Research status and development trend of gel polymer electrolytes in supercapacitors
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摘要: 新型固态超级电容器具有更高的机械稳定性、易操作性和耐温耐候性,既无传统固态电解质易泄露、不便于携带的缺点,也无液态聚合物电解质易腐蚀、易爆炸的风险,是极具市场前景的高功率储能型超级电容器。固态超级电容器需要电解质离子流动性好、导电率高、活性好和机械稳定性高。凝胶聚合物电解质因其具有安全性高、稳定性好和天然无污染性等特点,是目前固态聚合物电解质中适配度最高的一种电解质。根据电解质基底来源不同可以分为天然型和合成型两类聚合物电解质,复合聚合物电解质主要由聚合物基体、添加剂和电解质盐组成。复合聚合物电解质在超级电容器中既充当了导电介质,也起着隔膜的作用。本文综述了不同聚合物电解质的特点,阐述了聚合物电解质对超级电容器储能及电化学性能的影响与作用机制,最后提出了构建高效储能系统所面临的挑战和未来发展的聚焦点。Abstract: The new solid-state supercapacitor has higher mechanical stability, easy operability and temperature and weather resistance, neither the traditional solid-state electrolyte is easy to leak, not easy to carry the shortcomings, nor the liquid polymer electrolyte is easy to corrosion, easy to explode risk, is a high-power energy storage supercapacitor with great market prospects. Solid state supercapacitors require electrolyte ion mobility, high conductivity, good activity and high mechanical stability. Gel polymer electrolyte is the most suitable electrolyte in solid polymer electrolyte because of its high safety, good stability and natural pollution-free characteristics. According to the different sources of electrolyte base, it can be divided into two types of natural and synthetic polymer electrolytes. The composite polymer electrolyte is mainly composed of polymer base, additives and electrolyte salts. The composite polymer electrolyte acts as both a conductive medium and a diaphragm in the supercapacitor. In this paper, the characteristics of different polymer electrolytes are reviewed, and the influence and mechanism of polymer electrolytes on the energy storage and electrochemical performance of supercapacitors are described. Finally, the challenges and future development focus of building efficient energy storage systems are put forward.
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Key words:
- gel polymer electrolyte /
- natural type /
- composite form /
- supercapacitor /
- energy storage
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图 4 (a) 固态超级电容器(SSC)的装配过程示意图及基于SPI和HEC的交联原理图; (b) 在0.01赫兹到100千赫的频率范围内的能奎斯特图[18]
Figure 4. (a) Schematic illustration of the assembly process of Solid state supercapacitor(SSC) and schematic diagram of cross linked based on SPI and HEC; (b) Nyquist plots in a frequency range from 0.01 Hz to 100 kHz[18]
图 12 (a) SPS/PAM复合材料的制备工艺;(b) 交流电渗透形成机制的示意图;(c) 损耗模量(G'')与角频率的关系;(d) 5μm有序SPS颗粒在不同浓度下水凝胶的应力-应变曲线[34]
Figure 12. (a) Fabrication process of SPS/PAM composites; (b) The schematic diagram illustrating the formation mechanism of AC electroosmosis; (c) Angular frequency dependence of the loss modulus (G''); (d) The stress-strain curves of hydrogels at different concentrations of ordered 5 μm SPS particles[34]
图 14 (a) 低温、耐脱水和可拉伸电解质水凝胶的设计策略;(b) PAM/CNF/LiCl 50%水凝胶在25℃和−40℃下作为导线的示意图;(c) 在25℃、50% RH条件下将水凝胶保存150天后进行比较;(d) 不同温度下的CV曲线(扫描速率为10 mv /s)[50]
Figure 14. (a) Strategy used in the design of a conductive and stretchable electrolyte hydrogel with low temperature and dehydration tolerance;(b) Demonstration of PAM/CNF/LiCl 50% hydrogels functioning as conductive wires at 25℃ and −40℃; (c) visual comparison after holding the hydrogels for 150 days at 25℃ and 50% RH; (d) CV curves obtained at different temperatures (10 mV/s scan rate)[50]
图 17 (a) 硼酸盐电解液和电极相互作用的示意图;(b) 不同硼酸盐有机电解质在-40℃至115℃范围内的离子电导率和粘度;LiBOB-0.1、LiBOB-0.5和LiBOB-1样品在115℃的双电极体系中的:(c) Ragone图;(d) 比电容和温度的关系;(e) 由6个串并联电池点亮的红色LED(1.8 V)[59]
Figure 17. (a) Schematic diagram of the interaction between borate electrolyte and electrode; (b) ionic conductivity and viscosity of different borate organic electrolyte electrolytes in the temperature range of -40 to 115℃; Electrochemical performance of LiBOB-0.1, LiBOB-0.5 and LiBOB-1 samples in two-electrode system at 115℃, respectively: (c) Ragone plots; (d) Specific capacitances versus temperature; (e) Specific capacitances versus temperature[59]
表 1 复合凝胶聚合物电解质实例
Table 1. Example of composite gel polymer electrolyte
Base material Composite material Preparation method Strength of extension
MPaIonic conductivity s/m References CMC CA Double physical crosslinking 4.42 6.42 [66] PVA EG/H2O Double chemical crosslinking 15.5 0.48 [30] LiCl PVA Freeze-thaw cycle method 0.4 12.83 [51] BC PVA Freeze-thaw cycle method 0.41 13.89 [67] PAA GO Radical polymerization 6.1 16.81 [68] Notes:CMA is short for Carboxymethyl cellulose; CA is short for Carbonic anhydrase; PVA is short for Polyvinyl alcohol; EG is short for Ethylene glycol; BC is short for Bacterial cellulose; PAA is short for Polyacrylic acid; GO is short for Graphene oxide. 表 2 基于不同电解质的固态超级电容器性能对比统计表(不含氧化还原添加剂) [72]
Table 2. Statistical table of solid supercapacitors based on different electrolytes ( without redox additive ) [72]
Electrolyte Working voltage Specific capacitance/(F/g) Conductivity/(S/cm) Energy density/
(Wh/kg)Power density/ Cycling stability/ Hydrogel 1.6 V >100 The highest <20 <10 Better Organogel 4 V 100-200 Higher 18-25 <10 Ordinary Ionic gel 6 V 100-200 Higher Ordinary Ordinary Ordinary Inorganic matter Less <30 Lower Lower Lower Worse -
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