论文总字数：21562字

摘 要

锌空气电池工作时绿色环保、具有较好的比能量和能量密度。锌空气电池主要由空气电极、隔膜、锌电极和电解质几种成分组成。在锌空气电池工作时，液态电解质易发生挥发、渗漏、变质从而导致电池产生断路、发热等问题。但是聚合物电解质的产生能够有效改善以上问题。本文在综述聚合物电解质的分类、研究方法和锌-空气电池用碱性聚合物电解质研究进展的基础上，通过研究对以聚乙烯醇（PVA）为基质材料，选择共混的改性方法将具有良好吸水保水性能的聚丙烯酸钾（PAAK）为添加剂，用溶液浇筑活化处理分析了添加剂的添加含量、KOH浓度、温度、存储时间等对PVA-KOH碱性凝胶聚合物电解质离子电导率和电化学稳定性的影响。通过研究交流阻抗、X射线衍射、红外光谱、循环伏安法等测试手段对电解质膜的性能与结构进行了表征。研究结论得出：PAAK的加入降低了PVA整体的结晶度，增大了聚合物集体中的无定形区域，链段运动变得更加活跃。随着PAAK的增大，基体容纳KOH的能力增强，OH^-的增多意味着更高的离子电导率，但是当PAAK的比例上升到一定程度，PVA与PAAK的结合达到饱和，多余的PAAK会聚集在电解质膜表面影响整体的机械性能，甚至脱落破坏膜层结构。

关键词：碱性聚合物电解质；PVA-PAAK；锌空气电池；离子电导率；电化学稳定窗口

Preparation of PVA-PAAK-KOH polymer electrolyte for zinc air battery

Abstract

Zinc air battery is green and environment-friendly, with high specific energy and energy density. Zinc air battery is mainly composed of air electrode, diaphragm, zinc electrode and electrolyte. When the zinc air battery works, the liquid electrolyte is prone to volatilization, leakage and deterioration, which leads to the problems of open circuit and heating. However, the production of polymer electrolyte can effectively improve the above problems. Based on the review of the classification and research methods of polymer electrolytes and the research progress of alkaline polymer electrolytes for zinc air batteries, this paper studies the use of PAAK with good water absorption and water retention properties as additives by the blending modification method with polyvinyl alcohol (PVA) as the matrix material, and analyzes the additive content by solution pouring activation treatment The effects of volume, KOH concentration, temperature and storage time on ionic conductivity and electrochemical stability of PVA-KOH alkaline gel polymer electrolyte were studied. The properties and structures of the electrolyte films were characterized by means of AC impedance, X-ray diffraction, infrared spectrum and cyclic voltammetry. The results show that PAAK can decrease the crystallinity of PVA, increase the amorphous area of polymer, and make the segment motion more active. With the increase of PAAK, the ability of the matrix to hold KOH increases, and the increase of OH - means higher ionic conductivity. However, when the proportion of PAAK increases to a certain extent, the combination of PVA and PAAK reaches saturation, and the excess PAAK will gather on the surface of the electrolyte membrane, which will affect the overall mechanical properties, or even break off the membrane structure.

Key words: Basic Polymer Electrolyte; PVA-PAAK; Zinc–Air Battery; Ionic conductivity; Electrochemical stabilization window

目 录

摘 要 I

Abstract II

第一章 绪 论 1

1.1研究背景 1

1.2凝胶聚合物简介 2

1.2.1凝胶聚合物组成及其特点 2

1.2.2凝胶聚合物种类 2

1.2.3.1 无机填料 3

1.2.3.2 结构改性 4

1.3 PVA基聚合物电解质 4

1.3.1 PVA基聚合物电解质的研究进展 4

1.3.2 PVA基聚合物电解质的改性 5

1.3.3 PVA基聚合物电解质的制备 6

1.4小结 6

第二章 实验方法 7

2.1 实验原料及仪器 7

2.1.1 实验原料 7

2.1.2 实验仪器 7

2.2 实验方法 8

2.2.1 PVA-KOH碱性凝胶剂聚合物电解质膜制备 8

2.2.2 PVA-PAAK-KOH碱性凝胶剂聚合物电解质膜制备 8

2.2.3空气电极的制作 8

2.2.4锌电极的制作 9

2.2.5电池组装 9

2.2.5锌空气电池性能评估 9

2.3碱性聚合物电解质的表征方法与技术 9

2.3.1电化学性能测量 9

2.3.2聚合物电解质膜结构及其转变分析 10

第三章 实验结果分析与讨论 13

3.1结果与讨论 13

3.1.1 PAAK含量的影响 13

3.1.2含水量的影响 13

3.1.3温度的影响 13

3.1.4存储时间的影响 13

3.1.5 PVA-PAAK碱性凝胶聚合物电解质的电化学稳定性 14

3.1.6 XRD分析 14

3.1.7红外光谱分析 14

3.1.8 PVA-PAAK的聚合物共混膜 14

3.2本章小结 15

第四章 结论及展望 16

4.1本文结论 16

参考文献 17

致 谢 19

第一章 绪 论

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