钾离子电池聚合物正极：储能机制与优化策略

doi:10.1016/j.actphy.2026.100363

摘要/Abstract

摘要： 由于可调控的分子结构、丰富的氧化还原活性位点以及可持续的元素组成，聚合物正极在钾离子电池领域引起了越来越多的关注。与无机嵌入型正极相比，聚合物正极通常通过钾离子或电解液阴离子与有机官能团之间的可逆氧化还原反应来储存电荷，这些官能团包括羰基、酰亚胺、醌、偶氮、亚胺以及含氮杂环单元。其电化学性能不仅取决于活性位点本征的氧化还原化学特性，还受聚合物主链构型、π共轭程度、聚集行为、孔结构以及电极/电解液界面稳定性的影响。本文综述了聚合物正极在钾离子电池中的最新进展，重点关注钾储存机制与结构优化策略。从分子结构、离子-电极相互作用以及电荷转移动力学等角度，讨论了若干代表性机制，例如羰基配位、酰亚胺螯合、多电子氧化还原过程、双极性电荷补偿以及赝电容行为。此外，还从溶剂化/去溶剂化行为、局部配位环境和氧化还原位点利用等方面分析了K⁺、Li⁺和Na⁺之间的离子特异性差异。文中重点介绍了若干关键优化策略，包括聚合度调控、刚性π共轭主链设计、孔结构或三维网络构筑、导电复合以及电解液匹配。最后，讨论了当前仍面临的挑战与未来研究方向，以指导高性能钾离子电池聚合物正极的理性设计。

关键词: 钾离子电池, 聚合物正极, 储能机制, 优化策略

Abstract: Polymer cathodes have attracted growing interest for potassium-ion batteries (PIBs) due to their tunable molecular structures, abundant redox-active sites, and sustainable elemental compositions. Compared with inorganic intercalation-type cathodes, polymer cathodes typically store charge through reversible redox reactions between K⁺ ions or electrolyte anions and organic functional groups, including carbonyl, imide, quinone, azo, imine, and nitrogen-containing heterocyclic units. Their electrochemical performance is governed not only by the intrinsic redox chemistry of the active sites, but also by the polymer backbone configuration, π-conjugation degree, aggregation behavior, pore structure, and the stability of the electrode/electrolyte interface. This review summarizes recent progress in polymer cathodes for PIBs, with a focus on potassium-storage mechanisms and structural optimization strategies. Representative mechanisms, such as carbonyl coordination, imide chelation, multielectron redox processes, bipolar charge compensation, and pseudocapacitive behavior, are discussed from the perspectives of molecular structure, ion-electrode interactions, and charge-transfer kinetics. In addition, the ion-specific differences among K⁺, Li⁺, and Na⁺ are analyzed in terms of solvation/desolvation behavior, local coordination environments, and redox-site utilization. Key optimization strategies, including polymerization-degree control, rigid π-conjugated backbone design, porous or three-dimensional network construction, conductive compositing, and electrolyte matching, are highlighted. Finally, the remaining challenges and future research directions are discussed to guide the rational design of high-performance polymer cathodes for PIBs.

Key words: Potassium-ion battery, Polymer cathode, Energy storage mechanism, Optimization strategy

周驰, 袁泽宇, 胡志斌, 吴亚群, 段丽平, 杜忆忱, 周小四. 钾离子电池聚合物正极：储能机制与优化策略[J]. 物理化学学报, 2026, 42(11), 100363. doi: 10.1016/j.actphy.2026.100363

Chi Zhou, Zeyu Yuan, Zhibin Hu, Yaqun Wu, Liping Duan, Yichen Du, Xiaosi Zhou. Energy storage mechanisms and optimization strategies of polymer cathodes for potassium-ion batteries[J]. Acta Phys. -Chim. Sin. 2026, 42(11), 100363. doi: 10.1016/j.actphy.2026.100363

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2026.100363

https://www.whxb.pku.edu.cn/CN/Y2026/V42/I11/100363

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