Reactive selenium induced near-surface reconstruction to stabilize high-voltage, cobalt-free cathodes for high-rate, long-cycling lithium batteries

Abstract

The cobalt-free spinel LiNi_0.5Mn_1.5O₄ (LNMO) emerges as a high voltage and high energy density cathode candidate for next generation batteries, yet its practical application is challenged by intrinsic Mn dissolution, oxygen vacancy-driven structural degradation, and unstable electrode-electrolyte interphase. Herein, we demonstrate a reactive selenium (Se)-induced near-surface reconstruction strategy, which integrates SeO_x coating and Se element doping into the near-surface of LNMO through a one-step vapor-phase selenization process, stabilizing both the electrode-electrolyte interphase and the bulk lattice. During electrochemical cycling, the nanoscale-thick SeO_x coating layer evolves into a Li₂SeO_x-rich interfacial layer, facilitating rapid Li⁺ transport and enhancing mechanical resilience to suppress interfacial degradation caused by volume changes. Concurrently, near-surface Se doping forms O-transition metal (TM)-Se bonds that narrow the bandgap between Mn 3d and O 2p orbitals, thereby stabilizing lattice oxygen, suppressing Mn dissociation and structural deterioration. The near-surface reconstructed Se-LNMO cathode exhibits exceptional long-term cycling stability at high rates with a 0.018% capacity decay rate per cycle after 2000 cycles at 5C, outperforming previously reported LNMO materials. This simple yet effective “all-in-one” reactive Se infusion strategy serves as a universal paradigm for stabilizing high-voltage cathodes, opening up new avenues for the design of novel high-energy-density cathode materials.

Keywords

LNMO / long-term cycling stability / Se element doping / SeO_x coating

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