Molybdenum‐Doped Cobalt‐Free Cathode Realizing the Electrochemical Stability by Enhanced Covalent Bonding

Abstract The doping strategy effectively enhances the capacity and cycling stability of cobalt‐free nickel‐rich cathodes. Understanding the intrinsic contributions of dopants is of great importance to optimize the performances of cathodes. This study investigates the correlation between the structure modification and their performances of Mo‐doped LiNi _0.8 Mn _0.2 O ₂ (NM82) cathode. The role of doped Mo's valence state has been proved functional in both lattice structural modification and electronic state adjustment. Although the high‐valence of Mo at the cathode surface inevitably reduces Ni valence for electronic neutrality and thus causes ion mixing, the original Mo valence will influence its diffusion depth. Structural analyses reveal Mo doping leads to a mixed layer on the surface, where high‐valence Mo forms a slender cation mixing layer, enhancing structural stability and Li‐ion transport. In addition, it is found that the high‐valence dopant of Mo ⁶⁺ ions partially occupies the unfilled 4d orbitals, which may strengthen the Mo─O bond through increased covalency and therefore reduce the oxygen mobility. This results in an impressive capacity retention (90.0% after 200 cycles) for Mo‐NM82 cathodes with a high Mo valence state. These findings underscore the valence effect of doping on layered oxide cathode performance, offering guidance for next‐generation cathode development.