高回弹高粘性准固态聚合物电解质的制备及其柔性储能器件的构建

With the rapid development of wearable electronics, deformable displays and other flexible electronic products, flexible energy-storage devices have attracted enormous research interests. Stretchable polymer electrolytes are pivotal component elements for flexible energy-storage devices. However, the existing polymer electrolytes severely restrict the development of flexible energy-storage devices with high capacity and long life due to their poor elastic resilience, undesirable stickiness to flexible electrodes, poor tolerance to acid, alkali and polar electrolytes. Herein, we propose novel “elastic skeleton reinforcement” strategy to develop stretchable quasi-solid-state polymer electrolytes with excellent elastic resilience, strong stickiness, wide application scope including strong acidic and basic electrolytes as well organic ones. It starts with polyolefin elastomers and polar special rubbers as skeleton materials, followed by treatments such as immersion-precipitation, surface modification and in-situ radical polymerization, and γ-ray irradiation can also be utilized to achieve the moderate crosslink and graft modification of polar rubber. The effects of preparation methods on the microstructure, interfacial property, stickiness, elastic resilience, mechanical strength, conductivity and electrochemical performance will be systematically investigated. Besides, research interest will also be focused on the interaction mechanism at stretchable electrolyte/flexible electrode interface and the charge transport mechanism so as to provide theoretical basis and technical support for stretchable quasi-solid-state polymer electrolytes in the application of flexible energy-storage devices.

随着智能穿戴、可变形显示器等柔性电子产品的不断涌现，柔性储能器件引起人们广泛关注。聚合物电解质是决定柔性储能器件性能的关键材料。现有聚合物电解质存在回弹性差、与电极粘结不理想、耐酸碱或极性溶剂欠佳等问题，这是制约高容量长寿命柔性储能器件发展的瓶颈。本项目拟采用“弹性骨架增强”新策略来构建高回弹、高粘性、耐酸碱或极性溶剂的可拉伸准固态聚合物电解质。以聚烯烃弹性体或极性特种橡胶为骨架材料，分别集成浸入沉淀、表面修饰和原位自由基聚合等方法，以及运用γ-射线辐照手段实现对极性橡胶的适度交联和接枝改性，制备适用于强酸强碱和有机电解液体系的可拉伸聚合物电解质。重点研究制备方法对可拉伸电解质显微结构和界面性质的影响以及对其粘结性、回弹性、力学强度、电导率和电化学性质的影响规律。揭示可拉伸电解质与柔性电极间界面作用机制和电荷传输机理，为推动可拉伸聚合物电解质在柔性储能器件中应用提供理论依据和技术支撑。

智能穿戴等柔性电子产品的迅猛发展，对柔性储能器件提出更高的要求。聚合物电解质作为柔性储能器件的关键组件，尚存在回弹性差、与电极粘结不理想等瓶颈问题。本项目基于“弹性骨架增强”策略，创制了高回弹和高粘性可拉伸准固态聚合物电解质的新体系，并在高性能可拉伸超级电容器构建策略方面取得显著进展，主要成果包括：1..选用耐碱优异、回弹性好的聚烯烃弹性体为可拉伸基体，集成浸入沉淀相转化、辐照接枝和原位聚合等方法，构筑适用于强碱体系的聚烯烃弹性体多孔膜负载聚丙烯酸-氢氧化钾可拉伸准固态电解质，该电解质在150%应变下1000次拉伸循环后几乎不发生的塑性变形，并呈现142 mS cm-1的高离子电导率。通过改变反应参数和工艺条件，实现了聚合物电解质的孔结构和界面性质的调控。2..采用氟橡胶为弹性基体，运用模板成孔、化学交联和γ-射线辐照接枝改性等集成技术，制备适用于有机电解液体系的改性氟橡胶可拉伸准固态电解质，该电解质在100%应变下1000次拉伸循环后塑性变形仅为3.7%，离子电导率达8.1 mS cm-1，且具有优异的粘结性。系统研究了可拉伸电解质的化学组成和显微结构对其拉伸回弹性、粘结性和离子电导率的影响规律。3..制备一系列纳米碳负载π共轭聚合物或过渡金属化合物复为柔性电极；以高回弹和高粘结性的准固态电解质充当可拉伸基底，创立了“预拉伸-粘结-回缩”和“预拉伸-粘附-回缩-固化-溶胀”等器件组装方法，所组装的可拉伸超级电容器的能量密度高达65.2 Wh kg-1，且10000次循环后保持为87%。揭示可拉伸电解质与柔性电极间界面作用机理和电荷传输机制，为推进可拉伸准固态电解质在高性能可拉伸储能器件中应用提供理论指导和技术支撑。4. 创制出适于有机电解液体系的导电弹性体负载导电聚合物本征可拉伸电极，克服了常规柔性电极拉伸性差的缺陷，为制备高性能可拉伸储能器件提供新途径。.项目执行期间发表基金标注论文24篇，其中中科院一区13篇，二区5篇，申请发明专利6项，其中授权5项；作会议邀请报告3次，口头报告1次，获上海市技术发明一等奖1项。