Argyrodite Solid Electrolyte-Integrated Ni-Rich Oxide Cathode with Enhanced Interfacial Compatibility for All-Solid-State Lithium Batteries.

All-solid-state lithium batteries (ASSLBs) paired with an argyrodite sulfide solid electrolyte have become a candidate to take the world by storm for achieving high energy and safety. However, the undesirable interface design between a sulfide solid electrolyte and cathode is difficult to address its scalability production challenge. Particularly, the inferior interfacial contact between a sulfide solid electrolyte and cathode is an intractable obstacle for the large-scale commercial application of ASSLBs. Herein, an elaborately designed conformally in situ integration of a sulfide solid electrolyte onto a Ni-rich oxide cathode is proposed to overcome this issue through a facile tape casting method. In this unique integrated electrode structure, the sulfide solid electrolyte intimately makes contact with the Ni-rich oxide cathode, which significantly strengthens the solid-solid interfacial compatibility, as well as decreases the interfacial reaction resistances, thereby enabling rapid Li transportation and a stable interfacial structure. As a result, ASSLBs consisting of a sulfide solid electrolyte-integrated Ni-rich oxide cathode and Li anode exhibit high discharge capacity, excellent cyclic stability, and remarkable rate performance, which are superior to the cells with segregated structures composed of a Ni-rich oxide cathode, sulfide solid electrolyte, and Li anode. The features clearly indicate that the advanced interfacial contact between the cathode and solid electrolyte is responsible for ASSLBs with low polarization and fast reaction kinetics. Therefore, this work provides a rational proof-of-concept fabrication protocol for the reliable interfacial structure design of high-performance ASSLBs.