Searching for novel solid electrolytes is of great importance and challenge for all-solid-state Mg batteries. In this work, we develop an amorphous Mg borohydride ammoniate, Mg(BH4)2·2NH3, as a solid Mg electrolyte that prepared by a NH3 redistribution between 3D framework-γ-Mg(BH4)2 and Mg(BH4)2·6NH3. Amorphous Mg(BH4)2·2NH3 exhibits a high Mg-ion conductivity of 5 × 10−4 S cm−1 at 75 ℃, which is attributed to the fast migration of abundant Mg vacancies according to the theoretical calculations. Moreover, amorphous Mg(BH4)2·2NH3 shows an apparent electrochemical stability window of 0–1.4 V with the help of in-situ formed interphases, which can prevent further side reactions without hindering the Mg-ion transfer. Based on the above superiorities, amorphous Mg(BH4)2·2NH3 enables the stable cycling of all-solid-state Mg cells, as the critical current density reaches 3.2 mA cm−2 for Mg symmetrical cells and the reversible specific capacity reaches 141 mAh g−1 with a coulombic efficiency of 91.7% (first cycle) for Mg||TiS2 cells.
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