Operando Observation of the De-Evolution/Evolution Process of Hydrated LiOH in Moisture-Assisted Li–O₂ Batteries

All-solid-state Li–O 2 batteries that use ceramic electrolytes have been suggested to overcome the limitations posed by the decomposition of organic electrolytes. However, these systems show a low discharge capacity and high overpotential because the discharge product Li 2 O 2 has low electronic conductivity. In this study, all-solid-state planar-type Li–O 2 cells were constructed using a lithium anode, a Li 1·3 Al 0·3 Ti 1·7 (PO 4 ) (LATP) inorganic solid electrolyte, and an air electrode composed of a Pt grid pattern. The discharge/charge process was observed in real time in a humidified O 2 environment for the first time, which clarified both the hydration process of the discharge products and the charging process of the hydrated discharge products. The discharge product (LiOH) could be easily hydrated in water, which would facilitate ion transport, thereby increasing the discharge capacity and discharge voltage (vs Li/Li +; from 2.96 to 3.4 V). Thus, Li–O 2 cells with a high energy density and a capacity of 3600 mAh/g cathode were achieved using a planar Pt-patterned electrode in a humidified O 2 environment. This study is the first to demonstrate the hydration of the discharge products of a Li–O 2 cell in humidified O 2 . Based on a thorough understanding of the hydration phenomenon/mechanism, our findings suggest new strategies for developing high-energy-density all-solid-state Li–O 2 batteries using a simple, easy-to-manufacture planar Pt-patterned cathode.