In Situ Conversion of Artificial Proton‐Rich Shell to Inorganic Maskant Toward Stable Single‐Crystal Ni‐Rich Cathode

Abstract Single‐crystal high‐nickel oxide with an integral structure can prevent intergranular cracks and the associated detrimental reactions. Yet, its low surface‐to‐volume ratio makes surficial degradation a more critical factor in electrochemical performance. Herein, artificial proton‐rich (ammonium bicarbonate) shell is successfully introduced on the nickel‐rich LiNi_0.92Co_0.06Mn_0.02O₂ single crystals for in situ electrochemically conversing into inorganic maskant to enhance stability of cathode. The process is that the surficial enriched proton, once released from the ammonium bicarbonate shell (proton reservoir) during 1st charge, is immediately captured by LiPF₆, in situ electrochemically conversing to LiF and Li₃PO₄ sub‐nano particle dense maskant (sub‐nano F‐&P‐maskant). The in situ formed compact nano F‐&P‐maskant significantly resists the cathode against electrolyte attack and improves the surface stability of particles during long‐term cycling. Consequently, this surface modification enables 95% capacity retention after 100 cycles at a high voltage of 4.5 V in the half cell and 83% capacity retention after 800 cycles in the full cell. This work demonstrates a strategy for reconstructing the protective layer using the rational design of surficial enriched proton shells for advanced lithium batteries.