Surface nickel gradient tunes anionic redox activity to stabilize cobalt-free Li-rich cathodes

Constructing a gradient structure of transition metals (TMs) is promising to improve the electrochemical performance of layered oxide cathodes. However, the nickel gradient spinel layer on the surface of layer Li-rich cathodes is barely successful. Herein, we present a refining strategy of reductive gas to induce a Ni-gradient spinel layer on the surface of Li1.2Mn0.6Ni0.2O2 (LRNMO). The formed gradient spinel layer stabilizes the coordination environment at the interface and reduces oxygen loss. Moreover, the Ni gradient further maintains the reversibility of the Mn3+/Mn4+ redox couple, while the multiple valence states of Mn ions in the gradient layer enhance the electrochemical kinetics. The LRNMO with Ni-gradient spinel layer achieves an initial coulomb efficiency reaching 86.1% and maintaining an energy density of 667.9 Wh kg-1 after 200 cycles at 1 C. The surface gradient strategy is conducive to maintaining structural stability and provides support for the continued development of Li-ion batteries.