论文总字数：22319字

摘 要

可充碱锰电池具有容量大、开路电位高、污染小、可循环使用等优势。针对二氧化锰（EMD）电极的导电性能不佳，从而影响其电化学性能的问题。本文选用石墨烯（GN）、碳纳米管（CNT）和乙炔黑（AB）为导电剂。期望将GN、CNT、AB三种导电剂进行复配之后，可以形成类似于空间几何中点、线、面组成的三维导电网络，提高活性物质的电荷传导能力，从而改善电极的导电性能。本文通过恒流充放电、交流阻抗等电化学测试和SEM形貌观察，研究了单一导电剂及二元、三元复配对碱锰电池EMD电极电化学性能的影响。获得如下主要结论：

（1）单一导电剂的类型、添加量对EMD电极碱锰电池放电容量和循环寿命均具有重要影响。推荐最佳单一导电剂为20wt.%CNT，其首次放电比容量和50次循环后的容量保持率分别为：215.6mAh/g和51.67%。

（2）导电剂复配具有协同效应，可进一步提高EMD电极碱锰电池放电容量的和循环寿命。在导电剂总添加量为20wt%时，推荐二元导电剂CNT/AB的最佳质量比为2:1，其首次放电比容量和50次循环后的容量保持率分别为230.7mAh/g和56.19%。推荐三元导电剂CNT/GN/AB的最佳质量比为6:1:2，其首次放电比容量和50次循环后的容量保持率分别达到250.3mAh/g和65.68%。主要原因在于：CNT/GN/AB形成的三维导电网络能增加EMD颗粒之间的导电通路，提高EMD电极的导电性能。验证了本文EMD导电剂的选择设计思路。

关键词：碱锰电池 电解二氧化锰 导电剂 复配协同效应 电化学性能

Effect of conductive agent on the performance of manganese dioxide electrode for alkaline manganese dioxide battery

ABSTRACT

Rechargeable alkaline manganese dioxide batteries have the advantages of large capacity, high open-circuit potential, low pollution and recyclable use. However, the problem is that the conductivity of the manganese dioxide electrode is poor, which affects its electrochemical performance. In this paper, graphite (GN), carbon nanotube (CNT) and acetylene black (AB) were selected as conductive agents. It was expected that the combination of GN, CNT and AB will form a three-dimensional conductive network similar to the center point, line and plane of the space geometry, which will improve the charge conduction ability of the active material and thus improve the conductivity of the electrode. In this paper, the effects of single conductive agent and their combination on the electrochemical performance of EMD electrode for alkaline manganese dioxide batteries had been studied by constant current charge-discharge, AC impedance and SEM observation. The main conclusions are as follows:

⑴ The type and addition amount of single conductive agent have important influence on discharge capacity and cycle life of EMD electrode for alkaline manganese dioxide battery. The best single conductive agent is recommend by 20wt%CNT，The first discharge specific capacity and the capacity retention after 50 cycles are 215.6 mAh/g and 51.67% , respectively.

⑵ The combination of conductive agents have synergistic effect, which can further improve the discharge capacity and cycle life of EMD electrode for alkaline manganese dioxide battery. The optimum mass ratio of CNT/AB is 2:1，when the total content of conductive agent is 20wt% . The specific capacity of CNT/AB is 230.7 mAh/g and the capacity retention of CNT/AB is 56.19% after 50 cycles. The optimum mass ratio of CNT/GN/AB is 6:1:2. The specific capacity of CNT/GN/AB is 250.3 mAh/g and 65.68% after 50 cycles. The main reason is that the CNT/GN/AB three-dimensional conductive network can increase the conductive path between EMD particles and improve the conductivity of EMD electrode. The idea of selecting and designing EMD conductive agent is verified.

Keywords: Alkaline Manganese battery, Electrolytic manganese dioxide, Conductive agent, synergistic effect，Electrochemical performance

目 录

摘 要 I

ABSTRACT II

第一章 绪论 1

1.1论文研究背景及意义 1

1.2 碱性锌锰电池概述 2

1.2.1碱性锌锰电池的发展 2

1.2.2 碱锰电池的应用 2

1.3 碱锰电池原理^[9] 3

1.3.1 二氧化锰正极的反应过程 3

1.3.2 锌负极的反应过程 5

1.4 二氧化锰电极导电剂研究现状 5

第二章 研究目标、内容及方法 9

2.1研究目标 9

2.2 研究内容 9

2.3 实验材料、设备及研究方法 11

2.3.1 实验用材料及设备 11

2.3.2 电极片的制备及电池组装 12

2.3.3 测试方法 13

第三章 实验结果与讨论 15

3.1 导电剂种类对EMD电极交流阻抗的影响 15

3.2 二元复配导电剂对EMD电极交流阻抗的影响 16

3.2.1 CNT/AB质量比对EMD电极交流阻抗的影响 16

3.2.2 CNT/GN质量比对EMD电极交流阻抗的影响 17

3.3 三元复配导电剂对EMD电极交流阻抗的影响 18

3.4 不同导电剂对EMD电极充放电性能的影响 19

3.5不同导电剂EMD电极的SEM微观结构图 21

第四章 结论和展望 23

4.1 结论 23

4.2 问题与展望 23

参考文献 25

致谢 28

第一章 绪论

1.1论文研究背景及意义

科技的进步与发展带动着各类电子设配的更新迭代，其对电池的性能也提出了更高的要求，各种电池技术也在不断地研究与创新，各类电池正朝着比容量高、性能稳定、性价比高、污染低、安全性好等方向进行发展与创新^[1]。在电作为主要能源的现代社会中，作为储电的电池在能源利用方面起到了相当重要的作用。

锌锰电池已有一百多年的发展历程，并且始终在电池领域占领着一席之地。碱性锌锰电池具有性价比高，性能稳定，大电流连续放电性能优良，贮存时间久（可达五年），低温性能好等特点，深受国内外市场欢迎，是电池领域十分具有发展前途的产品之一^[2-3]。为满足如今的电子数码产品的使用需求，碱锰电池在快速充放电、大电流放电比容量和循环性能等方面需进一步研究。

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