duralith, Eskalith, Lithane, Lithizine, Lithobid, Lithonate, Lithotabs Priadel, Zabuyelite
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.008.239
KEGG
RTECS number
  • OJ5800000
UNII
CompTox Dashboard (EPA)
  • InChI=1S/CH2O3.2Li/c2-1(3)4;;/h(H2,2,3,4);;/q;2*+1/p-2 Y
    Key: XGZVUEUWXADBQD-UHFFFAOYSA-L Y
  • InChI=1/CH2O3.2Li/c2-1(3)4;;/h(H2,2,3,4);;/q;2*+1/p-2
    Key: XGZVUEUWXADBQD-NUQVWONBAY
  • [Li+].[Li+].[O-]C([O-])=O
Properties
Li
2CO
3
Molar mass 73.89 g/mol
Appearance Odorless white powder
Density 2.11 g/cm3
Melting point 723 °C (1,333 °F; 996 K)
Boiling point 1,310 °C (2,390 °F; 1,580 K)
Decomposes from ~1300 °C
  • 1.54 g/100 mL (0 °C)
  • 1.43 g/100 mL (10 °C)
  • 1.29 g/100 mL (25 °C)
  • 1.08 g/100 mL (40 °C)
  • 0.69 g/100 mL (100 °C)[1]
8.15×10−4[2]
Solubility Insoluble in acetone, ammonia, alcohol[3]
−27.0·10−6 cm3/mol
1.428[4]
Viscosity
  • 4.64 cP (777 °C)
  • 3.36 cP (817 °C)[3]
Thermochemistry
97.4 J/mol·K[3]
Std molar
entropy (S⦵298)
 90.37 J/mol·K[3]
−1215.6 kJ/mol[3]
−1132.4 kJ/mol[3]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Irritant
GHS labelling:
[5]
Warning
Hazard statements
 H302, H319[5]
Precautionary statements
 P305+P351+P338[5]
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
525 mg/kg (oral, rat)[6]
Safety data sheet (SDS) ICSC 1109
Related compounds
Other cations
 Sodium carbonate
Potassium carbonate
Rubidium carbonate
Caesium carbonate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Uses

Lithium carbonate is an important industrial chemical. Its main use is as a precursor for compounds used in lithium-ion batteries. Glasses derived from lithium carbonate are useful in ovenware. Lithium carbonate is a common ingredient in both low-fire and high-fire ceramic glaze. It forms low-melting fluxes with silica and other materials. Its alkaline properties are conducive to changing the state of metal oxide colorants in glaze, particularly red iron oxide (Fe
2O
3). Cement sets more rapidly when prepared with lithium carbonate, and is useful for tile adhesives. When added to aluminium trifluoride, it forms LiF which gives a superior electrolyte for the processing of aluminium.[9]

Rechargeable batteries

The main use of lithium carbonate (and lithium hydroxide) is as a precursor to lithium compounds used in lithium-ion batteries. In practice two components of the battery are made with lithium compounds: the cathode and the electrolyte.

The electrolyte is a solution of lithium hexafluorophosphate, while the cathode uses one of several lithiated structures, the most popular of which are lithium cobalt oxide and lithium iron phosphate. Lithium carbonate may be converted into lithium hydroxide before conversion to the compounds above.

Lithium prices

Medical uses
Main article: Lithium (medication)

In 1843, lithium carbonate was used to treat stones in the bladder. In 1859, some doctors recommended a therapy with lithium salts for a number of ailments, including gout, urinary calculi, rheumatism, mania, depression, and headache. In 1948, John Cade discovered the anti-manic effects of lithium ions. This finding led lithium, specifically the lithium carbonate, to be used to treat manias associated with bipolar disorder.[10]

Lithium carbonate is used as a psychiatric medication to treat mania, the elevated phase of bipolar disorder. Prescription lithium carbonate from a pharmacy is suitable for use as medicine in humans while industrial lithium carbonate is not since the latter may, for example, contain unsafe levels of toxic heavy metals or other toxicants. After ingestion, lithium carbonate is dissociated into pharmacologically active lithium ions (Li+) and (non-therapeutic) carbonate, with 300 mg of lithium carbonate containing approximately 8 mEq (8 mmol) of lithium ion.[8] According to the Food and Drug Administration (FDA), 300–600 mg of lithium carbonate taken two to three times daily is typical for maintenance of bipolar I disorder in adults,[8] where the exact dose given varies depending on factors such as the patient's serum lithium concentrations, which must be closely monitored by a physician to avoid lithium toxicity and potential kidney damage (or even kidney failure) from lithium-induced nephrogenic diabetes insipidus.[11][8] Dehydration and certain drugs, including NSAIDs such as ibuprofen, can increase serum lithium concentrations to unsafe levels whereas other drugs, such as caffeine, may decrease concentrations. In contrast to elements such as sodium, potassium, and calcium, there is no known cellular mechanism specifically dedicated to regulating intracellular lithium. Lithium can enter cells through epithelial sodium channels.[12] Lithium ions interfere with ion transport processes (see “sodium pump”) that relay and amplify messages carried to the cells of the brain.[13] Mania is associated with irregular increases in protein kinase C (PKC) activity within the brain. Lithium carbonate and sodium valproate, another drug traditionally used to treat the disorder, act in the brain by inhibiting PKC's activity and help to produce other compounds that also inhibit the PKC.[14] Lithium carbonate's mood-controlling properties are not fully understood.[15]

Health risks

Taking lithium salts has risks and side effects. Extended use of lithium to treat various mental disorders has been known to lead to acquired nephrogenic diabetes insipidus.[16] Lithium intoxication can affect the central nervous system and renal system and can be lethal.[17] Over a prolonged period of time, lithium can accumulate in the principal cells of the collecting duct and interfere with antidiuretic hormone (ADH), which regulates the water permeability of principal cells in the collecting tubule.[12] The medullary interstitium of the collecting duct system naturally has a high sodium concentration and actively attempts to maintain this. There is no known mechanism by which cells can distinguish lithium ions from sodium ions and damage to the kidney's nephrons may occur if lithium concentrations become too high, which for example can result from dehydration, hyponatremia, an unusually low sodium diet, or certain drugs.

Red pyrotechnic colorant

Lithium carbonate is used to impart a red color to fireworks.[18]

Properties and reactions

Unlike sodium carbonate, which forms at least three hydrates, lithium carbonate exists only in the anhydrous form. Its solubility in water is low relative to other lithium salts. The isolation of lithium from aqueous extracts of lithium ores capitalizes on this poor solubility. Its apparent solubility increases 10-fold under a mild pressure of carbon dioxide; this effect is due to the formation of the metastable bicarbonate, which is more soluble:[9]

Li
2CO
3 + CO
2 + H
2O ⇌ 2 LiHCO
3

The extraction of lithium carbonate at high pressures of CO
2 and its precipitation upon depressurizing is the basis of the Quebec process.

Lithium carbonate can also be purified by exploiting its diminished solubility in hot water. Thus, heating a saturated aqueous solution causes crystallization of Li
2CO
3.[19]

Lithium carbonate, and other carbonates of group 1, do not decarboxylate readily. Li
2CO
3 decomposes at temperatures around 1300 °C.

Production

Lithium is extracted from primarily two sources: spodumene in pegmatite deposits, and lithium salts in underground brine pools. About 82,000 tons were produced in 2020, showing significant and consistent growth.[20]

From underground brine reservoirs

As an example, in the Salar de Atacama in the Atacama desert of Northern Chile, SQM produces lithium carbonate and hydroxide from brine.[21][22]

The process involves pumping up lithium rich brine from below the ground into shallow pans for evaporation. The brine contains many different dissolved ions, and as the concentration increases, salts precipitate out of solution and sink. The remaining liquid (the supernatant) is used for the next step. The exact sequence of pans may vary depending on the concentration of ions in a particular source of brine.

In the first pan, halite (sodium chloride or common salt) crystallises. This has insufficient economic value and is discarded. The supernatant, with ever increasing concentration of dissolved solids, is transferred successively to the sylvinite (sodium potassium chloride) pan, the carnalite (potassium magnesium chloride) pan and finally a pan designed to maximise the concentration of lithium chloride. The process takes about 15 months. The concentrate (30-35% lithium chloride solution) is trucked to Salar del Carmen. There, boron and magnesium are removed (typically residual boron is removed by solvent extraction and/or ion exchange and magnesium by raising the pH above 10 with sodium hydroxide)[23] then in the final step, by addition of sodium carbonate, the desired lithium carbonate is precipitated out, separated, and processed.

Some of the by-products from the evaporation process may also have economic value.

There is considerable focus on the use of water in this water poor region. SQM commissioned a life-cycle analysis which concluded that water consumption for SQM's lithium hydroxide and carbonate is significantly lower than the average consumption in production from the main ore-based process, using spodumene. A more general LCA suggests the opposite for extraction from reservoirs as a whole.[24]

The majority of brine based production is in the "lithium triangle" in South America.

From 'geothermal' brine

Another potential source of lithium is the leachates of geothermal wells, which are carried to the surface.[25] Recovery of lithium has been demonstrated in the field; the lithium is separated by simple precipitation and filtration.[26] The process and environmental costs are primarily those of the already-operating well; net environmental impacts may thus be positive.[27]

The brine of United Downs Deep Geothermal Power project near Redruth is claimed by Cornish Lithium to be valuable due to its high lithium concentration (220 mg/L) with low magnesium (<5 mg/L) and total dissolved solids content of <29g/L,[28] and a flow rate of 40-60l/s.[24]

From ore

α-spodumene is roasted at 1100 °C for 1h to make β-spodumene, then roasted at 250 °C for 10 minutes with sulphuric acid.[29][21]

As of 2020, Australia was the world's largest producer of lithium intermediates,[30] all based on spodumene.

In recent years many mining companies have begun exploration of lithium projects throughout North America, South America and Australia to identify economic deposits that can potentially bring new supplies of lithium carbonate online to meet the growing demand for the product.[31]

From clay

Tesla Motors announced a revolutionary process to extract lithium from clay in Nevada using only salt and no acid. This was met with scepticism.[32]

From end of life batteries

A few small companies are actively recycling spent batteries, mostly focusing on recovering copper and cobalt. Some do recover lithium also.[33]

Other

In April 2017 MGX Minerals reported it had received independent confirmation of its rapid lithium extraction process to recover lithium and other valuable minerals from oil and gas wastewater brine. [34]

Electrodialysis has been proposed to extract lithium from seawater, but it is not commercially viable.[35]

Natural occurrence

Natural lithium carbonate is known as zabuyelite.[36] This mineral is connected with deposits of some salt lakes and some pegmatites.[37]

References
  1. Seidell, Atherton; Linke, William F. (1952). Solubilities of Inorganic and Organic Compounds. Van Nostrand.
  2. John Rumble (June 18, 2018). CRC Handbook of Chemistry and Physics (99 ed.). CRC Press. pp. 5–188. ISBN 978-1138561632.
  3. "lithium carbonate". Chemister.ru. 2007-03-19. Retrieved 2017-01-02.
  4. Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8
  5. Sigma-Aldrich Co., Lithium carbonate. Retrieved on 2014-06-03.
  6. Michael Chambers. "ChemIDplus - 554-13-2 - XGZVUEUWXADBQD-UHFFFAOYSA-L - Lithium carbonate [USAN:USP:JAN] - Similar structures search, synonyms, formulas, resource links, and other chemical information". Chem.sis.nlm.nih.gov. Retrieved 2017-01-02.
  7. "WHO Model List of Essential Medicines" (PDF). World Health Organization. October 2013. Retrieved 22 April 2014.
  8. "Lithium Carbonate Medication Guide" (PDF). U.S. FDA. Archived (PDF) from the original on 27 January 2022. Retrieved 27 January 2022.
  9. Ulrich Wietelmann, Richard J. Bauer (2005). "Lithium and Lithium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_393. ISBN 3527306730.{{cite encyclopedia}}: CS1 maint: uses authors parameter (link)
  10. Cade, J. F. (2000). "Lithium salts in the treatment of psychotic excitement. 1949". Bulletin of the World Health Organization. 78 (4): 518–520. ISSN 0042-9686. PMC 2560740. PMID 10885180.
  11. Amdisen A. (1978). "Clinical and serum level monitoring in lithium therapy and lithium intoxication". J. Anal. Toxicol. 2 (5): 193–202. doi:10.1093/jat/2.5.193.
  12. Lerma, Edgar V. "Renal toxicity of lithium". UpToDate. Retrieved 8 March 2022.
  13. "lithium, Lithobid: Drug Facts, Side Effects and Dosing". Medicinenet.com. 2016-06-17. Retrieved 2017-01-02.
  14. Yildiz, A; Guleryuz, S; Ankerst, DP; Ongür, D; Renshaw, PF (2008). "Protein kinase C inhibition in the treatment of mania: a double-blind, placebo-controlled trial of tamoxifen" (PDF). Archives of General Psychiatry. 65 (3): 255–63. doi:10.1001/archgenpsychiatry.2007.43. PMID 18316672.
  15. Lithium Carbonate at PubChem
  16. Richard T. Timmer; Jeff M. Sands (1999-03-01). "Lithium Intoxication". Journal of the American Society of Nephrology. 10 (3): 666–674. doi:10.1681/ASN.V103666. PMID 10073618. Retrieved 2017-01-02.
  17. Simard, M; Gumbiner, B; Lee, A; Lewis, H; Norman, D (1989). "Lithium carbonate intoxication. A case report and review of the literature" (PDF). Archives of Internal Medicine. 149 (1): 36–46. doi:10.1001/archinte.149.1.36. PMID 2492186. Archived from the original (PDF) on 2011-07-26. Retrieved 2010-09-11.
  18. "Chemistry of Fireworks".
  19. Caley, E. R.; Elving, P. J. (1939). "Purification of Lithium Carbonate". Inorganic Syntheses. Inorganic Syntheses. Vol. 1. pp. 1–2. doi:10.1002/9780470132326.ch1. ISBN 9780470132326.
  20. "Global lithium production 2020".
  21. "Sustainability of lithium production in Chile" (PDF). SQM. SQM. Retrieved 1 December 2020.
  22. Telsnig, Thomas; Potz, Christian; Haas, Jannik; Eltrop, Ludger; Palma-Behnke, Rodrigo (2017). Opportunities to integrate solar technologies into the Chilean lithium mining industry – reducing process related GHG emissions of a strategic storage resource. Solarpaces 2016: International Conference on Concentrating Solar Power and Chemical Energy Systems. AIP Conference Proceedings. Vol. 1850. p. 110017. Bibcode:2017AIPC.1850k0017T. doi:10.1063/1.4984491.
  23. Dry, Mike. "Extraction of Lithium from Brine – Old and New Chemistry" (PDF). Critical Materials Symposium, EXTRACTION 2018, Ottawa, August 26–29. Retrieved 1 December 2020.
  24. Early, Catherine (25 Nov 2020). "The new 'gold rush' for green lithium". Future Planet. BBC. Retrieved 2 December 2020.
  25. Parker, Ann. Mining Geothermal Resources Archived 17 September 2012 at the Wayback Machine. Lawrence Livermore National Laboratory
  26. Patel, P. (16 November 2011) Startup to Capture Lithium from Geothermal Plants. technologyreview.com
  27. Wald, M. (28 September 2011) Start-Up in California Plans to Capture Lithium, and Market Share Archived 8 April 2017 at the Wayback Machine. The New York Times
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  29. Meshram, Pratima; Pandey, B. D.; Mankhand, T. R. (1 December 2014). "Extraction of lithium from primary and secondary sources by pre-treatment, leaching and separation: A comprehensive review". Hydrometallurgy. 150: 192–208. doi:10.1016/j.hydromet.2014.10.012. Retrieved 2 Dec 2020.
  30. Jaskula, Brian W. (January 2020). "Mineral Commodity Summaries 2020" (PDF). U.S. Geological Survey. Retrieved 29 June 2020.
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  32. Scheyder, Ernest (24 Sep 2020). "Tesla's Nevada lithium plan faces stark obstacles on path to production". Reuters. Retrieved 2 December 2020.
  33. Serna-Guerrero, Rodrigo (5 November 2019). "A Critical Review of Lithium-Ion Battery Recycling Processes from a Circular Economy Perspective". Batteries. 5 (4): 68. doi:10.3390/batteries5040068.
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  35. Martin, Richard (2015-06-08). "Quest to Mine Seawater for Lithium Advances". MIT Technology Review. Retrieved 2016-02-10.
  36. David Barthelmy. "Zabuyelite Mineral Data". Mineralogy Database. Retrieved 2010-02-07.
  37. mindat.org

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