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

钟建铭; 代俊明; 张宇; 赵庆美; 张旭; 庄永兵

doi:10.11777/j.issn1000-3304.2023.23245

您当前的位置：

首页 >

文章列表页 >

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

研究论文 | 更新时间：2024-04-16

- 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
- Preparation and Properties of Composite Proton Exchange Membranes from Tröger's Base-based Polyimides/Polybenzimidazoles for Fuel Cells Operating in a Wide Temperature Range
- 高分子学报 2024年55卷第4期页码：452-461
- 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：
  
  E-mail: 300516@yangtzeu.edu.cn
  ybzhuang@ipe.ac.cn
- 基金信息：
  
  国家自然科学基金面上项目(基金号 52173210);江苏冰城氢能科技有限公司企业委托项目资助
- DOI：10.11777/j.issn1000-3304.2023.23245
  中图分类号：
- 纸质出版日期：2024-04-20，
  
  网络出版日期：2024-01-17，
  
  收稿日期：2023-10-09，
  
  录用日期：2023-11-15
- 稿件说明：
移动端阅览
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

references

Jiao K.; Xuan J.; Du Q.; Bao Z. M.; Xie B. A.; Wang B. W.; Zhao Y.; Fan L. H.; Wang H. Z.; Hou Z. J.; Huo S.; Brandon N. P.; Yin Y.; Guiver M. D. Designing the next generation of proton-exchange membrane fuel cells. Nature, 2021, 595(7867), 361-369. doi:10.1038/s41586-021-03482-7http://dx.doi.org/10.1038/s41586-021-03482-7

张永明, 唐军柯, 袁望章. 燃料电池全氟磺酸质子交换膜研究进展. 膜科学与技术, 2011, 31(3), 76-85. doi:10.3969/j.issn.1007-8924.2011.03.013http://dx.doi.org/10.3969/j.issn.1007-8924.2011.03.013

王保国. 新能源领域的质子交换膜研究与应用进展. 膜科学与技术, 2010, 30(1), 1-8. doi:10.3969/j.issn.1007-8924.2010.01.001http://dx.doi.org/10.3969/j.issn.1007-8924.2010.01.001

Qu E. L.; Hao X. F.; Xiao M.; Han D. M.; Huang S.; Huang Z. H.; Wang S. J.; Meng Y. Z. Proton exchange membranes for high temperature proton exchange membrane fuel cells: challenges and perspectives. J. Power Sources, 2022, 533, 231386. doi:10.1016/j.jpowsour.2022.231386http://dx.doi.org/10.1016/j.jpowsour.2022.231386

Dai J. M.; Zhang Y.; Gong C. L.; Wan Y. H.; Zhuang Y. B. Soluble polybenzimidazoles incorporating Tröger's base for high-temperature proton exchange membrane fuel cells. Chem. Eng. J., 2023, 466, 143151. doi:10.1016/j.cej.2023.143151http://dx.doi.org/10.1016/j.cej.2023.143151

Tang H. Y.; Geng K.; Wu L.; Liu J. J.; Chen Z. Q.; You W.; Yan F.; Guiver M. D.; Li N. W. Fuel cells with an operational range of -20 ℃ to 200 ℃ enabled by phosphoric acid-doped intrinsically ultramicroporous membranes. Nat. Energy, 2022, 7(2), 153-162. doi:10.1038/s41560-021-00956-whttp://dx.doi.org/10.1038/s41560-021-00956-w

张肖肖, 谭浩东, 陈匡胤, 周正, 付旭东, 张荣, 胡圣飞, 赵锋, 李骁, 刘清亭. 基于巯基改性磺化海泡石与聚(2, 5-苯并咪唑)原位复合的宽温域用质子交换膜. 高分子材料科学与工程, 2020, 36(3), 165-174. doi:10.16865/j.cnki.1000-7555.2020.0030http://dx.doi.org/10.16865/j.cnki.1000-7555.2020.0030

Yin B. B.; Wu Y. N.; Liu C. F.; Wang P.; Wang L.; Sun G. X. An effective strategy for the preparation of a wide-temperature-range proton exchange membrane based on polybenzimidazoles and polyacrylamide hydrogels. J. Mater. Chem. A, 2021, 9(6), 3605-3615. doi:10.1039/d0ta08872bhttp://dx.doi.org/10.1039/d0ta08872b

Song M. K.; Zhu X. B.; Liu M. L. A triazole-based polymer electrolyte membrane for fuel cells operated in a wide temperature range (25-150 ℃) with little humidification. J. Power Sources, 2013, 241, 219-224. doi:10.1016/j.jpowsour.2013.04.016http://dx.doi.org/10.1016/j.jpowsour.2013.04.016

Chen J. C.; Wu J. N.; Chen K. H. Synthesis and characterization of novel imidazolium-functionalized polyimides for high temperature proton exchange membrane fuel cells. RSC Adv., 2016, 6(40), 33959-33970. doi:10.1039/c6ra00628khttp://dx.doi.org/10.1039/c6ra00628k

Qu E. L.; Cheng G.; Xiao M.; Han D. M.; Huang S.; Huang Z. H.; Liu W.; Wang S. J.; Meng Y. Z. Composite membranes consisting of acidic carboxyl-containing polyimide and basic polybenzimidazole for high-temperature proton exchange membrane fuel cells. J. Mater. Chem. A, 2023, 11(24), 12885-12895. doi:10.1039/d2ta08904ahttp://dx.doi.org/10.1039/d2ta08904a

Kausar A. Progression from polyimide to polyimide composite in proton-exchange membrane fuel cell: a review. Polym. Plast. Technol. Eng., 2017, 56(13), 1375-1390. doi:10.1080/03602559.2016.1275688http://dx.doi.org/10.1080/03602559.2016.1275688

Zhang Y.; Dai J. M.; Lai H. A.; Wan Y. H.; Lee Y. M.; Zhuang Y. B. Finely adjusted intrinsically microporous copolyimide electrolyte membranes for fuel cells operating in a wide temperature range. Macromolecules, 2023, 56(12), 4681-4693. doi:10.1021/acs.macromol.3c00395http://dx.doi.org/10.1021/acs.macromol.3c00395

Zhang Y.; Lee W. H.; Seong J. G.; Bae J. Y.; Zhuang Y. B.; Feng S. C.; Wan Y. H.; Lee Y. M. Alicyclic segments upgrade hydrogen separation performance of intrinsically microporous polyimide membranes. J. Membr. Sci., 2020, 611, 118363. doi:10.1016/j.memsci.2020.118363http://dx.doi.org/10.1016/j.memsci.2020.118363

Xiao Y. M.; Shen X. Y.; Sun R. X.; Wang S. B.; Xiang J.; Zhang L.; Cheng P. G.; Du X. J.; Yin Z.; Tang N. Polybenzimidazole membrane crosslinked with quaternized polyaniline as high-temperature proton exchange membrane: enhanced proton conductivity and stability. J. Membr. Sci., 2022, 660, 120795. doi:10.1016/j.memsci.2022.120795http://dx.doi.org/10.1016/j.memsci.2022.120795

Qu L. J.; Wang Z. Q.; Guo X. Q.; Song W.; Xie F.; He L.; Shao Z. G.; Yi B. L. Effect of electrode Pt-loading and cathode flow-field plate type on the degradation of PEMFC. J. Energy Chem., 2019, 35, 95-103. doi:10.1016/j.jechem.2018.09.004http://dx.doi.org/10.1016/j.jechem.2018.09.004

Zhuang Y. B.; Seong J. G.; Do Y. S.; Jo H. J.; Lee M. J.; Wang G.; Guiver M. D.; Lee Y. M. Effect of isomerism on molecular packing and gas transport properties of poly(benzoxazole-co-imide)s. Macromolecules, 2014, 47(22), 7947-7957. doi:10.1021/ma501891mhttp://dx.doi.org/10.1021/ma501891m

Zhuang Y. B.; Seong J. G.; Do Y. S.; Jo H. J.; Cui Z. L.; Lee J.; Lee Y. M.; Guiver M. D. Intrinsically microporous soluble polyimides incorporating Tröger's base for membrane gas separation. Macromolecules, 2014, 47(10), 3254-3262. doi:10.1021/ma5007073http://dx.doi.org/10.1021/ma5007073

Zhuang Y. B.; Seong J. G.; Do Y. S.; Lee W. H.; Lee M. J.; Guiver M. D.; Lee Y. M. High-strength, soluble polyimide membranes incorporating Tröger's base for gas separation. J. Membr. Sci., 2016, 504, 55-65. doi:10.1016/j.memsci.2015.12.057http://dx.doi.org/10.1016/j.memsci.2015.12.057

Lu J. A.; Zhang Y.; Li J.; Fu M. F.; Zou G. X.; Ando S.; Zhuang Y. B. Tröger's base (TB)-based polyimides as promising heat-insulating and low-K dielectric materials. Macromolecules, 2023, 56(5), 2164-2174. doi:10.1021/acs.macromol.2c02148http://dx.doi.org/10.1021/acs.macromol.2c02148

冯鑫, 王玉辉, 赵宇霄, 于晓亮, 张培斌, 崔晶, 郭敏杰. 高综合性能无色透明聚酰亚胺薄膜的制备. 高分子学报, 2023, 54(8), 1219-1228. doi:10.11777/j.issn1000-3304.2022.22408http://dx.doi.org/10.11777/j.issn1000-3304.2022.22408

Hao J. K.; Jiang Y. Y.; Gao X. Q.; Xie F.; Shao Z. G.; Yi B. L. Degradation reduction of polybenzimidazole membrane blended with CeO2 as a regenerative free radical scavenger. J. Membr. Sci., 2017, 522, 23-30. doi:10.1016/j.memsci.2016.09.010http://dx.doi.org/10.1016/j.memsci.2016.09.010

Yang J. S.; Li Q. F.; Cleemann L. N.; Xu C. X.; Jensen J. O.; Pan C.; Bjerrum N. J.; He R. H. Synthesis and properties of poly(aryl sulfone benzimidazole) and its copolymers for high temperature membrane electrolytes for fuel cells. J. Mater. Chem., 2012, 22(22), 11185-11195. doi:10.1039/c2jm30217ahttp://dx.doi.org/10.1039/c2jm30217a

Cong Y. Y.; Yi B. L.; Song Y. J. Hydrogen oxidation reaction in alkaline media: from mechanism to recent electrocatalysts. Nano Energy, 2018, 44, 288-303. doi:10.1016/j.nanoen.2017.12.008http://dx.doi.org/10.1016/j.nanoen.2017.12.008

Zhang F.; Li N. W.; Cui Z. M.; Zhang S. B.; Li S. H. Novel acid-base polyimides synthesized from binaphthalene dianhydrie and triphenylamine-containing diamine as proton exchange membranes. J. Membr. Sci., 2008, 314(1-2), 24-32. doi:10.1016/j.memsci.2008.01.032http://dx.doi.org/10.1016/j.memsci.2008.01.032

Dai J. M.; Zhang Y.; Wang G.; Zhuang Y. B. Structural architectures of polymer proton exchange membranes suitable for high-temperature fuel cell applications. Sci. China Mater., 2022, 65(2), 273-297. doi:10.1007/s40843-021-1889-8http://dx.doi.org/10.1007/s40843-021-1889-8

施奕磊, 杨腊文, 蒋仲庆, 贾志舰, 蒋仲杰. 氧化石墨烯在质子交换膜中的应用研究进展. 膜科学与技术, 2015, 35(5), 114-121.

Wang P.; Lin J. J.; Wu Y. N.; Wang L. Construction of high-density proton transport channels in phosphoric acid doped polybenzimidazole membranes using ionic liquids and metal-organic frameworks. J. Power Sources, 2023, 560, 232665. doi:10.1016/j.jpowsour.2023.232665http://dx.doi.org/10.1016/j.jpowsour.2023.232665

Liu F. X.; Wang S.; Li J. S.; Tian X.; Wang X.; Chen H.; Wang Z. Polybenzimidazole/ionic-liquid-functional silica composite membranes with improved proton conductivity for high temperature proton exchange membrane fuel cells. J. Membr. Sci., 2017, 541, 492-499. doi:10.1016/j.memsci.2017.07.026http://dx.doi.org/10.1016/j.memsci.2017.07.026

浏览量

196

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

含四芳基咪唑结构的热重排气体分离膜的制备与性能研究

萘乙炔基封端的含硅聚酰亚胺的制备与性能

N-取代对聚苯并咪唑水/盐传输行为的影响研究

高综合性能无色透明聚酰亚胺薄膜的制备