Additive-Derived Surface Modification of Cathodes in All-Solid-State Batteries: The Effect of Lithium Difluorophosphate- and Lithium Difluoro(oxalato)borate-Derived Coating Layers

Sulfide-based electrolytes, with their high conductivity and formability, enable the construction of high-performance, all-solid-state batteries (ASSBs). However, the instability of the cathode-sulfide electrolyte interface limits the commercialization of these ASSBs. Surface modification of cathodes using the coating technique has been explored as an efficient approach to stabilize these interfaces. In this study, the additives lithium difluorophosphate (LiDFP) and lithium difluoro(oxalato)borate (LiDFOB) are used to fabricate stable cathode coatings via heat treatment. The low melting points of LiDFP and LiDFOB enable the formation of thin and uniform coating layers by a low-temperature heat treatment. All-solid-state cells containing LiDFP- and LiDFOB-coated cathodes show electrochemical performances significantly better than those comprising uncoated cathodes. Among all of the as-prepared coated cathodes, LiDFP-coated cathodes fabricated using a slightly lower temperature than the phase-transition temperature of LiDFP (320 °C) show the best discharge capacity, rate capability, and cyclic performance. Furthermore, cells comprising LiDFP-coated cathodes showed significantly low impedance. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy confirm the effectiveness of the LiDFP coating. LiDFP-coated cathodes minimized side-reactions during cycling, resulting in a significantly low cathode-surface degradation. Hence, this study highlights the efficiency of the proposed coating method and its potential to facilitate the commercialization of ASSBs. Overall, this study reports an effective technique to stabilize the cathode-electrolyte interface in sulfide-based ASSBs, which could expedite the practical implementation of these advanced energy-storage devices.