Design, Preparation and Visual Detection of Fluorophenyl Polynorbornene Anion Exchange Membrane with Single Quaternary Ammonium Salt

Yan Wang; Ruo-xin Li; Zhi-cheng Wu; Yue-feng Bai; Chao-fan Lan; Qiu-yue Xiao; Ping Hu; Hong-fu Li; Kang-min Niu; Yen Wei

doi:10.11777/j.issn1000-3304.2023.23119

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Design, Preparation and Visual Detection of Fluorophenyl Polynorbornene Anion Exchange Membrane with Single Quaternary Ammonium Salt

Research Article | 更新时间：2023-09-25

- Design, Preparation and Visual Detection of Fluorophenyl Polynorbornene Anion Exchange Membrane with Single Quaternary Ammonium Salt
  增强出版
- ACTA POLYMERICA SINICA Vol. 54, Issue 10, Pages: 1599-1612(2023)
- 作者机构：
  
  1.四川师范大学化学与材料科学学院成都 610066
  2.清华大学化学系北京 100084
  3.北京科技大学材料科学与工程学院北京 100083
- 作者简介：
  
  Yue-feng Bai, E-mail: baiyf@sicnu.edu.cn
  Yen Wei, E-mail: weiyen@tsinghua.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23119
  CLC：
- Published：20 October 2023，
  
  Published Online：25 August 2023，
  
  Received：03 May 2023，
  
  Accepted：21 June 2023
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王艳,李若馨,吴志成等.氟代苯基聚降冰片烯单阴离子交换膜的制备及损伤可视化检测[J].高分子学报,2023,54(10):1599-1612.

Wang Yan,Li Ruo-xin,Wu Zhi-cheng,et al.Design, Preparation and Visual Detection of Fluorophenyl Polynorbornene Anion Exchange Membrane with Single Quaternary Ammonium Salt[J].ACTA POLYMERICA SINICA,2023,54(10):1599-1612.
王艳,李若馨,吴志成等.氟代苯基聚降冰片烯单阴离子交换膜的制备及损伤可视化检测[J].高分子学报,2023,54(10):1599-1612. DOI： 10.11777/j.issn1000-3304.2023.23119.

Wang Yan,Li Ruo-xin,Wu Zhi-cheng,et al.Design, Preparation and Visual Detection of Fluorophenyl Polynorbornene Anion Exchange Membrane with Single Quaternary Ammonium Salt[J].ACTA POLYMERICA SINICA,2023,54(10):1599-1612. DOI： 10.11777/j.issn1000-3304.2023.23119.

摘要

具有高的离子电导率和碱性稳定性的碱性阴离子交换膜(AEMs)是制备碱性燃料电池的关键. 通过合理的分子设计，选用全烷烃基聚降冰片烯嵌段共聚物作为AEMs的主链，可有效避免AEMs在强碱条件下的降解. 同时在侧链中引入亲水性含氟苯基季铵盐作为离子导电基元，疏水性三乙基硅基团作为非导电基元，利用二者之间的亲疏水作用，在薄膜中形成可供OH

迁移的离子通道，有助于提高AEMs的电导率. 通过调节含氟苯基季铵盐中氟原子的数目，可以调节离子通道的大小，从而实现对薄膜电导率的调控. 另外，为了实现AEMs的损伤可视化监测，将具有聚集诱导发光作用的四苯乙烯基二降冰片烯酰亚胺作为交联单体引入聚合物中，通过烯烃的复分解反应，开环聚合制备得到单离子AEMs. 聚合物表现出优异的热稳定性(5%热失重温度

250 ℃)，力学性能(

= 36.56 MPa

=16.92%) 和耐碱性能(在6 mol/L NaOH溶液中浸泡7天后，电导率仅下降3.3%). 通过扫描电子显微镜可观测到微相分离形成的离子通道，与已报道的单离子AEMs相比，表现出较高的离子电导率(80 ℃，24 mS/cm). 在365 nm光照下，薄膜发出均匀的绿色荧光，损伤处则无荧光，实现了AEMs的可视化检测.

Abstract

Alkaline anion exchange membrane (AEMs) is an important component in the preparation of alkaline fuel cells

which should have high ionic conductivity and alkaline stability. In this work

we present a rationally designed block copolymer of polynorbornene as the backbone of AEMs

which maintains excellent stability in strong alkaline media. Furthermore

ionic conducting fluorophenyl quaternary ammonium salt and non-conducting triethyl silicon group are introduced in side chains to attain tunable polymer structures. Due to the hydrophilic and hydrophobic interactions

channels are formed in the polymer membrane for the transfer of hydroxide. In addition

in order to achieve nondestructive detection of AEMs

tetraphenyl ethylene with aggregation-induced luminescence

for the first time

is introduced as crosslinking monomer to prepare block copolymers

via

ring-opening metathesis polymerization with Grubbs II as catalyst. The copolymers exhibit excellent thermostability

mechanical properties and alkali resistance. The maximum stress and elongation at break of PNB-NOHPhF1-3Si-TPE are

= 36.56 MPa and

=16.92%

respectively

and the 5% weight lost temperature is over 250 ℃. Compared with the reported AEMs with single quaternary ammonium salt

the block copolymers PNB-NOHPhF1-3Si-TPE show better alkali resistance and higher conductivity of 24 mS/cm at 80 ℃. The ion channels formed by microphase separation can be observed with scanning electron microscopy (SEM) by scanning the polymer cross section. Under 365 nm UV-light

the film emits uniform green fluorescence. Because of the lack of fluorescence at the damage sites

the integrity of film is non-destructively visualized.

关键词

碱性阴离子交换膜聚降冰片烯开环易位聚合微相分离聚集诱导发光

Keywords

Alkaline anion exchange membranePolynorborneneRing-opening metathesis polymerizationMicrophase separationAggregation-induced emission

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