基于PVDF薄膜辐照接枝制备质子交换膜

doi:10.11949/j.issn.0438-1157.20160654

化工学报 ›› 2016, Vol. 67 ›› Issue (S1): 384-389.DOI: 10.11949/j.issn.0438-1157.20160654

• 材料化学工程与纳米技术 • 上一篇下一篇

基于PVDF薄膜辐照接枝制备质子交换膜

高金津^1,2, 李雪², 赵玉彬¹, 李微微², 赵阳², 王树博², 谢晓峰², 张振琳¹

1 燕山大学亚稳材料制备技术与科学国家重点实验室, 河北秦皇岛 066004;
2 清华大学核能与新能源技术研究院, 北京 100084

收稿日期:2016-05-11 修回日期:2016-05-25 出版日期:2016-08-31 发布日期:2016-08-31
通讯作者: 张振琳,leafzzl@163.com;谢晓峰,xiexf@tsinghua.edu.cn
基金资助:
国家高技术研究发展计划项目（2012AA051201）。

Preparation of proton exchange membrane by radiation-induced grafting of PVDF film

GAO Jinjin^1,2, LI Xue², ZHAO Yubin¹, LI Weiwei², ZHAO Yang², WANG Shubo², XIE Xiaofeng², ZHANG Zhenlin¹

1 State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, Hebei, China;
2 Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

Received:2016-05-11 Revised:2016-05-25 Online:2016-08-31 Published:2016-08-31
Supported by:
supported by the National High Technology Research and Development Program of China (2012AA051201).

摘要/Abstract

摘要：

含氟磺酸型质子交换膜是一类具有高热稳定性、化学稳定性及良好力学性能的离子交换膜，具有极其广阔的应用前景。采用⁶⁰Co辐照接枝技术，在聚偏氟乙烯（PVDF）基膜上产生自由基聚合位点，进而接枝对苯乙烯磺酰氯单体，经过一定条件酸碱处理得到一种新型偏氟磺酸型质子交换膜。并对其进行红外分析，结果显示PVDF膜上成功接枝上了对苯乙烯磺酰氯单体；定量研究了在相同辐照总剂量、不同剂量率条件下，所得质子交换膜的质子传导率、吸水率及离子交换容量与接枝率的关系，结果表明：当剂量率为40 Gy·min^-1时，所得质子交换膜接枝率为52.7%，吸水率为36.85%，80℃时质子传导率达到136 mS·cm^-1，离子交换容量为1.274 mmol·g^-1。

关键词: 辐照, 聚偏氟乙烯, 辐照接枝, 质子交换膜

Abstract:

Sulfonated proton exchange membrane is a kind of ion exchange membrane with high thermal stability, chemical stability and good mechanical properties, having extremely broad application prospects. Numerous free radicals can be generated when the poly(vinylidene fluoride)(PVDF) membrane was irradiated by ⁶⁰Co γ-source, acting as active sites for the graft of 4-sulfonyl chloride vinylbenzene monomer, thus the proton exchange membrane can be prepared by subsequent alkaline and acid treatment. And the structures of the monomer, the original PVDF and grafted PVDF membrane were confirmed by FT-IR spectra, indicating that the monomer had been successfully grafted into PVDF membrane. This proton exchange membrane shows good thermal stability, also can meet the requirement of the temperature of proton exchange membrane fuel cells. The relationship of the proton conductivity, water uptake, ionic exchange capacity with degree of graft at different does rate but same total does were studied. The results showed that when the does rate was 40 Gy·min^-1, the degree of graft of the membrane was 52.7%, ionic exchange capacity was 1.274 mmol·g^-1, water uptake was 36.85% and conductivity was 136 mS·cm^-1 at 80℃.

Key words: radiation, poly (vinylidene fluoride), irradiation grafting, proton exchange membrane

中图分类号:

TM911.4

高金津, 李雪, 赵玉彬, 李微微, 赵阳, 王树博, 谢晓峰, 张振琳. 基于PVDF薄膜辐照接枝制备质子交换膜[J]. 化工学报, 2016, 67(S1): 384-389.

GAO Jinjin, LI Xue, ZHAO Yubin, LI Weiwei, ZHAO Yang, WANG Shubo, XIE Xiaofeng, ZHANG Zhenlin. Preparation of proton exchange membrane by radiation-induced grafting of PVDF film[J]. CIESC Journal, 2016, 67(S1): 384-389.

参考文献 21

[1]	WANG H, CAPUANO G A. Behavior of raipore radiation-grafted polymer membranes in H2/O2 fuel cells[J]. J. Electrochem. Soc., 1998, 145(3):780-784.
[2]	FENG S G, SHANG Y M, WANG Y W, et al. Synthesis and crosslinking of hydroxyl-functionalized sulfonated poly (ether ether ketone) copolymer as candidates for proton exchange membranes[J]. Journal of Membrane Science, 2010, 352(1):14-21.
[3]	ZHOU T C, SHAO R, CHEN S, et al. A review of radiation-grafted polymer electrolyte membranes for alkaline polymer electrolyte membrane fuel cells[J]. Journal of Power Sources, 2015, 293(20):946-975.
[4]	GUZMAN G, PINTAURO P N, VERBRUGGE M W, et al. Analysis of radiation-grafted membranes for fuel cell electrolytes[J]. Journal of Applied Electrochemistry, 1992, 22(3):204-214.
[5]	BVCHI F N, GUPTA B, HAAS O,et al. Study of radiation-grafted FEP-G-polystyrene membranes as polymer electrolytes in fuel cells[J]. Electrochemical Acta, 1995, 40(3):345-353.
[6]	MOHAMED N. Radiation-grafted membranes for polymer electrolyte fuel cells:current trends and future directions[J]. Chemical Reviews, 2014, 114(24):12278-12329.
[7]	HOSOYA S, MATSUSHIMA K. Single-step radiation induced grafting for preparation of proton exchange membranes for fuel cell[J]. Journal of Endodontics, 2009, 339(1/2):115-119.
[8]	FERREIRA H P, PARRA D F, LUGAO A B. Radiation-induced grafting of styrene into poly(vinylidene fluoride) film by simultaneous method with two different solvents[J]. Radiation Physics & Chemistry, 2012, 81(9):1341-1344.
[9]	RALPH T R. Clean fuel cell energy for today[J]. Platinum Metals Review, 1999, 43(1):14-17.
[10]	SOPIAN K, WAN R W D. Challenges and future developments in proton exchange membrane fuel cells[J]. Renewable Energy, 2006, 31(5):719-727.
[11]	LI L, JIANG J Z, SHANG Y M, et al. Porous-PTFE reinforced composite membrane for fuel cell applications[J]. Chemical Industry & Engineering Progress, 2009, 28(8):1395-1399.
[12]	QIU J Y, LI M Y, NI J F, et al. Preparation of ETFE-based anion exchange membrane to reduce permeability of vanadium ions in vanadium redox battery[J]. Journal of Membrane Science, 2007, 297(1/2):174-180.
[13]	TAKASHI M, HIROKO Y. Radiation grafting of α,β,β-trifluorostyrene onto poly(ethylene-tetrafluoroethylene) film by pre-irradiation method(I):Effects of pre-irradiation dose, monomer concentration, reaction temperature, and film thickness[J]. Journal of Applied Polymer Science, 1989, 37(10):2817-2826.
[14]	HERMAN H, SLADE R C T, VARCO J R. The radiation-grafting of vinylbenzyl chloride onto poly (hexafluoropro-pylene-co-tetrafluoroethylene) films with subsequent conversion to alkaline anion-exchange membranes:optimi-zation of the experimental conditions and characterization[J]. Journal of Membrane Science, 2003, 218(1/2):147-163.
[15]	QIU J Y, NI J F, ZHAI M L, et al. Radiation grafting of styrene and maleic anhydride onto PTFE membranes and sequent sulfonation for applications of vanadium redox battery[J]. Radiation Physics & Chemistry, 2007, 76(11/12):1703-1707.
[16]	PATEL R, PARK J T, LEE W S, et al. Composite polymer electrolyte membranes comprising P(VDF-co-CTFE)-g-PSSA graft copolymer and zeolite for fuel cell applications[J]. Polymers for Advanced Technologies, 2009, 20(12):1146-1151.
[17]	GUBLER L, SLASKI M, WALLASCH F, et al. Radiation grafted fuel cell membranes based on co-grafting of α-methylstyrene and methacrylonitrile into a fluoropolymer base film[J]. Journal of Membrane Science, 2009, 339(1/2):68-77.
[18]	HARNED A M, SHERRILL W M, FLYNN D L, et al. High-load, soluble oligomeric benzenesulfonyl azide:application to facile diazo-transfer reactions[J]. Tetra-hedron, 2005, 61(51):12093-12099.
[19]	FENG S G, SHANG Y M, XIE X F, et al. Novel modification method to prepare cross-linked sulfonated poly (ether ether ketone)/silica hybrid membranes for fuel cells[J]. Journal of Power Sources, 2010, 195(19):6450-6458.
[20]	YU H Y, ZENG X M, XIANG Y, et al. A proton exchange membrane prepared by radiation grafting of p-styryltrime-thoxysilane into PTFE membrane[J]. Journal of Polymer, 2010, 10(7):842-848.
[21]	FENG S G, SHANG Y M, WANG S B, et al. Novel method for the preparation of ionically cross-linked sulfonated poly(arylene ether sulfonic)/polybenzimidazole composite membranes via in situ polymerization[J]. Journal of Membrane Science, 2010, 346(1):105-112.

基于PVDF薄膜辐照接枝制备质子交换膜

Preparation of proton exchange membrane by radiation-induced grafting of PVDF film

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