Thermal‐Induced Dopant Precipitation Enabling High‐Quality Surface Modification of LiCoO₂

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Surface modification is an effective approach for overcoming the interfacial degradations to enable high electrochemical performance of battery materials, yet it is still challenging to realize high‐quality surface modification with simple processing, low cost, and mass production. Herein, a thermal‐induced surface precipitation phenomenon is reported in a Ti‐dopped LiCoO 2 , which can realize an ultrathin (≈5 nm) and uniform surface modification by a simple annealing process. It is revealed that surface Li‐deficiency enables bulk Ti to precipitate and segregate on the non‐(003) surface facets, forming a Ti‐enriched disordered layered structure. Such a surface modification layer can not only stabilize the interfacial chemistry but also significantly improve the charge/discharge reaction kinetics, leading to much‐improved cycling stability and rate capability. Dopants surface precipitation is a unique outward diffusion process, which differs from the current surface modification techniques and further diversifies these approaches for realizing high‐quality surface modification of battery materials.