Composite polymer-ceramic electrolytes have shown considerable potential for high-energy-density Li-metal batteries as they combine the benefits of both polymers and ceramics. However, low ionic conductivity and poor contact with electrodes limit their practical usage. In this study, a highly conductive and stable composite electrolyte with a high ceramic loading is developed for high-energy-density Li-metal batteries. The electrolyte, produced through in situ polymerization and composed of a polymer called poly-1,3-dioxolane in a poly(vinylidene fluoride)/ceramic matrix, exhibits excellent room-temperature ionic conductivity of 1.2 mS cm-1 and high stability with Li metal over 1500 h. When tested in a Li|electrolyte|LiFePO4 battery, the electrolyte delivers excellent cycling performance and rate capability at room temperature, with a discharge capacity of 137 mAh g-1 over 500 cycles at 1 C. Furthermore, the electrolyte not only exhibits a high Li+ transference number of 0.76 but also significantly lowers contact resistance (from 157.8 to 2.1 Ω) relative to electrodes. When used in a battery with a high-voltage LiNi0.8 Mn0.1 Co0.1 O2 cathode, a discharge capacity of 140 mAh g-1 is achieved. These results show the potential of composite polymer-ceramic electrolytes in room-temperature solid-state Li-metal batteries and provide a strategy for designing highly conductive polymer-in-ceramic electrolytes with electrode-compatible interfaces.
Keywords: Li-metal batteries; in situ formations; low interfacial resistivities; polymer-in-ceramic; solid-state batteries.
© 2023 The Authors. Small published by Wiley-VCH GmbH.