Mitigating the Interfacial Degradation in Cathodes for High-Performance Oxide-Based Solid-State Lithium Batteries

Solid-state lithium batteries (SSLBs) are the promising next-generation energy storage systems because of their attractive advantages in terms of energy density and safety. However, the interfacial engineering and battery building are of huge challenges, especially for stiff oxide-based electrolytes. Herein, we construct SSLBs by a cosintering method using Li₃BO₃ as a sintering agent to bind the cathode materials LiNi_0.6Mn_0.2Co_0.2O₂ (NMC) and solid-state electrolytes Li_6.4La₃Zr_1.4Ta_0.6O₁₂. Small NMC primary particles are compared with large secondary particles to study the effects on interfacial adhesion, mechanical retention, internal resistance evolution, and electrochemical performance. Our results reveal that the interfacial resistance decreases during charging and increases during discharging, resulting in an overall increase in the interfacial resistance after one cycle. The main reason is attributed to the microcracks induced by the volumetric changes of NMC during the electrochemical process. The mechanical degradations at the interfaces accumulated upon cycling can cause capacity decay and low Coulombic efficiency. The SSLB constructed from small NMC primary particles shows regulation of particle distribution, mitigation in local volumetric change, and alleviation in mechanical degradation at the interfaces, leading to smaller resistance change and better electrochemical performance. The findings shed lights on designing SSLBs with good mechanical retention and electrochemical performance.