摘 要

在过去10年里，质子交换膜燃料电池（PEMFCs）作为具有高能量转换效率的零排放能源得到国内外普遍的重视。质子交换膜是燃料电池的核心组件之一，其性能直接影响了燃料电池的性能。目前高温质子交换膜是质子交换膜领域的研究热点。其中膦酸基有机-无机杂化质子交换膜是被研究的最为广泛的新材料之一。

本论文提出一种膦酸接枝有机/无极杂化质子交换膜的制备方法，先通过双键加聚的方式将乙烯基三乙氧基硅氧烷(A-151)和烯丙基聚氧乙烯聚氧丙烯环氧基醚(AEPH)加聚在一起。然后利用环氧开环的方式将氨基三甲叉膦酸(ATMP)化学键合在AEPH上，以将膦酸固定在质子交换膜中。红外光谱表明环氧基团成功发生了开环反应，且A-151中的硅氧烷成功水解缩聚了三维的Si-O-Si交联网络。通过对膦酸的键合情况分析，发现部分膦酸能有效的键合在质子交换膜中，不会随着水而发生渗漏。吸水率溶胀率测试表明质子交换膜的溶胀率随着吸水率的增大而增大，且质子交换膜具有较好的尺寸稳定性。氧化稳定性测试表明质子交换膜在室温下具有较好的氧化稳定性，而在80℃下氧化稳定性较差。质子交换膜的质子电导率随着温度的升高而升高，且在160℃下能达到1.12×10^-2 S cm^-1，满足高温无水质子传导的要求。

关键词：质子交换膜；膦酸；有机-无机；水解稳定性

Abstract

In the past decade, proton exchange membrane fuel cells (PEMFCs) have attracted much attention as emission-free power sources with high energy conversion efficiency. As one of the core components of PEMFCs, proton exchange membranes (PEMs) directly correlate with the performance of PEMFCs. However, there are few PEMs that fulfill the requirements for large-scale applications of PEMFCs. The organic-inorganic hybrid membranes possess advantages of both organic and inorganic phases and are considered to be promising PEMs in the PEMFC applications.

The paper puts forward a kind of phosphonic acid grafting organic/promise hybrid proton exchange membrane preparation method, first by means of polymerization of the vinyl triethoxy silane (A-151) and allyl polyethylene oxide ethyl poly acrylic epoxy eher, propylene oxygen (AEPH) we together. Then using epoxy ring opening of amino three fork phosphonic acid (ATMP) chemically bonded on the AEPH to phosphonic acid is fixed in the proton exchange membrane. Ftir showed that epoxy group success ring opening reaction happened, and A-151 siloxane success hydrolytic condensation of the three-dimensional Si-O-Si crosslinking network. Through the analysis of the bonding situation of phosphonic acid, phosphonic acid can effectively find part bonding in proton exchange membrane, will not happen with the water leakage. Water absorption test proves that the swelling ratio of the proton exchange membrane swelling rate increases with the increase of water absorption, and proton exchange membrane has good dimensional stability. Oxidation stability test showed that the proton exchange membrane has good oxidation stability at room temperature, and the poor oxidation stability under 80℃. The proton conductivity of proton exchange membrane as the temperature rises, and under 160℃ can reach 1.12x10^-2 S cm^-1, meet the requirements of high temperature zero water conduction son.

Keywords: Proton exchange membrane; phosphonic acid; organic-inorganic; hydrolytic stability.

目 录

摘 要 I

Abstract II

第一章 绪论 1

1.1 燃料电池 1

1.1.1 燃料电池介绍 1

1.1.2 燃料电池特点及分类 1

1.2 质子交换膜燃料电池 2

1.2.1 质子交换膜燃料电池的介绍 2

1.3 质子交换膜的研究现状 2

1.3.1 全氟磺酸基有机-无机杂化膜 3

1.3.2 聚芳醚砜（PAES）基有机-无机杂化膜 5

1.3.3 聚乙烯醇（PVA）基有机-无机杂化膜 5

1.3.4 聚苯并咪唑（PBI）基有机-无机杂化膜 6

1.3.5 其他有机-无机杂化膜 6

1.4 论文的主要研究目的 7

第二章 膦酸接枝有机/无机杂化质子交换膜的制备研究 8

2.1 实验药品、试剂 8

2.2 实验仪器 8

2.3 实验原理 8

2.3.1 AEPH与A-151反应 8

2.3.2 ATMP与AEPH之间的环氧开环反应 9

2.4 实验方法 9

2.5 膦酸接枝有机/无机杂化质子交换膜的性能测试 9

2.5.1 红外光谱测试(FT-IR) 9

2.5.2 膦酸的有效键合量测试 9

2.5.3 耐水解性测试 10

2.5.4 吸水率测试 10

2.5.5 溶胀率测试 10

2.5.6 耐氧化性测试 11

2.5.7 质子电导率测试 11

第三章 结果与讨论 12

3.1 红外光谱分析 12

3.2 膦酸的有效键合量测试 13

3.3 膜的水解稳定性分析 14

3.4 膜的氧化稳定性分析 14

3.5 质子电导率 15

第四章 结论 17

参考文献 18

致 谢 21