基于温度诱导相转变共聚物和导电聚合物的自隔断超级电容器

doi:10.6023/A23020055

摘要/Abstract

为了提高超级电容器等储能设备的使用安全性, 扩大其实际应用领域, 本工作针对现阶段最常见的储能设备热失控问题, 提出了一种智能高效的超级电容器自我隔断策略. 通过自由基聚合将N-异丙基丙烯酰胺和丙烯酰胺共聚得到热响应聚合物, 将其溶解在氯化锂水溶液中作为电解液, 与导电聚合物电极组合后得到自隔断超级电容器. 得益于热响应电解质的温度诱导相转变特性, 该超级电容器不仅具有高效的充放电特性, 而且在器件发生热失控后能自发地切断离子转移, 阻止器件的进一步恶化, 具有88.1%的自隔断效率; 其次, 共聚物在相转变后会发生皱缩, 对光线具有明显散射并呈现出低透过率的乳白色, 这就使得人们可以通过颜色变化排查发生热失控的故障器件. 因此, 本工作制备的智能且高安全性的超级电容器将进一步为储能设备的普及应用提供新的思路.

关键词: 超级电容器, 自隔断, 热失控, 热响应共聚物, 故障排查

In order to improve the safety of energy storage devices including supercapacitors and expand their practical application, this work proposes an intelligent yet efficient self-partition strategy for the most common problem of thermal runaway at this stage. Firstly, N-isopropylacrylamide (NIPAM) and acrylamide (AM) are copolymerized by free radical polymerization to obtain a thermally responsive copolymer, which is dissolved in lithium chloride aqueous solution as the electrolyte. Self-partition supercapacitors are obtained by combining this as-prepared electrolyte with conductive polymer electrodes. Benefiting from the temperature-induced phase transition characteristics of thermally responsive electrolyte, the supercapacitors not only have efficient charge-discharge characteristics but also automatically cut off the ion transfer after the thermal runaway of the device with a self-partition efficiency of 88.1%, preventing the further deterioration of the device. In addition, the copolymer will shrink after the phase change caused by thermal runaway, which scatters the light and shows milky white with low transmittance, making it possible to troubleshoot the faulty devices with thermal runaway through color change. Therefore, the intelligent and high-safety supercapacitors prepared in this work will further provide a potential reference for the popularization and application of energy storage devices.

Key words: supercapacitor, self-partition, thermal runaway, thermal response copolymer, troubleshooting

引用此文

李西安, 李孝坤. 基于温度诱导相转变共聚物和导电聚合物的自隔断超级电容器[J]. 化学学报, 2023, 81(5): 511-519.

Li Xian, Li Xiaokun. Self-partition Supercapacitor Based on Temperature-induced Phase Transition Copolymer and Conductive Polymer[J]. Acta Chimica Sinica, 2023, 81(5): 511-519.

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图/表 7

图1. (a) 自隔断超级电容器结构示意图; (b) 热响应共聚物制备流程; (c) 导电聚合物制备流程示意图

Figure 1. (a) Structure diagram of device; the preparation of (b) thermally responsive copolymer and (c) conductive polymer

图2. (a) 共聚物和导电聚合物红外光谱; (b) PEDOT的SEM图; 热响应共聚物在(c)室温的SEM和在(d)高温下的SEM图

Figure 2. (a) FTIR curves of the copolymer and conductive polymer; (b) SEM image of PEDOT; SEM images of thermally responsive copolymer at (c) 25 ℃ and (d) 50 ℃

图3. (a) 导电聚合物电极的CV曲线; (b) 恒电位极化下的光谱曲线; (c) 恒电流充放电曲线; (d) 交流阻抗图

Figure 3. (a) CV curves of conductive polymer electrode; (b) spectrum curves at potentiostatic polarization; (c) constant current charging and discharging curves; (d) AC impedance curve

图4. (a) 电容器的恒电流充放电曲线; (b) 倍率性能; (c) 离子电导率随温度变化曲线; (d) 热响应共聚物电解质随温度变化图

Figure 4. (a) The constant current charging and discharging curves of the capacitor; (b) rate performance; (c) the curves of ion conductivity changing with temperature; (d) temperature dependent images of thermally responsive copolymer electrolyte

图5. (a)几种电解质的离子电导率随温度的变化; (b)基于几种不同电解质的电容器的GCD曲线

Figure 5. (a) Ion conductivity of several electrolytes varies with temperature; (b) GCD curves of capacitors based on several different electrolytes

图6. (a) 电容器不同温度下充放电曲线; (b) 不同温度下的电容值; (c) 不同温度下的奈奎斯特图; (d) 透过率曲线变化

Figure 6. (a) Charging and discharging curves of capacitors at different temperatures; (b) capacitance values at different temperatures; (c) Nyquist plots at different temperatures; (d) variation of the transmittance curves

图7. (a) 电容器循环稳定性曲线; (b) 电容器升温-降温反复循环实验

Figure 7. (a) Cycle stability curves of the capacitor; (b) cyclic experiments of heating and cooling for the capacitor

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