LiLaZrO-co-LiNbO Surface Modification Improves the Interface Stability between Cathode and Sulfide Solid-State Electrolyte in All-Solid-State Batteries.

With the rapid development of energy storage and electric vehicles, thiophosphate-based all-solid-state batteries (ASSBs) are considered the most promising power source. In order to commercialize ASSBs, the interfacial problem between high-voltage cathode active materials and thiophosphate-based solid-state electrolytes needs to be solved in a simple, effective way. Surface coatings are considered the most promising approach to solving the interfacial problem because surface coatings could prevent direct physical contact between cathode active materials and thiophosphate-based solid-state electrolytes. In this work, LiLaZrO (LLZO) and LiNbO (LNO) coatings for LiCoO (LCO) were fabricated by in-situ interfacial growth of two high-Li conductive oxide electrolytes on the LCO surface and tested for thiophosphate-based ASSBs. The coatings were obtained from a two-step traditional sol-gel coatings process, the inner coatings were LNO, and the surface coatings were LLZO. Electrochemical evaluations confirmed that the two-layer coatings are beneficial for ASSBs. ASSBs containing LLZO-co-LNO coatings LiCoO (LLZO&LNO@LCO) significantly improved long-term cycling performance and discharge capacity compared with those assembled from uncoated LCO. LLZO&LNO@LCO||LiPSCl (LPSC)||Li-In delivered discharge capacities of 138.8 mAh/g, 101.8 mAh/g, 60.2 mAh/g, and 40.2 mAh/g at 0.05 C, 0.1 C, 0.2 C, and 0.5 C under room temperature, respectively, and better capacity retentions of 98% after 300 cycles at 0.05 C. The results highlighted promising low-cost and scalable cathode material coatings for ASSBs.