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Solid‐state sodium‐ion/metal batteries (SSSBs) are highly desirable for next‐generation energy storage systems, while very limited Na‐ion solid‐state electrolytes are explored. The borohydride‐based solid electrolytes are expected to achieve the high energy density target, due to their low redox potential, low Young's modulus as well as high stability toward alkali metals. However, the biggest challenge...