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Lithium hydroxide

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Lithium hydroxide
Lithium hydroxide

  Li+        O2−       H+
Lithium-hydroxide.jpg
Names
IUPAC name
Lithium hydroxide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.804 Edit this at Wikidata
68415
RTECS number
  • OJ6307070
UNII
UN number 2680
  • InChI=1S/Li.H2O/h;1H2/q+1;/p-1 checkY
    Key: WMFOQBRAJBCJND-UHFFFAOYSA-M checkY
  • InChI=1/Li.H2O/h;1H2/q+1;/p-1
    Key: WMFOQBRAJBCJND-REWHXWOFAT
  • [Li+].[OH-]
Properties
LiOH
Molar mass
  • 23.95 g/mol (anhydrous)
  • 41.96 g/mol (monohydrate)
Appearance
Odor none
Density
  • 1.46 g/cm3 (anhydrous)
  • 1.51 g/cm3 (monohydrate)
Melting point 462 °C (864 °F; 735 K)
Boiling point 924 °C (1,695 °F; 1,197 K) decomposes
  • (anhydrous:)
  • 12.7 g/100 mL (0 °C)
  • 12.8 g/100 mL (20 °C)
  • 17.5 g/100 mL (100 °C)
  • (monohydrate:)
  • 22.3 g/100 mL (10 °C)
  • 26.8 g/100 mL (80 °C)[1]
Solubility in methanol
  • 9.76 g/100 g (anhydrous; 20 °C, 48 hours mixing)
  • 13.69 g/100 g (monohydrate; 20 °C, 48 hours mixing)[2]
Solubility in ethanol
  • 2.36 g/100 g (anhydrous; 20 °C, 48 hours mixing)
  • 2.18 g/100 g (monohydrate; 20 °C, 48 hours mixing)[2]
Solubility in isopropanol
  • 0 g/100 g (anhydrous; 20 °C, 48 hours mixing)
  • 0.11 g/100 g (monohydrate; 20 °C, 48 hours mixing)[2]
Basicity (pKb) −0.04[3]
Conjugate base Lithium monoxide anion
−12.3·10−6 cm3/mol
  • 1.464 (anhydrous)
  • 1.460 (monohydrate)
Thermochemistry
2.071 J/g⋅K
−20.36 kJ/g
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Corrosive
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point Non-flammable
Lethal dose or concentration (LD, LC):
210 mg/kg (oral, rat)[4]
Safety data sheet (SDS) "ICSC 0913".
"ICSC 0914". (monohydrate)
Related compounds
Other anions
 Lithium amide
Other cations
 Sodium hydroxide
Potassium hydroxide
Rubidium hydroxide
Caesium hydroxide
Related compounds
 Lithium oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Lithium hydroxide is an inorganic compound with the formula LiOH.(H2O)n. Both the anhydrous and hydrated forms are white hygroscopic solids. They are soluble in water and slightly soluble in ethanol. Both are available commercially. While classified as a strong base, lithium hydroxide is the weakest known alkali metal hydroxide.


Production

The preferred feedstock is hard-rock spodumene, where the lithium content is expressed as % lithium oxide.

Lithium carbonate route

Lithium hydroxide is often produced industrially from lithium carbonate in a metathesis reaction with calcium hydroxide:[5]

Li2CO3 + Ca(OH)2 → 2 LiOH + CaCO3

The initially produced hydrate is dehydrated by heating under vacuum up to 180 °C.

Lithium sulfate route

An alternative route involves the intermediacy of lithium sulfate:[6][7]

α-spodumene → β-spodumene
β-spodumene + CaO → Li2O + ...
Li2O + H2SO4 → Li2SO4 + H2O
Li2SO4 + 2 NaOH → Na2SO4 + 2 LiOH.

The main by-products are gypsum and sodium sulphate, which have some market value.

Commercial setting

According to Bloomberg, Ganfeng Lithium Co. Ltd.[8] (GFL or Ganfeng)[9] and Albemarle were the largest producers in 2020 with around 25kt/y, followed by Livent (FMC) and SQM.[8] Significant new capacity is planned, to keep pace with demand driven by vehicle electrification. Ganfeng are to expand lithium chemical capacity to 85,000 tons, adding the capacity leased from Jiangte, Ganfeng will become the largest lithium hydroxide producer globally in 2021.[8]

Albemarle's Kemerton WA plant, originally planned to deliver 100kt/y has been scaled back to 50kt/yy.[10]

in 2023 AVZ Minerals,[11] an Australian company, are planning to produce the battery-grade high-purity Primary Lithium Sulphate (PLS) containing over 80% Lithium.[12] PLS is a lithium chemical new to the market in the production of lithium hydroxide (a precursor to lithium-ion battery).

In 2020 Tianqi Lithium's, plant in Kwinana, Western Australia is the largest producer, with a capacity of 48kt/y.[13]

Applications

Lithium ion batteries

Lithium hydroxide is mainly consumed in the production of cathode materials for lithium ion batteries such as lithium cobalt oxide (LiCoO2) and lithium iron phosphate. It is preferred over lithium carbonate as a precursor for lithium nickel manganese cobalt oxides.[14]

Grease

A popular lithium grease thickener is Lithium 12-hydroxystearate, which produces a general-purpose lubricating grease due to its high resistance to water and usefulness at a range of temperatures.

Carbon dioxide scrubbing

Further information: carbon dioxide scrubber

Lithium hydroxide is used in breathing gas purification systems for spacecraft, submarines, and rebreathers to remove carbon dioxide from exhaled gas by producing lithium carbonate and water:[15]

2 LiOH•H2O + CO2 → Li2CO3 + 3 H2O

or

2 LiOH + CO2 → Li2CO3 + H2O

The latter, anhydrous hydroxide, is preferred for its lower mass and lesser water production for respirator systems in spacecraft. One gram of anhydrous lithium hydroxide can remove 450 cm3 of carbon dioxide gas. The monohydrate loses its water at 100–110 °C.

Precursor

Lithium hydroxide, together with lithium carbonate, is a key intermediates used for the production of other lithium compounds, illustrated by its us in the production of lithium fluoride:[5]

LiOH + HF → LiF + H2O.

Other uses

It is also used in ceramics and some Portland cement formulations. Lithium hydroxide (isotopically enriched in lithium-7) is used to alkalize the reactor coolant in pressurized water reactors for corrosion control.[16]

Price

on 18 March 2021 the price has risen to US$11.50/kg[17]

In 2012, the price of lithium hydroxide was about $5-6/kg.[18]

In December 2020 it had risen to $9/kg[19]

See also

References

  1. ^ Lide, David R., ed. (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN 0-8493-0487-3.
  2. ^ a b c Khosravi J (2007). Production of Lithium Peroxide and Lithium Oxide in an Alcohol Medium. Chapter 9: Results. ISBN 978-0-494-38597-5.
  3. ^ Popov K, Lajunen LH, Popov A, Rönkkömäki H, Hannu-Kuure H, Vendilo A (2002). "7Li, 23Na, 39K and 133Cs NMR comparative equilibrium study of alkali metal cation hydroxide complexes in aqueous solutions. First numerical value for CsOH formation". Inorganic Chemistry Communications. 5 (3): 223–225. Retrieved 21 January 2017.
  4. ^ Chambers M. "ChemIDplus – 1310-65-2 – WMFOQBRAJBCJND-UHFFFAOYSA-M – Lithium hydroxide anhydrous – Similar structures search, synonyms, formulas, resource links, and other chemical information". chem.sis.nlm.nih.gov. Retrieved 12 April 2018.
  5. ^ a b Wietelmann U, Bauer RJ (2000). "Lithium and Lithium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_393. ISBN 3-527-30673-0. {{cite encyclopedia}}: More than one of |contribution= and |chapter= specified (help)
  6. ^ "Proposed Albemarle Plant Site" (PDF). Albemarle. Retrieved 4 December 2020.
  7. ^ "Corporate presentation" (PDF). Nemaska Lithium. May 2018. Retrieved 5 December 2020.
  8. ^ a b c "China's Ganfeng to Be Largest Lithium Hydroxide Producer". BloombergNEF. 10 September 2020. Retrieved 4 December 2020.
  9. ^ "Ganfeng Lithium Group". Ganfeng Lithium. Retrieved 25 March 2021.{{cite web}}: CS1 maint: url-status (link)
  10. ^ Stephens, Kate; Lynch, Jacqueline (27 August 2020). "Slowing demand for lithium sees WA's largest refinery scaled back". www.abc.net.au.
  11. ^ "AVZ Minerals Limited". AVZ Minerals Limited . Retrieved 25 March 2021.{{cite web}}: CS1 maint: url-status (link)
  12. ^ "Metallurgical test work confirms Manono Primary Lithium Sulphate suitable for battery production Feedstock". www.avzminerals.com.au. 13 January 2021. Retrieved 25 March 2021. {{cite web}}: External link in |author-link= (help)CS1 maint: url-status (link)
  13. ^ "Largest of its kind lithium hydroxide plant launched in Kwinana". Government of Western Australia. 10 September 2019. Retrieved 4 December 2020.
  14. ^ Barrera, Priscilla (27 June 2019). "Will Lithium Hydroxide Really Overtake Lithium Carbonate? | INN". Investing News Network. Retrieved 5 December 2020.
  15. ^ Jaunsen JR (1989). "The Behavior and Capabilities of Lithium Hydroxide Carbon Dioxide Scrubbers in a Deep Sea Environment". US Naval Academy Technical Report. USNA-TSPR-157. Archived from the original on 2009-08-24. Retrieved 2008-06-17.
  16. ^ Managing Critical Isotopes: Stewardship of Lithium-7 Is Needed to Ensure a Stable Supply, GAO-13-716 // U.S. Government Accountability Office, 19 September 2013; pdf
  17. ^ "LITHIUM AT THE LME". LME The London Metal Exchange. 18 March 2021. Retrieved 22 March 2021.{{cite web}}: CS1 maint: url-status (link)
  18. ^ "Lithium Prices 2012". investingnews.com. Investing News Network. Retrieved 12 April 2018.
  19. ^ "London Metal Exchange: Lithium prices". London metal exchange. Retrieved 4 December 2020.
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