Lithium-air (Li-air) batteries stand out among the post-Li-ion batteries due to their high energy density, which has rapidly progressed in the past years. Regarding the fundamental mechanism of Li-air batteries that discharge products produced and decomposed during charging and recharging progress, the reversibility of products closely affects the battery performance. Along with the upsurge of the mainstream discharge products lithium peroxide, with devoted efforts to screening electrolytes, constructing high-efficiency cathodes, and optimizing anodes, much progress is made in the fundamental understanding and performance. However, the limited advancement is insufficient. In this case, the investigations of other discharge products, including lithium hydroxide, lithium superoxide, lithium oxide, and lithium carbonate, emerge and bring breakthroughs for the Li-air battery technologies. To deepen the understanding of the electrochemical reactions and conversions of discharge products in the battery, recent advances in the various discharge products, mainly focusing on the growth and decomposition mechanisms and the determining factors are systematically reviewed. The perspectives for Li-air batteries on the fundamental development of discharge products and future applications are also provided.
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