Methylamine Lithium Borohydride as Electrolyte for All‐Solid‐State Batteries

Fast Li‐ion conductivity at room temperature is a major challenge for utilization of all‐solid‐state Li batteries. Metal borohydrides with neutral ligands are a new emerging class of solid‐state ionic conductors, and here we report the discovery of a new mono‐methylamine lithium borohydride with very fast Li(+) conductivity at room temperature. LiBH(4)⋅CH(3)NH(2) crystallizes in the monoclinic space group P2(1)/c, forming a two‐dimensional unique layered structure. The layers are separated by hydrophobic −CH(3) moieties, and contain large voids, allowing for fast Li‐ionic conduction in the interlayers, σ(Li(+))=1.24×10(−3) S cm(−1) at room temperature. The electronic conductivity is negligible, and the electrochemical stability is ≈2.1 V vs Li. The first all‐solid‐state battery using a lithium borohydride with a neutral ligand as the electrolyte, Li‐metal as the anode and TiS(2) as the cathode is demonstrated.