The rechargeable multivalent-ion batteries (MVIBs) that transfer Zn²⁺, Mg²⁺, Al³⁺, Ca²⁺ etc. as charge carriers, have become a research hotspot and been emerging as attractive candidates for grid energy storage in terms of cost, volumetric energy density and safety. But there is still a long way from their maturity due to the challenges related to the limited multivalent-ion diffusion kinetic. Unfortunately, the insightful understanding in this aspect is still at an early stage. In this review, considering the critical role of defect chemistry, we have highlighted the fundamental scientific understanding of its relationship with multivalent-ion migration in electrode materials of MVIBs. We first remarked on the basic principles of ion diffusion, from which we further discussed the key factors affecting ion migration and pointed out the critical issues of multivalent-ion diffusion. More importantly, how characteristic parameters of defect engineering cause changes in multivalent-ion diffusion behavior has been expounded in the areas of ion diffusion path and intrinsic structural parameters. The application of defective electrodes in MVIBs with advanced functions was also discussed. Finally, the future perspectives for important areas of defect chemistry for multivalent-ion migration were presented.

传输Zn ²⁺、Mg ²⁺、Al ³⁺、Ca ²⁺的可充电多价离子电池（MVIB）等作为电荷载体，已成为研究热点，并在成本、体积能量密度和安全性方面成为电网储能的有吸引力的候选者。但由于与有限的多价离子扩散动力学相关的挑战，它们距离成熟还有很长的路要走。不幸的是，这方面的深刻理解仍处于早期阶段。在这篇综述中，考虑到缺陷化学的关键作用，我们强调了对缺陷化学与 MVIB 电极材料中多价离子迁移关系的基本科学认识。我们首先介绍了离子扩散的基本原理，从中我们进一步讨论了影响离子迁移的关键因素，并指出了多价离子扩散的关键问题。更重要的是，缺陷工程的特征参数如何引起多价离子扩散行为的变化已在离子扩散路径和内在结构参数方面进行了阐述。还讨论了缺陷电极在具有先进功能的 MVIB 中的应用。最后，提出了多价离子迁移缺陷化学重要领域的未来前景。