摘 要：针对高稳定性、高活性全钒液流电池电解液以及高能量密度单液流电池沉积型电对及固体电极电化学性能与电解质溶液之间构效关系、高稳定性浓电解质溶液化学理论及作用机制等关键科学问题，以具备较大应用潜力的全钒双液流以及锌/镍、全铅单液流电池体系电解质的溶液化学为研究重点，通过电化学测试与材料物性表征相结合，深入研究了电解质溶液对全钒双液流以及碱性沉积型锌负极和电池性能的影响，阐明了电解液流速、锌沉积面容量和电流密度的关联；考察了不同种类的无机、有机添加剂以及添加剂中的官能团对电解液的热稳定性以及电化学活性的影响，深入研究了电解液溶液及添加剂对固体氧化镍正极活性和稳定性的影响，探讨了电解液添加剂与锌负极和氧化镍正极的相容性；研究了全铅单液流电池电解质溶液的物化性质，探明电解液组成对电极性能的影响规律；研究了电解液添加剂对全铅单液流电池电极性能的影响及其作用机制；考察了支持电解质对电解液的热力学稳定性、电化学活性以及循环稳定性等的影响，优化了电解液的组成，提高了电池充放电的能量效率和循环稳定性。重要的创新点包括以下方面：
（1）确定了对于全钒液流电池电解液的热稳定性和电化学性能具有积极作用的添加剂结构和支持电解质组成；
（2）阐明全铅单液流电池电解液中铅活性离子对电极性能的影响规律，优化了铅离子浓度；
（3）提出电解液中添加电解PbO2，降低沉积型PbO2电极极化，抑制铅累积和枝晶的新方法，获得了高活性、高沉积均匀性Pb负极和PbO2正极。
关键词：全钒液流电池 沉积型单液流电池 电解液 添加剂 电极
Abstract：The all vanadium redox flow battery， Zn/Ni， PbO2/Zn、PbO2/Cu（Cd） and all lead single flow battery systems with great application potential and electrolyte of high concentration are taken as the focus of research. Influence of some inorganic additives and organic additives with various functional groups on the thermal stability and electrochemical performance of electrolyte of vanadium redox flow battery were investigated. The improved electrochemical performance may be ascribed to more active sites provided by -NH2 group and the enhanced hydrophilicity of theelectrode provided by -NH2 and -SO3H groups. Effects of methanesulfonic acid as supporting electrolyte on thermal stability and electrochemical performance are investigated. The electrochemical results show that V（IV）/V（V） exhibits superior electrochemical activity and reversibility in the mixture of 3 M H2SO4 and 7 M methanesulfonic acid， and the diffusion coefficient of V（IV） species， exchange current density and reaction rate constant become larger in the mixture of 3 M H2SO4 and 7 M methanesulfonic acid. In a flowing electrolyte， the electrochemical reaction characteristics and kinetics of electrode process of the metallic zinc， copper， cadmium and lead deposition and dissolution were investigated. The suitable deposition substrates are determined. The electrolyte conditions under which the metal ions can be evenly and rapidly deposited with high area capacity and high efficiency are gained. The effect laws of electrolyte additive on metal deposition morphology and electrochemical activity and its mechanism of action were investigated. The relationship between electrolyte flowing speed， deposition area capacity and current density was investigated. The energy efficiency and stability of batteries in the process of electrode enlargement and under high deposition area capacity has been improved. The innovations include：
（1）The structure and component of additives that can improve the thermal stability and electrochemical performance of vanadium redox flow battery were determined.
（2）the effect laws of lead ions in the electrolyte of all lead single flow batteries on the performance of electrodes were clarified.
（3）The electrolytic PbO2 was added into the electrolyte， which lowered the over-potential of deposition type PbO2 electrodes and eliminated the accumulation of lead and the dendrite growth on the lead negative electrode.
Key Words：All vanadium redox flow battery；Deposition type single flow battery；Electrolyte；Additives；Electrode