A new crystalline phase derived from a 90LiBH4:10P2S5 mixture displays high lithium-ionic conductivity of log(σ/S cm(-1)) = -3.0 at 300 K. It is stable up to 473 K and has both a wide potential window of 0-5 V and favorable mechanical properties for battery assembly. Its incorporation into a bulk-type all-solid-state TiS2/InLi battery enabled repeated battery operation at 300 K.