Preparation and Properties of Composite Proton Exchange Membranes from Tröger's Base-based Polyimides/Polybenzimidazoles for Fuel Cells Operating in a Wide Temperature Range

Jian-ming Zhong; Jun-ming Dai; Yu Zhang; Qing-mei Zhao; Xu Zhang; Yong-bing Zhuang

doi:10.11777/j.issn1000-3304.2023.23245

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Preparation and Properties of Composite Proton Exchange Membranes from Tröger's Base-based Polyimides/Polybenzimidazoles for Fuel Cells Operating in a Wide Temperature Range

Research Article | 更新时间：2024-04-16

- Preparation and Properties of Composite Proton Exchange Membranes from Tröger's Base-based Polyimides/Polybenzimidazoles for Fuel Cells Operating in a Wide Temperature Range
- Acta Polymerica Sinica Vol. 55, Issue 4, Pages: 452-461(2024)
- 作者机构：
  
  1.长江大学化学与环境工程学院荆州 434023
  2.中国科学院过程工程研究所生化工程国家重点实验室北京 100190
  3.中国科学院大学化学工程学院北京 100049
- 作者简介：
  
  Qing-mei Zhao, E-mail: 300516@yangtzeu.edu.cn
  Yong-bing Zhuang, E-mail: ybzhuang@ipe.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23245
  CLC：
- Published：20 April 2024，
  
  Published Online：17 January 2024，
  
  Received：09 October 2023，
  
  Accepted：15 November 2023
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钟建铭, 代俊明, 张宇, 赵庆美, 张旭, 庄永兵. 含朝格尔碱基聚酰亚胺-聚苯并咪唑宽温域复合质子交换膜的制备和性能. 高分子学报, 2024, 55(4), 452-461

Zhong, J. M.; Dai, J. M.; Zhang, Y.; Zhao, Q. M.; Zhang, X.; Zhuang, Y. B. Preparation and properties of composite proton exchange membranes from Tröger's base-based polyimides/polybenzimidazoles for fuel cells operating in a wide temperature range. Acta Polymerica Sinica, 2024, 55(4), 452-461
钟建铭, 代俊明, 张宇, 赵庆美, 张旭, 庄永兵. 含朝格尔碱基聚酰亚胺-聚苯并咪唑宽温域复合质子交换膜的制备和性能. 高分子学报, 2024, 55(4), 452-461 DOI： 10.11777/j.issn1000-3304.2023.23245.

Zhong, J. M.; Dai, J. M.; Zhang, Y.; Zhao, Q. M.; Zhang, X.; Zhuang, Y. B. Preparation and properties of composite proton exchange membranes from Tröger's base-based polyimides/polybenzimidazoles for fuel cells operating in a wide temperature range. Acta Polymerica Sinica, 2024, 55(4), 452-461 DOI： 10.11777/j.issn1000-3304.2023.23245.

摘要

针对氢燃料电池对宽温域质子交换膜材料的迫切应用需求，合成了新型含Tröger's base (TB)结构的聚苯并咪唑(TB-PBI-N)，并以之为填料与含TB基聚酰亚胺(PI-TB-N)共混，制备了5种不同比例的磷酸掺杂复合质子交换膜. 通过傅里叶红外光谱(FTIR)、核磁氢谱(

H-NMR)、热失重分析(TGA)和拉伸试验等表征了质子交换膜的结构、机械性能、热及氧化稳定性、酸吸收、溶胀度、质子电导率(

)及氢/空燃料单电池的功率密度(PD)，探究了TB-PBI-N填料的添加对复合膜性能的影响. 结果表明：磷酸掺杂前复合膜的拉伸强度为87.3~129.5 MPa，掺杂后膜的拉伸强度为3.7~9.5 MPa，磷酸吸收率为235.3%~288.7%，溶胀率为13.9%~25.0%，可在30~160 ℃传导质子，

和PD最高分别可达94.3 mS/cm和334.6 mW/cm

. TB-PBI-N填料的添加改善了复合膜的机械性能及磷酸掺杂膜的尺寸稳定性. 另外，填料TB-PBI-N的TB结构具有额外的碱基位点，可提供一定的酸吸附能力，从而提升了

. 其中，复合膜TB-PI-5PBI的拉伸强度为116.8 MPa，磷酸掺杂后膜的

=67.7 mS/cm (160 ℃、0% RH)，在30、80和160 ℃下，电池的功率密度分别达到58.9、224.7和334.6 mW/cm

，具有无湿度环境宽温域范围应用前景.

Abstract

For proton exchange membranes used in fuel cells

it is critical to develop materials that can withstand a wide range of industrially relevant temperatures. In this work

novel polybenzimidazole (TB-PBI-N) containing Tröger's base (TB) units was synthesized and used as a filler to be blended with TB-based polyimide (PI-TB-N) for five types of phosphoric acid-doped composite proton exchange membranes. The chemical structures

mechanical properties

thermal and oxidative stability

acid adsorption

swelling ratios

proton conductivity (

) and power density of H

O/air fuel cells (PD) of the composite membranes were characterized by Fourier transform infrared spectroscopy (FTIR)

magnetic resonance spectroscopy (

H-NMR)

thermogravimetric analysis (TGA)

and tensile tests. The effect of incorporated TB-PBI-N filler on the properties of the composite membranes were investigated in details. The results showed that the tensile strength of the composite membranes without phosphoric acid doping were 87.3-129.5 MPa

and 3.7-9.5 MPa for the acid doped membranes. The phosphonic acid uptake were 235.3%-288.7% after doping with the swelling ratios ranging between 13.9%-25.0%

and the composite membranes can conduct protons at wide temperature range from 30 ℃ to 160 ℃. The maximum

and PD of the composite membranes reached up to 94.3 mS/cm and 334.6 mW/cm

respectively. Furthermore

it was found that the introduction of TB-PBI-N filler improved the mechanical properties and the dimensional stability for the phosphoric acid doped membranes. In addition

the TB units in TB-PBI-N have additional base sites

which enhanced acid adsorption capacity and greatly improved the

values of the membranes. Among the five membrane types

the TB-PI-5PBI membrane showed a tensile strength of 116.8 MPa

proton conductivity of 67.7 mS/cm (160 ℃

0% RH). More importantly

the PD values of the fuel cells reached 58.9

224.7 and 334.6 mW/cm

at 30

80 and 160 ℃

respectively

indicating excellent application prospect in a wide temperature range under non-humidity environment.

关键词

聚酰亚胺聚苯并咪唑朝格尔碱基质子交换膜复合膜

Keywords

PolyimidepolybenzimidazoleTröger's baseProton exchange membranesComposite membranes

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Related Institution

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State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tiangong University

College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology

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