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Lithium hexafluorophosphate

Lithium hexafluorophosphate is an inorganic compound with the formula LiPF<sub>6</sub>. It is a white crystalline powder.

Production

LiPF<sub>6</sub> is manufactured by reacting phosphorus pentachloride with hydrogen fluoride and lithium fluoride

PCl<sub>5</sub> + LiF + 5 HF → LiPF<sub>6</sub> + 5 HCl

Chemistry

The salt is relatively stable thermally, but loses 50% weight at 200&nbsp;°C (392&nbsp;°F). It hydrolyzes near 70&nbsp;°C (158&nbsp;°F) according to the following equation forming highly toxic HF gas:

LiPF<sub>6</sub> + 4 H<sub>2</sub>O → LiF + 5 HF + H<sub>3</sub>PO<sub>4</sub>

Owing to the Lewis acidity of the Li<sup>+</sup> ions, LiPF<sub>6</sub> also catalyses the tetrahydropyranylation of tertiary alcohols.

In lithium-ion batteries, LiPF<sub>6</sub> reacts with Li<sub>2</sub>CO<sub>3</sub>, which may be catalysed by small amounts of HF:

LiPF<sub>6</sub> + Li<sub>2</sub>CO<sub>3</sub> → POF<sub>3</sub> + CO<sub>2</sub> + 3 LiF

Application

The main use of LiPF<sub>6</sub> is in commercial secondary batteries, an application that exploits its high solubility in polar aprotic solvents. Specifically, solutions of lithium hexafluorophosphate in carbonate blends of ethylene carbonate, dimethyl carbonate, diethyl carbonate and/or ethyl methyl carbonate, with a small amount of one or many additives such as fluoroethylene carbonate and vinylene carbonate, serve as state-of-the-art electrolytes in lithium-ion batteries. This application takes advantage of the inertness of the hexafluorophosphate anion toward strong reducing agents, such as lithium metal, as well as of the ability of [PF6-] to passivate the positive aluminium current collector.

References