【作者】 王璐；

【导师】 司士辉；

【作者基本信息】 中南大学 ， 化学， 2014， 硕士

【摘要】 摘要：聚苯胺具备优异的导电性、氧化还原特性及环境稳定性,合成方法简单且成本较低,可作为二次电池的正极材料。柔性石墨纸是一种质量轻、易制得且价格便宜的半导体材料,可作为锌-聚苯胺二次电池的正极的基体。本文依照以上思路从以下三方面进行研究：(1)对比研究几种不同的集流体材料作聚苯胺电极基体对聚苯胺正极的电化学性能影响,研究结果表明：自行制备的石墨纸是一种更好的正极集流体材料。聚苯胺电极的基体运用循环伏安法氧化处理后使用,聚苯胺／石墨纸正极的最佳制备条件可通过正交实验得出。扫描电镜和傅立叶变换红外光谱分析结果证明：两基体上聚苯胺均为翠绿亚胺结构,石墨纸为正极基体与金箔基体相比,基体上附着的聚苯胺膜更致密。从充放电循环测试的结果中可以看出,放电电流密度为0.3mA/cm2时,该电池的放电比容量为158.34mAh/g,充放电100次后,放电比容量较第一次仅下降12.84%。(2)研究对正极掺杂0.03mol/L的5种无机离子及化合物对水溶液锌-聚苯胺／石墨纸二次电池的电化学性能影响。研究了自制有机醇、自制有机胺及二苯胺磺酸钠对正极的最佳掺杂比例。与未掺杂锌-聚苯胺／石墨纸二次电池进行电化学测试比较,结果表明：掺杂Fe3+Ni2+,6×10-3mol/L二苯胺磺酸钠有助于提高电池的放电比容量；掺杂1.5%的自制有机醇,0.02g自制有机胺对电池放电比容量和循环性能均有提高作用；掺杂Co2+,Mn2+有助于提高电池的循环性能。掺杂V205电池性能不仅没提升,还会导致循环效率降低。(3)研究以柔性石墨纸作集流体的锌-聚苯胺填充式电池。电化学测试结果表明：电化学方法合成的聚苯胺混合正极填充材料组成的锌-聚苯胺电池能在较大电流密度下充放电,且随着电流强度的增大,放电比容量减小；在电流密度为3.18mA/cm2寸,最佳正极填充混合材料质量为0.1g；在正极的制备过程中混合适量石墨粉可提升锌-聚苯胺二次电池的放电比容量,在混合石墨粉的基础上掺杂自制有机醇或自制有机胺可提高锌-聚苯胺电池的电化学性能。更多还原

【Abstract】 Polyaniline can be used as the positive electrode material of rechargeable battery, because it had excellent conductivity, reversible redox properties and environmental stability. It was simple to synthesis and it was a low cost material. Flexible graphite paper was a kind of semiconductor material which was light weight, easily obtained and low cost, it could be used as the current collector of the cathode of the zinc-polyaniline secondary battery. In this paper, we study the following three aspects in accordance with the above ideas:(1) A comparison study on the electrochemical properties of several different sets of current collector materials which were used as the substrate for polyaniline electrode was done. The result showed that the flexible graphite paper which prepared by my own showed better electrochemical properties as a current collector for cathode. The graphite papers oxidized by cyclic voltammetry were used as the substrate for the praperation of polyaniline films. The optimized factors for preparation polyaniline/graphite paper cathode were obtained through Orthogonal experiments. FTIR results suggested that polyaniline in emeraldine salt form, and SEM micrographs showed that the compact polyaniline was obtained on the graphite paper substrate. We made the conclusion that the specific capacity of the zinc-polyaniline/graphite paper rechargeable battery was158.34mAh/g under a constant current of0.3mA/cm2, the specific capacity fell only12.84%after100times of charge and discharge.(2) The influence of co-doping five metal ions or inorganic o,xide at the concentration of0.03mol/L on the electrochemical performance of aqueous zinc-polyaniline/graphite paper rechargeable batteries was investigated. The best doping concentrations of mixed organic alcohol, mixed organic amine and sodium diphenylaminesulfonate on the cathode was obtained. Compared the alloyed battery electrochemical properties with unalloyed zinc polyaniline/graphite paper battery, the experiment results showed that:the polyaniline electrode dopped by Fe3+, Ni2+,6×10-3 mol/L sodium diphenylaminesulfonate had improved the discharge capacity of the cell, the cathode dopped by mixed organic alcohol with the doping percentage composition was1.5%or0.02g mixed organic amine could increased both the discharge capacity and the performance of the battery. The polyaniline dopped by Co2+, Mn2+could improved the performance of the cell, the anode dopped by V2O5decreased the discharge capacity, what’s worse, the performance became lower.(3) Discussed the zinc-polyaniline solid-state battery with the graphite paper as current collector. The electrochemical results showed that the zinc-polyaniline battery which cathode was made by the mixed polyaniline material synthesis by electrochemical method could discharge under a higher current density, the discharge capacity became smaller as the current density became higher. When the current density was3.18mA/cm, the ideal quality of the mixed polyaniline material was0.1g. The polyaniline cathode mixed by graphite powder could improved the discharge capacity of the zinc-polyaniline battery. The positive electrode which mixed with graphite powder dopped by mixed organic alcohol or mixed organic amine could improved the electrochemical performance of the cell.更多还原