<p>Sodium-ion batteries (SIBs) exhibit significant potential for large-scale energy storage systems due to the abundance and low cost of sodium resources. Triggering lattice oxygen redox (LOR) in P2-type transition metal oxides is considered a promising approach to enhance energy density in SIB cathodes, providing high operating potential and substantial capacity. However, irreversible phase transitions associated with LOR, particularly from prisms (P-type stacking) to octahedrons (O-type stacking), lead to severe structural distortions and sluggish Na<sup>+</sup> diffusion kinetics. In this work, an Al-substitution strategy is proposed to suppress the formation of O-type stacking and instead promote the formation of a beneficial Z phase. The flexible Al-O bonds accommodate asymmetric variations in their occupied states during the sodiation process, mitigating local structural distortions through Al-O bond contraction. Stabilization of the local structure ensures the maintenance of a robust Na<sup>+</sup> diffusion pathway. As a result, the Al-substituted cathode achieves a low Na<sup>+</sup> diffusion barrier of 0.47 eV and delivers a capacity of 86 mAh/g even at a high current density of 1 A/g within 1.5–4.5 V, maintaining 62.5% capacity retention over 100 cycles.</p>

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Fast oxygen redox enabled by flexible Al–O bonds in P2-type layered oxides for sodium batteries

  • Xinyin Cai,
  • Nan Wang,
  • Xun-Lu Li,
  • Haobo Bai,
  • Lu Ma,
  • Zulipiya Shadike,
  • Junliang Zhang

摘要

Sodium-ion batteries (SIBs) exhibit significant potential for large-scale energy storage systems due to the abundance and low cost of sodium resources. Triggering lattice oxygen redox (LOR) in P2-type transition metal oxides is considered a promising approach to enhance energy density in SIB cathodes, providing high operating potential and substantial capacity. However, irreversible phase transitions associated with LOR, particularly from prisms (P-type stacking) to octahedrons (O-type stacking), lead to severe structural distortions and sluggish Na+ diffusion kinetics. In this work, an Al-substitution strategy is proposed to suppress the formation of O-type stacking and instead promote the formation of a beneficial Z phase. The flexible Al-O bonds accommodate asymmetric variations in their occupied states during the sodiation process, mitigating local structural distortions through Al-O bond contraction. Stabilization of the local structure ensures the maintenance of a robust Na+ diffusion pathway. As a result, the Al-substituted cathode achieves a low Na+ diffusion barrier of 0.47 eV and delivers a capacity of 86 mAh/g even at a high current density of 1 A/g within 1.5–4.5 V, maintaining 62.5% capacity retention over 100 cycles.