Electronic Resonance Network Stabilized Crystal Structure in High-Nickel Cathodes for Lithium-Ion Batteries

Abstract

High-nickel layered oxides are considered key cathode materials for high-energy-density lithium-ion batteries due to their high specific capacity. However, the spin state localization of Ni³⁺ (t_2g⁶e_g¹) leads to severe Jahn–Teller distortion and structural degradation, limiting their cycling stability. This study proposes a high-entropy transition metal (TM) regulation strategy, which introduces multicomponent vacant orbital TM ions (Mn, Ti, Nb, Ta, W, and Mo) to construct a Ni-OO-TM electronic resonance network, promoting the delocalization of Ni³⁺ e_g electrons, thereby suppressing spin disorder and enhancing structural stability. On the basis of this, a high-entropy high-nickel cathode material (HE-LNF, LiNi_0.8Fe_0.14Mn_0.01Ti_0.01Nb_0.01Ta_0.01W_0.01Mo_0.01O₂) was designed. Combining first-principles calculations with experimental characterization, the weakening effect of electronic resonance on magnetic frustration was revealed: This effect increases the phase transition temperature to 294.23°C by reducing the amplitude of lattice vibrations, while electronic delocalization reduces local nuclear repulsion, maintaining excellent structural stability with minimal lattice strain evolution after cycling. Electrochemical testing shows that HE-LNF maintains a capacity retention rate of 91% after 100 cycles at a 0.33-C rate, significantly outperforming traditional high-nickel materials. This study provides new insights into the design of high-stability high-nickel cathodes based on electronic structure regulation.

Keywords

cathode / electronic resonance / high entropy / metal ions / orbitals

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