Insights into interfacial chemistry of Ni-rich cathodes and sulphide-based electrolytes in all-solid-state lithium batteries.

All-solid-state lithium batteries (ASSLBs) have attracted increasing attention recently because they are more safe and have higher energy densities than conventional lithium-ion batteries. In particular, ASSLBs composed of Ni-rich cathodes, sulphide-based solid-state electrolytes (SSEs) and lithium metal anodes have been regarded as the most competitive candidates. Ni-rich cathodes possess high operating potential, high specific energy and low cost, and sulphide-based SSEs have excellent ionic conductivity comparable to that of liquid electrolytes. However, severe parasitic reactions and chemo-mechanical issues hinder their practical application. Herein, the structure, ionic conductivity, chemical or electrochemical stability and mechanical property of sulphide-based SSEs are introduced. Critical interfacial problems between Ni-rich cathodes and sulphide-based SSEs, including chemical or electrochemical parasitic reactions, space charge layer effect, mechanical stress and contact loss, are summarised. The corresponding solutions including coating layer construction and structure design are expounded. Finally, the remaining challenges are discussed, and perspectives are outlined to provide guidelines for the future development of ASSLBs.