基于植酸框架构筑燃料电池用阴离子导电膜

doi:10.12422/j.issn.1006-396X.2023.01.010

摘要/Abstract

摘要：

在聚乙烯醇聚合物基质中原位引入植酸、甲醇、水、九水合硝酸铬和N,N?二甲基甲酰胺的混合液（植酸与九水合硝酸铬形成具有立体结构的金属有机框架结构），以戊二醛为交联剂，将聚乙烯醇聚合物交联为网状结构，由此构筑一系列内部含有基于植酸构筑的多孔金属有机框架结构（MOF）及适合燃料电池使用的阴离子导电膜（MOF@PVA）；通过调节阴离子导电膜中Cr³⁺的质量分数，对其结构及性能进行优化。结果表明，制得的导电膜形貌平整均一，内部含有大量可供OH^-迁移和涵养水分子的孔结构；导电膜的电导率、含水率、机械性能均随着Cr³⁺质量分数的增加而增加。其中，当m（Cr³⁺）/m(导电膜)=0.012时，导电膜的电导率最高，为24.9 mS/cm；导电膜在80 oC、3 mol/L NaOH溶液中浸泡168 h后，电导率仅下降8%。

关键词: 阴离子导电膜, 电导率, 耐碱性, 植酸, MOF

Abstract:

This paper in situ introduced a mixture of phytic acid,methanol,water,chromium nitrate nonahydrate,N,N?dimethylformamide in polyvinyl alcohol casting solution, where phytic acid and chromium nitrate nonahydrate formed a metal organic framework (MOF) with a three?dimensional structure. Glutaraldehyde was the crosslinking agent to crosslink polyvinyl alcohol into a network structure, and a series of anion exchange membranes with a porous MOF were constructed for fuel cells（MOF@PVA）. During the experiment, the structure and properties of the membranes were optimized by adjusting the Cr³⁺ content. Characterization and performance test results show that the obtained composite membranes are flat and uniform in morphology, with a large number of pore structures available for OH^- migration and retention of water molecules. Additionally, membrane conductivity, water content, and mechanical properties increase with the rising Cr³⁺ mass fractions. When m(Cr³⁺)/m(conductive film) is 0.012, the conductivity is the highest, that is 24.9 mS/cm. The membrane conductivity is only reduced by 8% after being immersed in a 3 mol/L NaOH solution at 80 $℃$ for 168 hours.

Key words: Anion exchange membrane, Conductivity, Alkaline resistance, Phytic acid, MOF

中图分类号:

TQ152

刘盈汐, 王吉林, 王璐璐, 曲志强. 基于植酸框架构筑燃料电池用阴离子导电膜[J]. 石油化工高等学校学报, 2023, 36(1): 74-80.

Yingxi Liu, Jilin Wang, Lulu Wang, Zhiqiang Qu. Phytic Acid Framework⁃Based Alkaline Anion Exchange Membrane Construction for Fuel Cells[J]. Journal of Petrochemical Universities, 2023, 36(1): 74-80.

图/表 11

图1 导电膜的结构示意图

Fig.1 Sketch diagram of conductive film

图2 导电膜的红外光谱

Fig.2 FT?IR of conductive film

图3 导电膜的热重曲线

Fig.3 TGA curve of conductive film

图4 导电膜的表面形貌

Fig.4 Surface morphology of conductive film

图5 导电膜的机械性能曲线

Fig.5 Mechanical property curve of conductive film

图6 导电膜的溶胀度和含水率

Fig.6 SR and WU of conductive film

图7 导电膜的电导率曲线

Fig.7 Conductivity graph of conductive film

图8 导电膜的阿伦尼乌斯曲线

Fig.8 Arrhenius plots of conductive film

表1 不同导电膜的离子交换量和电导率对比

Table 1 Comparison of ion exchange capacity and conductivity of different conductive films

导电膜	离子交换量/(mmol∙g^-1)	温度/ºC	电导率/(mS·cm^-1)	文献
M⁃0.012	0.93	80	24.9	本研究
NBu₄⁃ZIF⁃8	－	25	6.2×10^-4	[16]
MIL⁃100⁃Cr⁃OH	－	50	2.1×10^-2	[17]
[Ni₂(μ⁃pymca)₃]OH∙nH₂O	－	90	5.6×10^-2	[18]
PVA⁃ZIF8i⁃48	－	60	2.6×10^-1	[9]
PIL⁃MIL⁃101⁃Cr	1.02	20	36.6	[8]
c6PAES⁃4IM⁃2.2	2.20	20	3.8	[19]
c6PAES⁃NIM⁃1.9	1.80	20	2.1	[19]
c6PAES⁃QA⁃2.0	1.90	20	1.6	[19]

图9 导电膜在80 ℃、3 mol/L NaOH溶液中浸泡240 h的耐碱性

Fig.9 The alkaline resistance of the conductive film after immersion in the 3 mol/L NaOH solution for 240 h at 80 ℃

图10 M?0.012导电膜的单电池性能

Fig.10 Single cell performance of M?0.012 conductive film

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