论文总字数：21752字

摘 要

由于化石燃料再生缓慢，化石燃料资源逐渐枯竭，加上气候变化、空气和水污染等环境问题，导致能源需求稳定增长，人们一直在寻找替代能源载体。当使用来自太阳能或风能的清洁电力时，电池有望缓解当前的能源和环境问题。由于绿色能源和电动汽车自身特点，我们必须加大对储能体系的研发。

在很多器件装置都能应用到锂离子电池，其拥有很高的能量密度，并且在可充电性上表现良好，是作为储能的好选择。然而，由于使用易燃的有机电解质，安全问题一直受到关注，锂离子电池的大规模使用受到限制。铅酸电池和锂离子电池变得不再满足人们的需求。锌基水性电池由于具有较高的能量密度，在空气和水溶液中保持良好的化学稳定性，并且锌的来源丰富，使用成本低，因而可取代其他类的电池。然而常见的锌镍电池能够循环充放电的次数较少，这是由于ZnO在电解质溶液中不稳定，充电时发生不均匀的锌沉积。同时锌电极产生的沉积物，逐渐演变为树突状沉积物（锌枝晶），把隔膜刺穿，导致内部短路，除了枝晶的形成，锌阳极的钝化层还缩短了循环寿命，因为活性锌转化为相对绝缘的氧化锌，增加了锌电极的内部电阻。

本课题是将锌镍电池的负极进行结构设计，使其在电解液中稳定，从而解决钝化及溶解问题。实验中采用的方法是高导电碳包覆氧化锌：首先，在碳布（CC）上生长ZnO作为电池的负极，以CC代替了传统的二维金属集电器，这样电极不仅继承了CC的高导电性，还能够承受电解液的腐蚀性；其次，通过原位生成ZIF-8，经退火诱导生成的碳壳层不仅能有效缓解氧化锌的溶解，而且可以提升其导电性。由于增加了表面积且导电，能有效分散电荷，电荷的均匀分散有利于锌的均匀沉积，从而抑制枝晶的生长。

关键词：锌基水性电池 锌枝晶 钝化 溶解

The Research on Electrode Materials of Aqueous Zinc-Ion Batteries

Abstract

Because of the slow regeneration rate of fossil fuels, some resources are gradually depleted, coupled with environmental issues such as climate change, air and water pollution, resulting in stable growth of energy demand, people have been looking for alternative energy carriers. When using clean power from solar or wind energy, batteries are expected to alleviate current energy and environmental problems. Due to the characteristics of green energy and electric vehicles, we must increase the research and development of energy storage system.

Many devices can be applied to lithium-ion batteries, which have high energy density and good performance in recharge ability. It is a good choice for energy storage. However, due to the use of flammable organic electrolytes，safety issues have been concerned, and the large-scale use of lithium-ion batteries is limited. Lead acid batteries and lithium-ion batteries are no longer meeting people's needs. At present, the hot research direction is aqueous zinc-Ion batteries, which can maintain good chemical stability in air and solution under the premise of high energy density. Moreover, zinc has rich sources and low cost. So it can replace other kinds of batteries. However, the common zinc nickel battery can charge and discharge less times, which due to the instability of ZnO in the electrolyte solution and the uneven zinc deposition during charging. At the same time, the deposit produced by zinc electrode gradually evolves into dendritic deposit (zinc dendrite), which can pierce the diaphragm, cause the positive and negative poles to connect together, cause short circuit, reduce the safety performance of the battery and may terminate the battery life.

In this paper, the negative electrode of Zn Ni battery is designed to be stable in the electrolyte, so as to solve the problem of passivation and dissolution. Firstly, ZnO was grown on the carbon cloth (CC) as the negative electrode of the battery CC replaces the traditional two-dimensional metal collector, so the electrode not only inherits the high conductivity of CC, but also can withstand the corrosion of electrolyte; secondly, ZIF-8 is generated in situ, and the carbon shell generated by annealing induction can not only effectively alleviate the dissolution of zinc oxide, but also improve its conductivity. Due to the increase of surface area and conductivity the charge can be effectively dispersed. The uniform dispersion of charge is conducive to the uniform deposition of zinc, thus inhibiting the growth of dendrites.

Key Words: Aqueous Zinc-Ion batteries; Zinc dendrite; Passivation; Dissolution

目 录

摘 要 I

Abstract II

第一章 绪论 1

1.1研究背景及意义 1

1.1.1 研究背景 1

1.1.2 研究意义 2

1.2 研究现状 2

1.2.1 正极研究 3

1.2.2 负极研究 3

1.3 锌镍电池的发展历史及工作原理 5

1.3.1 锌镍电池的发展历史 5

1.3.2 锌镍电池的工作原理 7

1.4 锌负极存在的问题及解决途径 7

1.4.1 锌负极面临问题 7

1.4.2 解决途径 7

1.5 本论文研究内容 8

第二章 实验与表征 10

2.1 实验试剂与仪器 10

2.1.1 实验药品 10

2.1.2 实验仪器 10

2.2实验过程 11

2.2.1碳布的处理 11

2.2.2 水热合成ZnO 11

2.2.3 合成ZnO/Carbon cloth 11

2.2.4 合成ZIF-8 11

2.2.4 电池组装 12

2.3 材料的基本表征 12

2.3.1扫描电子显微镜(SEM) 12

2.3.2 X射线衍射（XRD） 12

2.4 电化学表征 13

2.4.1循环伏安测试（CV） 13

2.4.2交流阻抗测试（EIS） 13

2.4.3充放电测试 13

第三章 结果与讨论 14

3.1 物理表征（SEM amp; XRD） 14

3.1.1 ZnO/Carbon cloth的形貌表征（SEM） 14

3.1.2 ZnO/Carbon cloth/ZIF-8的形貌表征（SEM） 15

3.1.3 晶体结构分析（XRD） 16

3.2 电化学表征 17

3.2.1循环伏安曲线 17

3.2.2 离子电导率 17

3.2.3循环性能 18

第四章 结论与展望 19

4.1 结论 19

4.2 展望 19

参考文献 20

致 谢 23

第一章 绪论

1.1 研究背景及意义

1.1.1 研究背景

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