Stabilizing Ni‐rich Single‐crystalline LiNi0.83Co0.07Mn0.10O2 Cathodes Using Ce/Gd Co‐doped High‐entropy Composite Surfaces

Ni-rich layered oxides are promising lithium-ion batteries (LIBs) cathode materials for their high reversible capacity, but they suffer from fast structural degradation during cycling. Here, we report the Ce/Gd incorporated single-crystalline LiNi0.83Co0.07Mn0.10O2 (SC-NCM) cathode materials with significantly enhanced cycling stability. The Gd ions are adequately incorporated in SC-NCM while Ce ions are prone to aggregate in the outer surface, resulting in the formation of a high-entropy zone in the near-surface of SC-NCM, including a Gd doped LiCeO2 (LCGO) shell and Ce/Gd dopant-concentrated layer. The high-entropy zone can effectively inhibit the oxygen evolution and prevent the formation of oxygen vacancies. Meanwhile, it leads to a greatly improved H2-H3 phase transformation reversibility and mitigated stress/strain caused by Li-ion extraction/insertion during (de)lithiation process. The synergetic effects of reduced oxygen vacancies concentration and mitigated stress/strain can effectively prevent the in-plane migration of TM ions, lattice planar gliding as well as the formation of intragranular nanocracks. Consequently, Ce/Gd incorporated SC-NCM (SC-NCM@CG2) delivers a high initial discharge specific capacity of 219.7 mAh g(-1) at 0.1 C and an excellent cycling stability with a capacity retention of 90.2 % after 100 cycles at 1.0 C.