水溶液储钠聚合物的设计、合成与电化学表征

Aqueous sodium ion batteries are considered as promising electric energy storage technology for large scale stationary because of their advantages of low cost, safety and better environmental compatibility. However, Na-host materials for the aqueous sodium ion batteries are extremely limited because of the narrow electrochemical window of aqueous electrolytes and the strict restrictions of the metal oxide lattices on the larger Na+. Therefore, it is important to search and develop new generations of Na-host materials for aqueous batteries. Flexible polymer materials seem to be promising candidates because of their resource abundance, structural diversity and less restrictions on the cation size. In this study, we intend to design and synthesis self-doped polymers and carbonyl polymers as the cathode and anode materials to construct all organic aqueous sodium ion batteries. Following are the specific contents：Na-rich cathodes are developed by grafting the p-doped conducting polymers with ionizable sodium alkyl, while Na-defect anodes are developed by grafting the n-doped conducting polymers with carbonyl groups; The effect of the polymer structures and aqueous electrolytes on the electrochemical properties of the electrodes will be investigated by studying the electrochemical performances of the polymer electrodes；The reaction mechanism of the polymer electrodes will be revealed to provide theoretical guidance for the regular design and applications of new generations of all-organic aqueous Na-ion batteries with low cost and environmental friendliness.

水溶液钠离子电池价格低廉、安全性高且环境友好，是一种极具前景的大规模储能体系。然而，受制于水溶液的电化学窗口以及无机刚性晶格对于体积较大的钠离子的限制作用，可供选择的电极材料有限且可逆容量偏低。因此，探寻和发展新型正负极材料是发展水溶液钠离子电池的一个重要方向。本研究拟利用聚合物柔性骨架对于阳离子的尺寸限制较小，资源丰富且结构多样，设计合成不同结构的自掺杂聚合物阴极和共轭羰基聚合物阳极，构建全有机水溶液钠离子电池。具体研究内容包括：在p-掺杂的导电聚合物主链上接枝烷基钠盐，n-掺杂的导电聚合物主链上接枝共轭羰基，分别构建富钠的聚合物正极体系和贫钠的聚合物负极体系；通过研究聚合物电极在水溶液钠离子电池中的电化学行为，探索不同聚合物结构、电解液组分对电化学性质的影响；进一步研究聚合物在水溶液中储钠的电化学反应机理，为发展清洁、廉价的全有机水溶液钠离子电池提供理论基础知识和技术支持。

水溶液钠离子电池资源丰富、价格低廉、环境友好，在规模储能领域极具应用前景。聚合物材料结构多样、化学可控性强，对阳离子的限制较小，基于聚合物构建的水溶液钠离子电池在资源与成本上极具优势。本项目围绕以聚合物为电极材料的（水溶液）钠离子电池而展开，设计合成了一系列结构稳定、理论容量高的聚合物材料，如导电聚合物（聚苯胺、聚吡咯、聚并苯）、羰基化合物（聚酰亚胺、聚氨基蒽醌）等，系统地研究了此类聚合物的化学结构与储钠性能的构效关系。进一步结合理论模拟以及分子设计，构建亚铁氰根掺杂的聚苯胺（PAn），二苯胺磺酸钠掺杂的聚吡咯（PPy/DS）两种水溶液储钠正极体系以及聚酰亚胺、多活性聚氨基蒽醌两类水溶液储钠负极体系。结合正负极容量匹配、电解液匹配以及库伦匹配的原理，构建了1~2套具有实用价值的水溶液钠离子电池体系。进一步通过非原位表征手段分析了聚合物的储钠反应过程的结构变化与反应机理，为进一步发展清洁廉价且高性能的储能材料与器件提供了理论指导与技术支持。