Tape‐Cast NMC‐LLZO‐LBO‐based Composite Cathodes for Solid‐State Lithium Batteries

In order to increase the industrial appeal of solid‐state batteries (SSBs) based on garnet Li 7 La 3 Zr 2 O 12 (LLZO), the possibility of manufacturing them using scalable production processes such as tape casting must be demonstrated. In particular, the scalable production of thick, high‐capacity oxide‐ceramic composite cathodes based on Ni‐rich LiNi x Mn y Co z O 2 (NMC) remains a key challenge on the path to realizing ceramic SSBs with competitive energy densities. The limited thermal compatibility between NMC and LLZO during sintering requires the use of a sintering aid such as Li 3 BO 3 (LBO), which, however, impairs the rheological stability of tape casting slurries. In this work, we have developed a new tape‐casting process for thick oxide‐ceramic composite cathodes by establishing a slurry formulation that is compatible with multiphase cathode compositions and enables the reproducible fabrication of composite NMC cathode tapes with high active material loading. Two cathode configurations are investigated: NMC‐LLZO‐LBO composite cathodes, where LLZO serves as the catholyte, and LLZO‐free NMC‐LBO cathodes. After cosintering, the residual porosity of the ceramic cathodes is infiltrated with a polymer electrolyte with and without conductive carbon additives to form hybrid polymer‐ceramic SSBs. By systematically correlating cathode chemistry, secondary phase formation, and electrochemical performance, this study demonstrates how cathode chemistry and the balance between ionic and electronic transport pathways influence capacity utilization and cycle stability in thick, tape‐cast NMC‐based composite cathodes.