四甲基氢氧化铵改性聚偏氟乙烯接枝苯乙烯磺化膜的制备和性能

doi:10.7503/cjcu20180042

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 2062.doi: 10.7503/cjcu20180042

四甲基氢氧化铵改性聚偏氟乙烯接枝苯乙烯磺化膜的制备和性能

刘琪¹, 郭贵宝¹(), 安胜利², 刘金彦¹

1. 内蒙古科技大学化学与化工学院, 2. 材料与冶金学院, 包头 014010

收稿日期:2018-01-12 出版日期:2018-09-07 发布日期:2018-08-03
作者简介:
联系人简介: 郭贵宝, 男, 博士, 教授, 主要从事高分子膜材料应用研究. E-mail: guogb@imust.cn
基金资助:
国家自然科学基金(批准号: 21463016)、内蒙古自治区自然科学基金[批准号: 2017MS(LH)0515]和高等学校科学研究基金(批准号: NJZY18148)资助.

Preparation and Properties of Tetramethyl Ammonium Hydroxide Modified Polyvinylidene Fluoride with Styrene Sulfonated Membranes^†

LIU Qi¹, GUO Guibao^1,^*(), AN Shengli², LIU Jinyan¹

1.School of Chemistry and Chemical Engineering, 2. School of Materials and Metallurgy, Inner Mongolia University of Science & Technology, Baotou 014010, China

Received:2018-01-12 Online:2018-09-07 Published:2018-08-03
Contact: GUO Guibao E-mail:guogb@imust.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No. 21463016), the Inner Mongolia Autonomous Region Natural Science Foundation, China[No. 2017MS(LH)0515] and the Scientific Research Projects in Institutions of Higher Learning, China(No. NJZY18148).

摘要/Abstract

摘要：

使用四甲基氢氧化铵(TMAH)甲醇溶液在液相中改性聚偏氟乙烯(PVDF), 挥发溶剂得到改性聚偏氟乙烯膜(g-PVDF-M), 再以过氧化苯甲酰(BPO)为引发剂, 将苯乙烯接枝到g-PVDF-M膜中, 磺化后制得改性聚偏氟乙烯接枝苯乙烯磺化(PVDF-g-PSSA)膜. 利用傅里叶变换红外光谱(FTIR)和能谱仪的扫描电子显微镜分析了PVDF-g-PSSA膜(TMAH-25)的结构、形貌及硫元素分布情况. 通过电化学工作站和气相色谱仪研究了TMAH在甲醇中的不同含量对PVDF-g-PSSA膜质子电导率和甲醇渗透率的影响. 结果表明, TMAH使PVDF脱去HF生成碳碳双键, 并且苯乙烯接枝到改性的聚偏氟乙烯膜中, 磺化后S元素在PVDF-g-PSSA膜内部均匀分布; PVDF-g-PSSA膜的质子电导率和甲醇渗透率随TMAH在甲醇溶液中质量分数的增加而增大; TMAH的质量分数为25%时, PVDF-g-PSSA膜的电导率达1.28×10^-2 S/cm, 甲醇渗透率为4.58×10^-7 cm²/s. 热重分析(TGA)表明, PVDF-g-PSSA膜的热稳性良好, 耐热温度高达195 ℃, PVDF-g-PSSA膜作为电解质材料的直接甲醇燃料单电池(DMFC)功率密度达到16.45 mW/cm².

关键词: 直接甲醇燃料电池, 聚偏氟乙烯, 四甲基氢氧化铵, 苯乙烯

Abstract:

Poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid)(PVDF-g-PSSA) membranes were synthesized via grafting styrene onto PVDF and then sulfonation. The PVDF of N-methylpyrrolidone solvent was initially modified by ammonium tetramethyl hydroxide(TMAH) methanol solution, and then the modified PVDF membrane was made after volatiling solvent. The styrene was grafted to the modified PVDF membrane, which utilized benzoyl peroxide(BPO) as the initiator. The microstructures, morphologies and sulfur distribution in the membranes were characterized by Fourier transform infrared spectroscope(FTIR), scanning electron microscopy(SEM), and energy-dispersive X-ray spectroscopy(EDX). Meanwhile, the effects of the TMAH mass fraction in methanol on proton conductivities and methanol permeabilities were investigated. The results indicated that PVDF was dehydrofluorinated by TMAH and carbon-carbon double bonds were obtained. The styrene was successfully grafted onto the modified PVDF membrane; the sulfur distribution in the interior and exterior of the membrane was homogeneous. The proton conductivities and methanol permeabilities of the PVDF-g-PSSA membranes increased with the increasing of TMAH mass fraction in methanol solution. When the TMAH mass fraction in methanol solution was 25%, the proton conductivity of the PVDF-g-PSSA membrane was 1.28×10^-2 S/cm and the methanol permeability was 4.58×10^-7 cm²/s, respectively. The membranes exhibited good thermal stability up to approximately 195 ℃. The peak power density of direct methanol fuel cell(DMFC) with above membrane was 16.45 mW/cm².

Key words: Direct methanol fuel cell, Polyvinylidene fluoride, Tetramethyl ammonium hydroxide, Styrene

中图分类号:

O631
O646

TrendMD:

刘琪, 郭贵宝, 安胜利, 刘金彦. 四甲基氢氧化铵改性聚偏氟乙烯接枝苯乙烯磺化膜的制备和性能. 高等学校化学学报, 2018, 39(9): 2062.

LIU Qi,GUO Guibao,AN Shengli,LIU Jinyan. Preparation and Properties of Tetramethyl Ammonium Hydroxide Modified Polyvinylidene Fluoride with Styrene Sulfonated Membranes^†. Chem. J. Chinese Universities, 2018, 39(9): 2062.

图/表 15

Scheme 1 Schematic procedures of PVDF-g-PSSA

Fig.1 Relationship between the content of TMAH and degree of grating(DOG) of pretreated PVDF

Fig.2 Effect of grating reaction temperature on degree of grating of PVDF-g-PSSA membranes

Fig.3 Effect of grating reaction time on the degree of grating of PVDF-g-PSSA membranes

Fig.4 Effect of the concentration of styrene on the degree of grating of PVDF-g-PSSA membranes

Fig.5 Effect of the concentration of BPO on the degree of grating of PVDF-g-PSSA membranes

Fig.6 Impendence of PVDF-g-PSSA membrane

Fig.7 Effects of TMAH consumption on conductivity(A) and ion exchange capacity(B) of PVDF-g-PSSA membranes

Table 1 Measurent results of the yield strength(δ), elongation at break(ε), swelling degree and water uptake of samples

Sample	δ/MPa	ε(%)	SD(%)	WU(%)
Nafion117	10.40	38.8	19.2	24.3
TMAH-10	13.42	43.8	6.4	9.3
TMAH-15	16.85	40.4	13.2	16.2
TMAH-20	18.67	37.4	15.3	25.4
TMAH-25	21.29	34.6	18.3	32.1
TMAH-30	14.12	36.4	21.2	37.8

Fig.8 IR spectra of PVDF(a), g-PVDF-M(b), PVDF-g-PS(c) and PVDF-g-PSSA(d) membranes

Fig.9 Wide-scan XPS spectra of PVDF(A) and PVDF-g-PSSA(B) membranes

Fig.10 SEM images of PVDF-g-PSSA membrane(A, B)and distribution of fluorine(C) and sulfur(D) on the surface of the cross-section of the membrane measured by EDX (A) Surface of PVDF-g-PSSA membrane; (B) cross-section of PVDF-g-PSSA membrane.

Fig.11 TGA curves of PVDF(a) and PVDF-g-PSSA(b) membranes

Fig.12 Effect of TMAH consumption on methanol permeability of PVDF-g-PSSA

Fig.13 Performance of single cell with PVDF-g-PSSA membrane(TMAH-25)

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四甲基氢氧化铵改性聚偏氟乙烯接枝苯乙烯磺化膜的制备和性能

Preparation and Properties of Tetramethyl Ammonium Hydroxide Modified Polyvinylidene Fluoride with Styrene Sulfonated Membranes^†

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四甲基氢氧化铵改性聚偏氟乙烯接枝苯乙烯磺化膜的制备和性能

Preparation and Properties of Tetramethyl Ammonium Hydroxide Modified Polyvinylidene Fluoride with Styrene Sulfonated Membranes†

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Preparation and Properties of Tetramethyl Ammonium Hydroxide Modified Polyvinylidene Fluoride with Styrene Sulfonated Membranes^†