紫外光交联法制备全固态聚合物电解质

doi:10.11949/0438-1157.20211460

化工学报 ›› 2022, Vol. 73 ›› Issue (1): 441-450.DOI: 10.11949/0438-1157.20211460

• 材料化学工程与纳米技术 • 上一篇下一篇

紫外光交联法制备全固态聚合物电解质

郑哲楠^1,²(),高翔¹(),罗英武¹,黄杰²

^1.化学工程联合国家重点实验室，浙江大学化学工程与生物工程学院，浙江杭州 310027
^2.福建省现代分离分析科学与技术重点实验室，闽南师范大学化学化工与环境学院，福建漳州 363000

收稿日期:2021-10-13 修回日期:2021-11-25 出版日期:2022-01-05 发布日期:2022-01-18
通讯作者: 高翔
作者简介:郑哲楠(1991—)，女，博士，讲师，zhenan@zju.edu.cn
基金资助:
国家自然科学基金项目(21875213);福建省自然科学基金项目(2020J01805);福建省中青年教师教育科研项目(JAT200339)

Preparation of all-solid-state polymer electrolyte by ultraviolet cross-linking method

Zhenan ZHENG^1,²(),Xiang GAO¹(),Yingwu LUO¹,Jie HUANG²

^1.State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^2.Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, College of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, Fujian, China

Received:2021-10-13 Revised:2021-11-25 Online:2022-01-05 Published:2022-01-18
Contact: Xiang GAO

摘要/Abstract

摘要：

制约全固态聚合物电解质开发应用的瓶颈在于如何同时实现高离子电导率与高机械强度。采用可逆加成断裂链转移（RAFT）溶液聚合技术，以3-环己烯-1-亚甲基丙烯酸酯（CEA）为后交联单体，聚乙二醇甲醚丙烯酸酯（PEGMA）为导离子单体，制备了不同链结构的全固态聚合物电解质，再通过硫醇-烯烃之间的“点击化学”反应形成化学交联网络结构。所制备的三嵌段共聚物电解质具有独立的导离子中间嵌段，且交联单体位于分子链两端，从而能够同时满足离子电导率与机械强度的要求。该三嵌段共聚物电解质在60℃下的离子电导率为6.13×10^-5 S/cm，并应用于磷酸亚铁锂/锂（LiFePO₄/Li）全固态电池。所得电池在0.5 C下循环130圈后，放电比容量为139.1 mAh/g，容量保持率为97.8%，库仑效率高于99.0%，显示出良好的电化学性能。

关键词: 电化学, 电解质, 聚合物, 全固态锂电池, 聚合物电解质, RAFT自由基聚合, 链结构与性能关系

Abstract:

In the application of all-solid-state polymer electrolyte (SPE), the bottleneck is how to meet the requirements of ion conductivity and mechanical strength simultaneously. Aiming at the above problem, this paper adopts the reversible addition fragmentation chain transfer (RAFT) solution polymerization technology to synthesize SPEs with different chain structures. The SPEs apply the cyclohex-3-enylmethyl acrylate (CEA) as post-crosslinking monomer and the poly(ethylene glycol) methyl ether acrylate (PEGMA) as ion-conducting monomer. A chemically cross-linked network structure was formed by the “click chemistry” reaction between the double bond on the cyclohexene in CEA and the mercaptan. The prepared triblock copolymer electrolyte has independent ion-conducting blocks while the crosslinking monomers concentrating at both ends of the molecular chain, thus meeting the demands of mechanical strength and ionic conductivity simultaneously. The prepared triblock copolymer electrolyte presented ionic conductivity of 6.13×10^-5 S/cm at 60℃. The lithium iron phosphate/lithium (LiFePO₄/Li) all-solid-state battery using the prepared triblock copolymer electrolyte presented specific discharge capacity of 139.1 mAh/g after 130 cycles at 0.5 C. The retention rate was 97.8% while the coulombic efficiency remained above 99.0%, showing good electrochemical performance.

Key words: electrochemistry, electrolytes, polymers, all-solid-state lithium battery, polymer electrolytes, RAFT radical polymerization, relationship between chain structure and properties

中图分类号:

TQ 152

郑哲楠, 高翔, 罗英武, 黄杰. 紫外光交联法制备全固态聚合物电解质[J]. 化工学报, 2022, 73(1): 441-450.

Zhenan ZHENG, Xiang GAO, Yingwu LUO, Jie HUANG. Preparation of all-solid-state polymer electrolyte by ultraviolet cross-linking method[J]. CIESC Journal, 2022, 73(1): 441-450.

图/表 15

图1 3-环己烯-1-亚甲基丙烯酸酯(CEA)的合成机理

Fig.1 Scheme of synthesis of cyclohex-3-enylmethyl acrylate (CEA)

图2 聚乙二醇甲醚丙烯酸酯-3-环己烯-1-亚甲基丙烯酸酯共聚物的核磁氢谱

Fig.2 1H NMR spectrum of P(PEGMA-co-CEA)

图3 聚合物电解质与季戊四醇四(3-巯基丙酸)酯(PETMP)的紫外光交联反应机理

Fig.3 Scheme of UV crosslinking reaction of the synthesized polymer electrolyte and PETMP

图4 聚乙二醇甲醚丙烯酸酯均聚物的DSC曲线

Fig.4 DSC curve of PPEGMA homopolymer

图5 三嵌段共聚物电解质与无规共聚物电解质的DSC曲线与DSC微分曲线

Fig.5 DSC curves and DSC derivative curves of TRI and RAN

图6 三嵌段共聚物电解质的线性黏弹区间测试

Fig.6 Determination of the linear viscoelastic range of TRI

图7 三嵌段共聚物电解质与无规共聚物电解质的复数模量及损耗角正切随频率的变化关系

Fig.7 Relationship between G*, tanδ and frequency of TRI and RAN

图8 采用三嵌段共聚物电解质与电解液的LiFePO4/Li电池的倍率性能(测试温度：三嵌段共聚物电解质为60℃，电解液为30℃)

Fig.8 Rate performance of LiFePO4/Li cell using TRI and commercial liquid electrolyte (The test temperature for TRI was 60℃, while that for liquid electrolyte was 30℃)

图9 采用三嵌段共聚物电解质(a)与电解液(b)的LiFePO4/Li电池在不同测试倍率下的充放电曲线

Fig.9 Charge/discharge profiles of LiFePO4/Li cells using TRI (a) and commercial liquid electrolyte (b) under different test rates

图10 采用三嵌段共聚物电解质与电解液的LiFePO4/Li电池的Nyquist图(测试温度：三嵌段共聚物电解质为60℃，电解液为30℃，插图为半圆区域的局部放大图)

Fig.10 Nyquist plots of LiFePO4/Li cells using TRI and commercial liquid electrolyte after rate performance tests and at discharge state (the test temperature for TRI was 60℃, while that for liquid electrolyte was 30℃; the inset image is a partial enlargement of the semicircular)

图11 采用三嵌段共聚物电解质的LiFePO4/Li电池的循环性能(测试温度为60℃，充/放电倍率均为0.5 C)

Fig.11 Cycling performance of LiFePO4/Li cell using TRI and its corresponding coulombic efficiencies (the test temperature was 60℃ and the test rate was 0.5 C for both charge and discharge procedures)

图12 采用三嵌段共聚物电解质的LiFePO4/Li电池经过不同循环次数后的Nyquist图(测试温度为60℃，内嵌图为半圆区域的局部放大图)

Fig.12 Nyquist plots of LiFePO4/Li cell using TRI after different amounts of cycles and at discharge state (the test temperature was 60℃, the inset image is a partial enlargement of the semicircular)

图A1 3-环己烯-1-亚甲基丙烯酸酯(CEA)的分子式与核磁氢谱

Fig. A1 1H NMR spectrum and structural formula (inset) of cyclohex-3-enylmethyl acrylate (CEA)

图A3 聚乙二醇甲醚丙烯酸酯(PEGMA)的分子式与核磁氢谱

Fig.A3 1H NMR spectrum and structural formula (inset) of poly(ethylene glycol) methyl ether acrylate (PEGMA)

图A2 3-环己烯-1-亚甲基丙烯酸酯(CEA)的气相色谱

Fig.A2 Gas chromatogram of cyclohex -3-enylmethyl acrylate (CEA)

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紫外光交联法制备全固态聚合物电解质

Preparation of all-solid-state polymer electrolyte by ultraviolet cross-linking method

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