A critical review on Li-ion transport, chemistry and structure of ceramic-polymer composite electrolytes for solid state batteries.

In the transition to safer, more energy-dense solid state batteries, polymer-ceramic composite electrolytes may offer a potential route to achieve simultaneously high Li-ion conductivity and enhanced mechanical stability. Despite numerous studies on the polymer-ceramic composite electrolytes, disagreements persist on whether the polymer or the ceramic is positively impacted in their constituent ionic conductivity for such composite electrolytes, and even whether the interface is a blocking layer or a highly conductive lithium ion path. This lack of understanding limits the design of effective composite solid electrolytes. By thorough and critical analysis of the data collected in the field over the last three decades, we present arguments for lithium conduction through the bulk of the polymer, ceramic, or their interface. From this analysis, we can conclude that the unexpectedly high conductivity reported for some ceramic-polymer composites cannot be accounted for by the ceramic phase alone. There is evidence to support the theory that the Li-ion conductivity in the polymer phase increases along this interface in contact with the ceramic. The potential mechanisms for this include increased free volume, decreased crystallinity, and modulated Lewis acid-base effects in the polymer, with the former two to be the more likely mechanisms. Future work in this field requires understanding these factors more quantitatively, and tuning of the ceramic surface chemistry and morphology in order to obtain targeted structural modifications in the polymer phase.