Enhanced Surface Interactions Enable Fast Li+ Conduction in Oxide/Polymer Composite Electrolyte

Li+-conducting oxides are considered better ceramic fillers than Li+-insulating oxides for improving Li+ conductivity in composite polymer electrolytes owing to their ability to conduct Li+ through the ceramic oxide as well as across the oxide/polymer interface. Here we use two Li+-insulating oxides (fluorite Gd0.1Ce0.9O1.95 and perovskite La0.8Sr0.2Ga0.8Mg0.2O2.55) with a high concentration of oxygen vacancies to demonstrate two oxide/poly(ethylene oxide) (PEO)-based polymer composite electrolytes, each with a Li+ conductivity above 10(-4) S cm(-1) at 30 degrees C. Li solid-state NMR results show an increase in Li+ ions (>10 %) occupying the more mobile A2 environment in the composite electrolytes. This increase in A2-site occupancy originates from the strong interaction between the O2- of Li-salt anion and the surface oxygen vacancies of each oxide and contributes to the more facile Li+ transport. All-solid-state Li-metal cells with these composite electrolytes demonstrate a small interfacial resistance with good cycling performance at 35 degrees C.