Preparation and Properties of Densely Cross-linked Fluorinated Poly(arylene ether) Anion Exchange Membranes

Meng-yi Zhao; Yu Chen; Wen-zheng Zhang; Dong-yang Chen

doi:10.11777/j.issn1000-3304.2021.21228

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Preparation and Properties of Densely Cross-linked Fluorinated Poly(arylene ether) Anion Exchange Membranes

Research Article | 更新时间：2024-10-08

- Preparation and Properties of Densely Cross-linked Fluorinated Poly(arylene ether) Anion Exchange Membranes
- ACTA POLYMERICA SINICA Vol. 53, Issue 2, Pages: 153-164(2022)
- 作者机构：
  
  福州大学材料科学与工程学院福州 350116
- 作者简介：
  
  Dong-yang Chen, E-mail: dongyang.chen@fzu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2021.21228
  CLC：
- Published：20 February 2022，
  
  Published Online：12 November 2021，
  
  Received：14 August 2021，
  
  Revised：29 September 2021，
- 稿件说明：
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赵梦依,陈煜,张文政等.局部密集交联含氟聚芳醚阴离子交换膜的制备与性能[J].高分子学报,2022,53(02):153-164.

Zhao Meng-yi,Chen Yu,Zhang Wen-zheng,et al.Preparation and Properties of Densely Cross-linked Fluorinated Poly(arylene ether) Anion Exchange Membranes[J].ACTA POLYMERICA SINICA,2022,53(02):153-164.
赵梦依,陈煜,张文政等.局部密集交联含氟聚芳醚阴离子交换膜的制备与性能[J].高分子学报,2022,53(02):153-164. DOI： 10.11777/j.issn1000-3304.2021.21228.

Zhao Meng-yi,Chen Yu,Zhang Wen-zheng,et al.Preparation and Properties of Densely Cross-linked Fluorinated Poly(arylene ether) Anion Exchange Membranes[J].ACTA POLYMERICA SINICA,2022,53(02):153-164. DOI： 10.11777/j.issn1000-3304.2021.21228.

摘要

为开发同时具有阴离子传导率高、钒离子渗透率低、机械性能和化学稳定性优异的阴离子交换膜(AEM)，本文以逐步缩聚法合成了含叔胺基的含氟聚芳醚(FPAE)，然后以十溴丙基柱[5

]

芳烃(P5Br)作为交联剂，通过P5Br上的溴烷基与FPAE上的叔胺基之间的亲核取代反应进行交联，最后用碘甲烷将剩余叔胺基季铵化，制得一系列局部密集交联含氟聚芳醚阴离子交换膜QAFPAE-P5Br-

. 研究结果表明，所有膜在极性非质子溶剂中都具有较高的凝胶含量，证明已形成高效交联结构. 随着交联剂含量从0.5%增加到5%，膜的吸水率、溶胀率、阴离子传导率和VO

透过率逐渐降低，而离子选择性、拉伸强度、面电阻和氧化稳定性逐渐增加. 交联剂含量为1%的QAFPAE-P5Br-1%膜同时具有较低的面电阻和VO

透过率，综合性能优异. 以QAFPAE-P5Br-1%组装的全钒液流电池(VRFB)在80 mA·cm

-2

的电流密度下具有86.5%的能量效率，比以Nafion 212组装的VRFB高出7.7%. 另外，以QAFPAE-P5Br-1%组装的VRFB还具有优异的循环稳定性、放电容量保持率和抗自放电性能. 可见，局部密集交联是一种提高VRFB用AEM综合性能的有效方法.

Abstract

In order to develop anion exchange membranes (AEMs) with simutaneously good anion conductivity

low vanadium ion permeability

excellent mechanical property

and high chemical stability

a fluorinated poly-(arylene ether) (FPAE) containing tertiary amine groups was condensation polymerized and then cross-linked with decabromopropyl pillar[5

]

arene (P5Br)

via

the nucleophilic substitution reaction. After that

iodomethane was introduced to convert the remaining tertiary amine g

roups into quaternary ammonium groups. A series of densely cross-linked FPAE AEMs

namely QAFPAE-P5Br-

were prepared with high gel contents in polar aprotic solvents. As the loading amount of P5Br is increased from 0.5% to 5%

the water uptake

swelling ratio

anion conductivity and VO

permeability of the membranes are decreased

but the ion selectivity

tensile strength

area resistance and oxidative stability of the membranes are increased. The QAFPAE-P5Br-1% with only 1% of P5Br loaded has both low area resistance and low VO

permeability

which are promising for VRFB applications. At a current density of 80 mA·cm

-2

the VRFB assembled with QAFPAE-P5Br-1% shows an energy efficiency of 86.5%

which is 7.7% higher than that of the VRFB assembled with Nafion 212. Besides

the VRFB assembled with QAFPAE-P5Br-1% has excellent cycling stability

high discharge capacity retention and good anti-self-discharge performance. Therefore

the dense cross-linking is an effective protocol to enhance the overall performance of AEMs.

关键词

全钒液流电池阴离子交换膜聚芳醚密集交联氧化稳定性

Keywords

Vanadium redox flow batteryAnion exchange membranePoly(arylene ether)Dense cross-linkingOxidative stability

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