The electrochemical performance and structural stability of sodium-ion battery is substantially dependent on the occupancy and distribution of Na⁺ in cathode materials. However, it is challenging to simultaneously regulate the occupancy and optimize the distribution of Na⁺ in cathodes for higher capacity and superior cyclability. Here we attempt to adjust the arrangement of Na⁺ in layered cathode materials by applying a combination approach, including enhancing the Na content, disrupting transition metal ordering and strengthening Na⁺-TMⁿ⁺ electrostatic force. Through detailed structural characterizations on cathodes, it is revealed that the rearrangement of Na⁺ at two distinct Wyckoff positions can be realized in Li/Ti-codoped Na_2/3Ni_1/3Mn_2/3O₂ cathodes, contributing to outstanding rate performance and smooth kinetic process. In addition, the inhibited P2-O2 phase transition and intact lattice structure is closely related to the rearranged Na layer and strengthened transition metal slab, jointly resulting in excellent long cycling performance with 90.2% capacity retention after 200 cycles at 1 C (150 mA/g). This work sheds new light on the role of different Na sites and provides a universal and practical approach to adjusting the Na⁺ distribution in P2-type cathode materials.

钠离子电池的电化学性能和结构稳定性很大程度上取决于正极材料中钠^{离子的占据和分布。}然而，同时调节占有率和优化正极中 Na ⁺的分布以获得更高的容量和优异的可循环性是一项挑战。在这里，我们尝试通过组合方法来调整层状正极材料中 Na ^{+的排列，包括提高 Na 含量、破坏过渡金属有序性和增强 Na +} -TM ^{n +}静电力。通过对正极的详细结构表征，揭示了 Na ^+的重排在 Li/Ti 共掺杂的 Na _2/3 Ni _1/3 Mn _2/3 O ₂正极中，可以实现两个不同的 Wyckoff 位置，有助于出色的倍率性能和平稳的动力学过程。此外，受抑制的 P2-O2 相变和完整的晶格结构与重排的 Na 层和强化的过渡金属板密切相关，共同导致优异的长循环性能，在 1 C 下循环 200 次后容量保持率为 90.2%（150 mA/ G）。这项工作揭示了不同Na位点的作用，并为调整P2型正极材料中的Na ^{+分布提供了一种通用且实用的方法。}