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Abstract Anti‐perovskites X3BA, as the electrically inverted derivatives of perovskites ABX3, have attracted tremendous attention for their good performances in multiple disciplines, especially in energy storage batteries. The Li/Na‐rich antiperovskite (LiRAP/NaRAP) solid‐state electrolytes (SSEs) typically show high ionic conductivities and high chemical/electrochemical stability toward the Li‐metal anode, illustrating their great potential for applications in the Li‐metal batteries (LMBs) using nonaqueous liquid electrolyte or all‐solid‐state electrolyte. The antiperovskites have been studied as artificial solid electrolyte interphase for Li‐metal anode protection, film SSEs for thin‐film batteries, and low melting temperature solid electrolyte enabling melt‐infiltration for the manufacture of all‐solid‐state lithium batteries. Transition metal‐doped LiRAPs as cathodes have demonstrated a high discharge specific capacity and good rate capability in the Li‐ion batteries (LIBs). Additionally, the underlying scientific principles in antiperovskites with flexible structural features have also been extensively studied. In this review, we comprehensively summarize the development, structural design, ionic conductivity and ion transportation mechanism, chemical/electrochemical stability, and applications of some antiperovskite materials in energy storage batteries. The perspective for enhancing the performance of the antiperovskites is also provided as a guide for future development and applications in energy storage. |
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