Eliminating the Mn 3d Orbital Degeneracy to Suppress the Jahn–Teller Distortion for Stable MnO₂ Cathode

Abstract

The cycle stability of manganese‐based oxides cathode for sodium‐ion supercapacitor is impeded by severe structural collapse due to the Jahn–Teller (J–T) distortion of [MnO6] octahedra as Mn4+ is reduced to Mn3+. Herein, MnO2 cathode is stabilized by Mg2+ ions confinement between transition metal slabs. The Mg2+ confinement induces the transformation from original cubic [MnO6] octahedra to compressed configuration (com‐MnO2), resulting in the elimination of Mn 3d orbital degeneracy, thereby alleviating the structural deformation of [Mn3+O6] octahedra by suppressing J–T distortion during the reduction of Mn4+. As a result, the prepared com‐MnO2 exhibits greatly improved cycling stability with 99.1% retention of its initial capacity after 20 000 cycles due to inhibited J–T distortion. Additionally, an enhanced capacity of 434 F g−1 at 1 A g−1, a rate capacity of 275 F g−1 at 20 A g−1 can be achieved by com‐MnO2. The in situ XRD, Raman spectra reveal the reversible structural transformation during a cycle. It is concluded that the elimination of Mn 3d orbital degeneracy plays a crucial role in suppressing J–T distortion, which is conducive to in‐depth understanding of electron structure of transition metal oxides toward cycling performance.