A Universal Method for Enhancing the Structural Stability of Ni-Rich Cathodes Via the Synergistic Effect of Dual-Element Cosubstitution

Ni-rich layered cathodes suffer detrimental structural changes due to irreversible phase transformation (IPT). Precisely surface structural reconstruction through foreign element doping is a potential method to alleviate IPT propagation. The structure of surface reconstructed layer is greatly determined by the foreign element content and species. Herein, small doses of Ti and Al were co-substituted in LiNi_0.92Co_0.08O₂ to synergistically regulate the surface reductive Ni distribution, consequently constructing thin rock salt phase at the particle surface. This homogeneous rock salt phase combined with the strong Ti−O and Al−O bonds generated a reversible H2−H3 phase transition and further eliminated IPT propagation. Moreover, the suppressed IPT propagation converted the two-phase (H2 and H3) coexistence to a quasi-single-phase transition. This eliminated the strong internal strains caused by a significant lattice mismatch. The Ti and Al co-substituted LiNi_0.92Co_0.08O₂ exhibited outstanding capacity retention and excellent structural stability. Similar improvements were observed with W or Zr and Al cosubstitution in Ni-rich layered cathodes. This study proposes a universal method for comprehensive improvement of structural stability based on the synergistic effect of dual-element cosubstitution in Ni-rich layered oxide cathodes, which is being explored for production of high-cycle-stability lithium-ion batteries.