Concepts in sodium oxide cathode composite structures have captured widespread attention; however, the detailed monitoring and accurate control of composite structural evolution during charge and discharge process remain challenging, especially for complex triphases and other similar systems. Here, we report the accurate manipulation of multiphase structural evolution during high-voltage cycling with improved electrochemical performance and adjustable sodium ion intercalation/deintercalation electrochemical behavior via rational chemical element substitution using a series of Fd-3m spinel and layered P2/P3 heterostructures as proof-of-concept materials. Multiphase evolutions as a function of chemical substitution during high-voltage cycling are demonstrated. Meanwhile, we also monitor the dynamic formation process during calcination and observe the atomic arrangement of triphase heterostructure through various advanced characterization techniques. Overall, this study reveals controllable multiphase structural evolution in a model system and explores the related fundamental science required for future development of high-performance sodium-ion batteries.

氧化钠阴极复合结构的概念已引起广泛关注；然而，在充放电过程中对复合材料结构演变的详细监测和准确控制仍然具有挑战性，尤其是对于复杂的三相和其他类似系统。在这里，我们报告了通过使用一系列Fd -3 m 的合理化学元素取代，在高压循环过程中准确操纵多相结构演化，具有改进的电化学性能和可调的钠离子嵌入/脱嵌电化学行为。尖晶石和分层 P2/P3 异质结构作为概念验证材料。证明了作为高压循环过程中化学取代函数的多相演变。同时，我们还监测煅烧过程中的动态形成过程，并通过各种先进的表征技术观察三相异质结构的原子排列。总体而言，这项研究揭示了模型系统中可控的多相结构演化，并探索了高性能钠离子电池未来发展所需的相关基础科学。