Abstract
Development of commercial solid-state batteries so far been hindered by the individual limitations of inorganic and organic solid-electrolytes, motivating hybrid concepts. However, room-temperature performance of hybrid-solid electrolytes is still insufficient in terms of ion conductivity, where especially the role and impact of the inorganic and organic interphases is largely unexplored. A key challenge is to assess the Li-ion transport over the interfaces directly and relate this to the surface chemistry. Here the lithium-ion conductivity in hybrid-solid electrolytes, the interface structure and Li+ interface transport was investigated by state-of-art solid-state nuclear magnetic resonance methodologies. In a hybrid-solid Polyethylene oxide polymer – inorganic electrolyte, two representative types of ionic liquids, having a different miscibility with the polymer, were used as a benchmark to tailor the local environment at the interface between the inorganic and organic solid electrolytes species. The poor miscibility ionic liquid wets the polymer-inorganic interface and raises the local polarizability, thereby lowering the diffusional barrier, which activates the high conductivity of the inorganic solid-electrolyte, resulting in and overall room temperature conductivity of 0.25 mS/cm. A very high critical current density of 0.25 mA/cm2 versus a Li-metal anode is achieved, demonstrating improved stability, and a LiFePO4 – Li-metal full solid-state cell can be cycled at room temperature at an Coulombic efficiency of 99.9%. The local interface environment between the solid electrolyte phases in hybrid solid electrolytes, is thus demonstrated to be the bottleneck and tailoring the interface properties appears a viable route towards the design of highly conducting hybrid-solid electrolyte concepts.
Measuring and tailoring Li-ion interfacial transport in hybrid solid electrolytes
