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Careful Answer: SOMETIMES. But ALWAYS check the label of the lithium battery in question to make sure it is rated for "1.5v" before attempting to use it as a replacement for an alkaline battery.

Explanation:

Alkaline primary batteries have a nominal voltage of 1.5v per cell.

Lithium primary ("primary"=disposable) batteries USUALLY have a nominal voltage of "3v" per cell.

There are some Lithium primary cells, AA's for example, that have a nominal voltage of 1.5v per cell which makes them a suitable replacement for alkaline batteries.

To complicate matters, however, there are rechargeable lithium-ion cells in the AA format which have a nominal voltage of 3.6v per cell, and more commonly there are "Lithium Phosphate" AA's which have a nominal voltage of 3.2v or 3.3v per cell. Using either of these as a replacement for alkaline batteries would be potentially destructive for both the batteries and the device you install them in.

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