It has been extensively tested for use in commercial secondary batteries, an application that exploits its high solubility in nonpolar solvents.

[2] As an electrolyte in lithium-ion batteries, LiBF4 offers some advantages relative to the more common LiPF6.

It exhibits greater thermal stability[3] and moisture tolerance.

[4] For example, LiBF4 can tolerate a moisture content up to 620 ppm at room temperature whereas LiPF6 readily hydrolyzes into toxic POF3 and HF gases, often destroying the battery's electrode materials.

Because LiBF4 and other alkali-metal salts thermally decompose to evolve boron trifluoride, the salt is commonly used as a convenient source of the chemical at the laboratory scale:[5] LiBF4 is a byproduct in the industrial synthesis of diborane:[5][6] LiBF4 can also be synthesized from LiF and BF3 in an appropriate solvent that is resistant to fluorination by BF3 (e.g. HF, BrF3, or liquified SO2):[5]