Mitigation of Jahn–Teller distortion and Na+/vacancy ordering in a distorted manganese oxide cathode material by Li substitution

Layered manganese-based oxides are promising candidates as cathode materials for sodium-ion batteries (SIBs) due to their low cost and high specific capacity. However, the Jahn–Teller distortion from high-spin Mn³⁺ induces detrimental lattice strain and severe structural degradation during sodiation and desodiation. Herein, lithium is introduced to partially substitute manganese ions to form distorted P′2-Na_0.67Li_0.05Mn_0.95O₂, which leads to restrained anisotropic change of Mn–O bond lengths and reinforced bond strength in the [MnO₆] octahedra by mitigation of Jahn–Teller distortion and contraction of MnO₂ layers. This ensures the structural stability during charge and discharge of P′2-Na_0.67Li_0.05Mn_0.95O₂ and Na⁺/vacancy disordering for facile Na⁺ diffusion in the Na layers with a low activation energy barrier of ∼0.53 eV. It exhibits a high specific capacity of 192.2 mA h g⁻¹, good cycling stability (90.3% capacity retention after 100 cycles) and superior rate capability (118.5 mA h g⁻¹ at 1.0 A g⁻¹), as well as smooth charge/discharge profiles. This strategy is effective to tune the crystal structure of layered oxide cathodes for SIBs with high performance.

Li-Substitution in P′2-Na_0.67MnO₂ mitigates the anisotropic change of Mn–O bonds and Na/vacancy ordering, and hence significantly promotes its cycling stability and rate capability as a cathode material for sodium-ion batteries.