Rechargeable multivalent metal batteries (MMBs) are considered as promising alternatives to Li-ion and Pb-acid batteries for grid-scale energy storage applications due to the multi-electron redox capability of metal anodes. However, the conventional inorganic cathodes used in MMBs face challenges with the sluggish diffusivity and poor storage of charge-dense multivalent cations in their crystal lattice. Organic electrode materials (OEMs), on the other hand, offer several advantages as MMB cathodes, including flexible structural designability, high resource availability, sustainability, and a unique ion-coordination storage mechanism. This review explores the intrinsic connection between the structural features of OEMs and their charge storage performance, aiming to unveil key design principles for organic molecules used in various MMB applications. We begin with an overview of the fundamental aspects of different MMBs (i.e., Zn/Mg/Ca/Al batteries), covering electrolyte selection, metal stripping/plating electrochemistry, and the fundamentals of cathode operation. From a theoretical understanding of redox activities, we summarize the properties of different redox sites and correlate the electrochemical properties of OEMs with various structural factors. This analysis further leads to the introduction of critical design considerations for different types of OEMs. We then critically review a wide range of organic compounds for MMBs, from small organic molecules to redox-active polymers and covalent-organic frameworks, focusing on their structure-property relationships, key electrochemical parameters, and strengths and shortcomings for multivalent ion storage. Finally, we discuss the existing challenges and propose potential solutions for further advancing OEMs in MMBs.

可充电多价金属电池（MMBs）由于金属阳极的多电子氧化还原能力，被认为是锂离子电池和铅酸电池在电网规模储能应用中的有前途的替代品。然而，传统用于MMBs的无机阴极在晶体晶格中面临着缓慢的扩散性和对电荷密集的多价阳离子的存储性差的问题。另一方面，有机电极材料（OEMs）作为MMBs阴极提供了几个优势，包括灵活的结构设计性、高资源可用性、可持续性和独特的离子-配位存储机制。本综述探讨了OEMs的结构特征与其储电性能之间的内在联系，旨在揭示用于各种MMB应用的有机分子的关键设计原则。我们首先概述了不同MMBs（即，Zn/Mg/Ca/Al电池）的基本方面，涵盖了电解质选择、金属剥离/电镀电化学以及阴极操作的基础知识。从对氧化还原活性的理论理解出发，我们总结了不同氧化还原位点的性质，并将OEMs的电化学性质与各种结构因素相关联。这一分析进一步引出了对不同类型OEMs的关键设计考虑因素的介绍。然后，我们对用于MMBs的广泛有机化合物进行了深入回顾，从小型有机分子到氧化还原活性聚合物和共价有机框架，重点研究了它们的结构-性质关系、关键电化学参数以及在多价离子存储方面的优缺点。最后，我们讨论了现有的挑战，并为在MMBs中进一步推进OEMs提出了潜在解决方案。