Configuring PSx tetrahedral clusters in Li-excess Li7P3S11 solid electrolyte

We demonstrate that the Li-ion conductivity can be improved by adding a certain amount of Li (x = 0.25–0.5) as a charge carrier to the composition of glass-ceramic Li7+xP3S11. Structural analysis clarified that the structural changes caused by the ratio of ortho-thiophosphate tetrahedra PS43− and pyro-thiophosphate ditetrahedra P2S74− affect the Li-ion conductivity. The ratio of PS43− and P2S74− varies depending on x and the highest Li-ion conductivity (2.5 × 10−3 S cm−1) at x = 0.25. All-solid-state LiNi0.8Co0.15Al0.05O2/Li7.25P3S11/In-metal cell exhibits the discharge capacity of 106.2 mAh g−1. This ion conduction enhancement from excess Li is expected to contribute to the future design of sulfide-type electrolytes.