Promoted Stability and Reaction Kinetics in Ni-Rich Cathodes via Mechanical Fusing Multifunctional LiZr₂(PO₄)₃ Nanocrystals for High Mass Loading All-Solid-State Lithium Batteries

Sulfide all-solid-state lithium battery (ASSLB) with nickel-rich layered oxide as the cathode is promising for next-generation energy storage system. However, the Li + transport dynamic and stability in ASSLB are hindered by the structural mismatches and the instabilities especially at the oxide cathode/sulfide solid electrolyte (SE) interface. In this work, we have demonstrated a simple and highly effective solid-state mechanofusion method (1500 rpm for 10 min) to combine lithium conductive NASICON-type LiZr 2 (PO 4 ) 3 nanocrystals (∼20 nm) uniformly and compactly onto the surface of the single crystallized LiNi 0.8 Co 0.1 Mn 0.1 O 2, which can also attractively achieve Zr 4+ doping in NCM811 and oxygen vacancies in the LZPO coating without solvent and annealing. Benefiting from the alleviated interface mismatches, sufficient Li + ion flux through the LZPO coating, promoted structural stabilities for both NCM811 and sulfide SE, strong electronic coupling effect between the LZPO and NCM811, and enlarged (003) d -spacing with enriched Li + migration channels in NCM811, the obtained LZPO-NCM811 exhibits superior stability (185 mAh/g at 0.1C for 200 cycles) and rate performance (105 mAh/g at 1C for 1300 cycles) with high mass loading of 27 mg NCM /cm 2 in sulfide ASSLB. Even with a pronounced 54 mg NCM /cm 2, LZPO-NCM811 manifests a high areal capacity of 9.85 mAh/cm 2 . The convenient and highly effective interface engineering strategy paves the way to large-scale production of various coated cathode materials with synergistic effects for high performance ASSLBs.