Improving Li-ion interfacial transport in hybrid solid electrolytes

The development of commercial solid-state batteries has to date been hindered by the individual limitations of inorganic and organic solid electrolytes, motivating hybrid concepts. However, the room-temperature conductivity of hybrid solid electrolytes is still insufficient to support the required battery performance. A key challenge is to assess the Li-ion transport over the inorganic and organic interfaces and relate this to surface chemistry. Here we study the interphase structure and the Li-ion transport across the interface of hybrid solid electrolytes using solid-state nuclear magnetic resonance spectroscopy. In a hybrid solid polyethylene oxide polymer-inorganic electrolyte, we introduce two representative types of ionic liquid that have different miscibilities with the polymer. The poorly miscible ionic liquid wets the polymer-inorganic interface and increases the local polarizability. This lowers the diffusional barrier, resulting in an overall room-temperature conductivity of 2.47 × 10^-4 S cm^-1. A critical current density of 0.25 mA cm^-2 versus a Li-metal anode shows improved stability, allowing cycling of a LiFePO₄-Li-metal solid-state cell at room temperature with a Coulombic efficiency of 99.9%. Tailoring the local interface environment between the inorganic and organic solid electrolyte components in hybrid solid electrolytes seems to be a viable route towards designing highly conducting hybrid solid electrolytes.