Stabilizing the Deep Sodiation Process in Layered Sodium Manganese Cathodes by Anchoring Boron Ions

Advanced high-energy-density sodium-ion batteries (SIBs) are inseparable from cathode materials with high specific capacities. Layered manganese-rich oxides (Na_xMnO₂, 0.6 ≤ x ≤1) are promising cathode materials owing to their ease of intercalation and extraction of a considerable amount of sodium ions. However, lattice interactions, especially electrostatic repulsive forces and anisotropic stresses, are usually caused by deep desodiatin/sodiation process, resulting in intragranular cracks and capacity degradation in SIBs. Here, boron ions are introduced into the layered structure to build up B─O─Mn bonds. The regulated electronic structure in Na_0.637B_0.038MnO₂ (B-NMO) materials inhibits the deformation of MnO₆ octahedra, which finally achieves a gentle structural transition during the deep sodiation process. B-NMO electrode exhibits a high capacity (141 mAh g^–1) at 1 C with a capacity retention of 81% after 100 cycles. Therefore, anchoring boron to manganese-rich materials inhibits the detrimental structural evolution of deep sodiation and can be used to obtain excellent cathode materials for SIBs. © 2023 Wiley-VCH GmbH.