Unveiling Nickel Chemistry in Stabilizing High‐Voltage Cobalt‐Rich Cathodes for Lithium‐Ion Batteries

Abstract A practical solution is presented to increase the stability of 4.45 V LiCoO 2 via high‐temperature Ni doping, without adding any extra synthesis step or cost. How a putative uniform bulk doping with highly soluble elements can profoundly modify the surface chemistry and structural stability is identified from systematic chemical and microstructural analyses. This modification has an electronic origin, where surface‐oxygen‐loss induced Co reduction that favors the tetrahedral site and causes damaging spinel phase formation is replaced by Ni reduction that favors octahedral site and creates a better cation‐mixed structure. The findings of this study point to previously unspecified surface effects on the electrochemical performance of battery electrode materials hidden behind an extensively practiced bulk doping strategy. The new understanding of complex surface chemistry is expected to help develop higher‐energy‐density cathode materials for rechargeable batteries.