论文总字数：19948字

摘 要

锌离子电池制备简单，原料无毒且廉价易得，同时具有很高的比容量和比功率，可快速充电，循环寿命高。在中性环境中，锌的自腐蚀也得到了很大的改善，反应平稳，无明显的发热现象，其优良的性能使得其未来有望在电子产品和交通运输上得到广泛的应用。

锌离子电池的电化学行为是正极二氧化锰通过锰的价态转换来存储二价锌离子，由α-MnO₂作为正极，锌作为负极以及中性的ZnSO₄或Zn(NO₃)₂水溶液作为液相电解质组成。本文选用水热法制备纳米MnO₂粉体并测试其在锌离子电池中的性能，同时研究导电剂种类及其加入量对锌离子电池的影响，从而为锌离子电池的研究和应用提供实验依据。

水热法二氧化锰制备实验表明，在160℃反应温度下，反应时间为较短的2h时，无法生成α-MnO₂。当反应时间延长至4h，纳米棒状α-MnO₂开始生成，且所获得的水热2号（4h）的充放电性能明显优于水热1号（6h）。导电剂的种类及加入量对锌离子电池性能的影响研究表明：正负极对导电剂的含量需求是不同的，这主要和正负极活性物质的导电性能以及颗粒大小有关。与以人工石墨为导电剂的电池相比，以乙炔黑为导电剂的锌离子电池，其稳定性好，比电容高，恒流放电性能更好，循环寿命更长，放电比容量高达350mAh/g。

关键词：锌离子电池 水热法 纳米α-MnO₂ 制备 充放电性能

Preparation of Nano-α-MnO₂ by Hydrothermal Method

And Its Application in the Cell

ABSTRACT

The preparation of the zinc ion battery is simple, the raw material is avirulent, cheap and easy to obtain, and this battery has high specific capacity and specific power, which can be quickly charged and has high cycle life. In a neutral environment, zinc corrosion has also been greatly improved, smooth reaction, no obvious fever phenomenon. Its excellent performance makes the future is expected to get extensive application in the electronics and transportation.

The electrochemical behavior of zinc ion battery is that manganese dioxide in positive pole stores two valent zinc ions by manganese valence conversion. Zinc ion battery makes α-MnO₂ as the positive pole and zinc as the negative pole, and ZnSO₄ or Zn (NO₃) ₂ neutral water solution as the liquid electrolyte. This paper intends to prepare nano-MnO₂ powder by hydrothermal method and test its performance of the zinc ion battery, and study the effect of different kinds, adding amount of conductive agent for zinc ion battery, thus for the research and application of zinc ion battery provide experimental basis.

Preparation experiments of nano-α-MnO₂ by hydrothermal method show that when the reaction time is shorter than 2h, the hydrothermal reaction is not complete and α-MnO₂ can not be generated when the reaction temperature is 160℃. When the reaction time was prolonged, α-MnO2 began to be generated. Meanwhile the charge-discharge performance of the hydrothermal No.2 (4h) was significantly better than that of the hydrothermal No.1 (6h). In the research of the effect in two kinds of conductive agent with different adding amount of zinc ion battery, the conductive agent content requirements of positive pole and the negative pole are different, this is because electrical properties and particle size of the positive and negative electrode material. Compared with the battery with artificial graphite as conductive agent, the zinc ion battery with acetylene black as conductive agent has good stability, high specific capacitance, better discharge performance and longer cycle life and discharge specific capacity up to 350mAh/g.

Keywords: Zinc ion battery；Hydrothermal synthesis；Nanosized α-MnO₂；

Preparation；Charge-dischagre performance

目 录

摘 要 I

ABSTRACT II

第一章 绪 论 1

1.1 研究背景及意义 1

1.2 MnO₂的晶体结构 3

1.3 MnO₂的制备方法 5

1.3.1 MnO₂常用制备方法及现状 5

1.3.2 MnO₂的水热制备法及反应方式 6

1.4 电池中的导电剂及其应用 8

1.5 研究目的及内容 9

第二章 实验研究方法 10

2.1 实验材料 10

2.2 实验仪器与规格 10

2.3 实验方法 11

2.3.1 纳米α-MnO₂的制备 11

2.3.2纳米α-MnO₂的表征与测试 12

2.3.4 锌离子电池的组装和电化学性能测试 14

第三章 实验结果与分析 16

3.1 反应产物的结构分析与比较 16

3.2 导电剂种类及添加量对电池性能的影响 18

第四章 结 论 23

参考文献 24

致 谢 26

第一章 绪 论

1.1 研究背景及意义

能源、材料和信息被誉为21世纪的三大支柱，而随着工业的迅速发展，能源短缺和环境污染成为人类正在面临的两大严峻考验，因此，新的清洁能源的研究引起了国内外研究者的广泛关注。解决这一问题的出路，除了开发新能源外，改善现有能源采集技术也是一个至关重要的方案。在所有已知的能源中，电能是最为方便和洁净的一种，也是应用最为广泛的一种。而电能除了由电机产生之外，另一种方式便是通过电池。一次电池制备简单，价格低廉，但其不可循环使用的缺点使其对资源产生了巨大的消耗和浪费。二次电池以其环保可循环的特点更是成为当下科技的研究热点。

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