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林产化学与工业 ›› 2021, Vol. 41 ›› Issue (4): 51-61.doi: 10.3969/j.issn.0253-2417.2021.04.008

• 研究报告 • 上一篇    下一篇

具有抗冻特性的水凝胶电解质的制备及其在固态超级电容器中的应用

张盖同1, 宋晓丽3, 杨福生1, 南静娅1,2, 储富祥1,2, 王春鹏1,2,*()   

  1. 1. 中国林业科学研究院 林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室; 江苏省林业资源高效加工利用协同创新中心, 江苏 南京 210042
    2. 中国林业科学研究院 林业新技术研究所, 北京 100091
    3. 山东省临沂市生态环境局兰陵县分局, 山东 临沂 276000
  • 收稿日期:2020-12-03 出版日期:2021-08-28 发布日期:2021-08-31
  • 通讯作者: 王春鹏 E-mail:wangcpg@163.com
  • 作者简介:王春鹏, 研究员, 博士生导师, 主要从事生物基高分子材料及胶黏剂的研究; E-mail: wangcpg@163.com
    张盖同(1996-), 男, 山东济宁人, 硕士生, 从事生物基功能材料的研究工作
  • 基金资助:
    国家重点研发计划国际合作专项(2017YFE0106800)

Preparation of Anti-freezing Hydrogel Electrolyte and Its Application in Solid-state Supercapacitors

Gaitong ZHANG1, Xiaoli SONG3, Fusheng YANG1, Jingya NAN1,2, Fuxiang CHU1,2, Chunpeng WANG1,2,*()   

  1. 1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province; Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing 210042, China
    2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China
    3. Lanling County Branch of Linyi Ecological Environment Bureau, Linyi 276000, China
  • Received:2020-12-03 Online:2021-08-28 Published:2021-08-31
  • Contact: Chunpeng WANG E-mail:wangcpg@163.com

摘要:

以大豆蛋白(SPI)、聚乙烯醇(PVA)和丙烯酰胺(AAm)为原料,过硫酸铵(APS)为引发剂,N,N'-亚甲基双丙烯酰胺(MBAA)为交联剂,氯化锂为电解质盐,N,N,N',N'-四甲基乙二胺(TEMED)为促进剂制备得到具有抗冻特性的SPI-PVA-PAAm/LiCl水凝胶电解质,在低温条件下,探究了其力学性能以及组装成超级电容器后的电化学性能。研究结果表明:水凝胶电解质SPI-PVA-PAAm/LiCl具有优异的抗冻特性,这是由于一定浓度的LiCl降低了水凝胶电解质中纯水的凝固点,抑制了水分子的结晶行为。在环境温度由25℃降低至-20℃后,水凝胶电解质SPI-PVA-PAAm/LiCl仍具有较好的力学性能和离子电导率;随着LiCl用量的增加,SPI-PVA-PAAm/LiCl压缩性能呈现先增大后减小的趋势,离子电导率呈现增大的趋势。在经历80%的压缩应变循环10次后,LiCl浓度为5 mol/L的水凝胶电解质(S-Li-5),应力保持率>100%,塑性变形率 < 25%,能量损耗系数 < 0.33。利用LiCl浓度15 mol/L的水凝胶电解质(S-Li-15)与碳纳米管纸组装成固态超级电容器,在环境温度由25℃降低至-20℃时,器件能够保持80%以上的比电容(由GCD曲线计算),并且可经受0~70%的压缩应变而不发生损坏,仍可正常工作;此外,电流密度为8.12 A/g时,器件在-20℃下经历1 000次循环后的电容保持率为91%。

关键词: 大豆蛋白, 聚乙烯醇, 水凝胶电解质, 超级电容器, 抗冻性能

Abstract:

An anti-freezing hydrogel electrolyte(SPI-PVA-PAAm/LiCl) was synthesized, in which soybean protein isolates (SPI), ployvinyl alcohol(PVA) and acrylamide(AAm) were used as raw materials, ammonium persulfate(APS) was used as the initiator, N, N'-methylenebisacrylamide(MBAA) was used as the covalent crosslinker, LiCl was used as the electrolyte salt, and N, N, N', N'-tetramethylethylenediamine(TEMED) was used as the accelerator. Under low temperature conditions, the mechanical properties of the hydrogel electrolyte were analyzed, and the electrochemical properties of the solid-state supercapacitor based on this hydrogel electrolyte were investigated. The results showed that the hydrogel electrolyte had excellent anti-freezing propertity, because a certain molar concentration of LiCl reduced the freezing point of pure water in the hydrogel electrolyte and inhibited the crystallization behavior of water molecules. When the environmental temperature was reduced from 25℃ to -20℃, the hydrogel electrolyte still showed good mechanical properties and ionic conductivity. With the increase of the amount of LiCl, the compression performance of the hydrogel electrolyte firstly increased and then decreased, and the ionic conductivity increased. After 10 cycles of 80% compression strain, the stress retention rate, plastic deformation rate and energy loss coefficient of the hydrogel electrolyte with LiCl concentration of 5 mol/L(S-Li-5) were more than 100%, less than 25% and 0.33, respectively. The hydrogel electrolyte with LiCl concentration of 15 mol/L(S-Li-15) and CNTs were used to assemble the solid supercapacitor whose electrochemical performance was evaluated. When the ambient temperature was reduced from 25℃ to -20℃, the specific capacitance of assembled supercapacitor calculated by GCD curve could be maintained above 80%, and 0-70% compression strain could be withstood without damage, and the supercapacitor could still work normally; In addition, when the current density was 8.12 A/g, the capacitance retention rate of the device was higher than 91% after 1 000 cycles at -20℃.

Key words: soybean protein, polyvinyl alcohol, hydrogel electrolyte, supercapacitor, anti-freezing

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