Elevating Cycle Stability and Reaction Kinetics in Ni‐Rich Cathodes Through Tailored Bulk and Interface Chemistry for Sulfide‐Based All‐Solid‐State Lithium Batteries

Abstract Sulfide‐based all‐solid‐state lithium batteries (ASSLBs) featuring Ni‐rich layered oxide cathodes are emerging as the leading contenders for the next generation of rechargeable batteries with outstanding safety and energy density characteristics. However, the composites of Ni‐rich oxides and sulfide electrolytes continue to grapple with persistent challenges encompassing structural deterioration, adverse interfacial parasitic reactions, and sluggish kinetics within the carbon‐free cathodes. Here, a synergistic design to circumvent these issues via the coupling of Zr/F co‐doping and conductive cyclized polyacrylonitrile (cPAN) coating to tailor both the bulk and surface chemistry of the Ni‐rich layered oxide LiNi_0.83Co_0.12Mn_0.05O₂ (NCM83125) cathode is proposed. The cathode subjected to this coordinated modification strategy showcases exceptional performance in sulfide‐based ASSLBs. It demonstrates robust cycling performance, with a capacity retention of 95% observed after 300 cycles at a rate of 0.2 C, alongside satisfactory rate performance, achieving a capacity of 109 mAh g^‒1 at a high rate of 3 C.