TMAH改性聚偏氟乙烯一步法接枝聚PSPMA膜的制备和性能

doi:10.11901/1005.3093.2018.112

材料研究学报

2018, Vol. 32

Issue (9): 706-712 DOI: 10.11901/1005.3093.2018.112

本期目录 | 过刊浏览

TMAH改性聚偏氟乙烯一步法接枝聚PSPMA膜的制备和性能

黄强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包头 014010
2 内蒙古科技大学材料与冶金学院包头 014010

Preparation and Property of Proton Exchange Membranes Synthesized via One-step Grafting PSPMA onto Poly(vinylidene fluoride) Modified by TMAH

Qiang HUANG¹, Guibao GUO¹(

), Shengli AN², Jinyan LIU¹

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

引用本文:

黄强, 郭贵宝, 安胜利, 刘金彦. TMAH改性聚偏氟乙烯一步法接枝聚PSPMA膜的制备和性能[J]. 材料研究学报, 2018, 32(9): 706-712.
Qiang HUANG, Guibao GUO, Shengli AN, Jinyan LIU. Preparation and Property of Proton Exchange Membranes Synthesized via One-step Grafting PSPMA onto Poly(vinylidene fluoride) Modified by TMAH[J]. Chinese Journal of Materials Research, 2018, 32(9): 706-712.

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摘要:

使用四甲基氢氧化铵(TMAH)甲醇溶液改性聚偏氟乙烯(PVDF)一步法接枝聚(3-磺酸丙基甲基丙烯酸)(PSPMA),制备了聚偏氟乙烯接枝聚(3-磺酸丙基甲基丙烯酸)PVDF-g-PSPMA膜。使用傅里叶变换红外光谱(FTIR)和能谱扫描电镜(SEM-EDX)表征了膜的结构、形貌和硫元素分布,并使用电化学综合测试仪和气相色谱仪研究了TMAH对PVDF-g-PSPMA膜电导率和甲醇渗透率的影响。结果表明,TMAH使PVDF脱HF产生碳碳双键并将PSPMA成功接枝到聚偏氟乙烯上,硫元素在膜内外分布均匀。随着TMAH在甲醇溶液中含量的提高PVDF-g-PSPMA膜的质子电导率和甲醇渗透率随之提高;TMAH含量为20%时,膜电导率达到8.39×10^-2 S∙cm^-1、甲醇渗透率为8.92×10^-7 cm²∙s^-1。热重分析(TGA)的结果表明,膜的热稳定性良好,耐热温度高达270℃。使用该膜作为电解质材料的直接甲醇燃料电池(DMFC),其功率密度达到18.87 mW∙cm^-2。

关键词 ：高分子材料, 质子交换膜, 一步法, 四甲基氢氧化铵, 聚偏氟乙烯, 3-磺酸丙基甲基丙烯酸

Abstract：

Methanol solution of tetramethylammonium hydroxide (TMAH) modified poly(vinylidene fluoride) (PVDF) was directly grafted with poly (sulfopropyl methacrylate) via a one-step process to synthesis proton exchange membranes of (PVDF-g-PSPMA). The microstructures, morphologies, and distributions of sulfur in the membrane were characterized using Fourier transform infrared spectroscope (FTIR), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The influence of the TMAH on proton conductivity and methanol permeability of these membranes were also investigated. Results show that PVDF was dehydrofluorinated by TMAH and produced carbon-carbon double bond. SPMA was successfully grafted onto PVDF, the distribution of sulfur was homogeneous in the interior and surface of the membrane. The proton conductivity and methanol permeability coefficient of the membrane increase with the content of TMAH, and when the content of TMAH was 20% the proton conductivity of membrane was 8.39×10^-2 S∙cm^-1at ambient temperature, and the methanol permeability coefficient was 8.92×10^-7 cm²∙s^-1. Thermo gravimetric analysis (TGA) confirmed that the membranes possess good thermal stability up to approximately 270℃. The peak power density of direct methanol fuel cell (DMFC) assembled with above membrane was 18.87 mW∙cm^-2.

Key words： polymer materials proton exchange membrane one-step poly (vinylidene fluoride) tetramethyl ammonium hydroxide poly (sulfopropyl methacrylate)

收稿日期: 2018-01-17

ZTFLH:

TQ325.4

基金资助:国家自然科学基金(21463016),内蒙古自治区自然科学基金(2017MS(LH)0515),高等学校科学研究(NJZY18148)

作者简介:

作者简介黄强,男,1996年生,本科生

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https://www.cjmr.org/CN/10.11901/1005.3093.2018.112 或 https://www.cjmr.org/CN/Y2018/V32/I9/706

图1 纯PVDF膜、改性PVDF膜和PVDF-g-PSPMA膜的红外光谱图

图2 PVDF-g-PSPMA膜的表面和截面扫描电镜照片

图3 PVDF-g-PSPMA膜的SEM照片和膜截面区域上硫和氟的分布

图4 PVDF-g-PSPMA膜接枝率和质子电导率与TMAH的用量的关系

图5 PVDF-g-PSPMA膜质子电导率和IEC与TMAH的用量的关系

表1 试样膜的拉伸强度(TS)、溶胀度(SD)和吸水率(WU)

图6 TMAH用量对甲醇渗透率的影响

图7 PVDF-g-PSPMA膜和纯PVDF膜的热失重曲线

图8 PVDF-g-PSPMA和Nafion 117膜的单电池开路电压

图9 电导率(σ)与最大功率密度关系

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