自提出之日起，全钒液流电池备受研究人员青睐，因其具有安全环保、结构灵活等特点，被用作大规模的清洁一次能源的储存与转换。发展至今，全球各地已经修建了若干全钒液流储能电站，但是全钒液流电池在运行过程中存在体积失衡、浓度失衡和价态失衡，严重影响电池的循环寿命与放电容量和效率，正负极电解液的跨膜输运是重要原因，为了实时准确地得到电解液的跨膜输运动力学需要发展电解液在线检测技术，从工程应用的角度出发，也需要对电解液进行实时在线检测；电极的活性与分布对全钒液流电池的能量密度与极化造成影响，其中负极电极的析氢副反应也对电极的活性产生影响，需要进一步探究负极电极的反应动力学。基于以上，本论文从全钒液流电池负极电解液与电极材料出发，对电解液的在线检测、跨膜输运动力学以及负极电极的钒离子反应和析氢副反应的反应动力学与分布展开了研究，主要内容有：搭建了基于光谱在线检测法的全钒液流电池负极电解液荷电状态（State of Charge, SOC）与体积的在线检测平台，配制并测试了一系列负极电解液标准样品的吸光度数值，并获得了负极电解液在605 nm、640 nm波长下的吸光度与V2+、V3+浓度的关系式。通过联用两关系式，实现了对全钒液流电池的负极电解液SOC的在线检测，并进一步研究了200圈充放电循环过程中全钒液流电池负极电解液的变化。结果表明，充放电循环时，由于H3O+与钒离子的正负极不对称输运，充电时H3O+与钒离子从正极输运至负极、放电时H3O+与钒离子从负极输运至正极，整体表现出负极电解液的钒离子与体积持续减少，其中电解液的失衡主要分为急剧失衡阶段（1 ~ 10圈）、过渡阶段（10 ~ 70圈）与平稳失衡阶段（70圈以后）。搭建了基于全反射传感检测的电极原位检测系统，并用于检测负载Bi的石墨毡用于全钒液流电池负极电极时的电极表面钒离子反应与析氢副反应的分布。我们发现，大量析氢会造成Bi的脱落，对负极钒离子反应的活性影响较小，然而会造成电极表面钒离子反应的分布变得不均匀，可逆性变差；大量析氢同时会大大提高析氢起始电位，同时造成析氢副反应活性分布变得不均匀，有利于抑制负极电极材料的析氢副反应的发生。

Since its inception, the all-vanadium flow battery has been favored by researchers for its safety, environmental friendliness, and structural flexibility, and has been used as a large-scale storage and conversion of clean primary energy. To date, several all-vanadium liquid flow energy storage plants have been built around the world, but all-vanadium liquid flow batteries suffer from volume imbalance, concentration imbalance and valence imbalance during operation, which seriously affects the cycle life and discharge capacity and efficiency of the battery, and the transmembrane transport of the positive and negative electrolyte is an important cause. In order to obtain real-time and accurate kinetics of electrolyte transport across the membrane requires the development of online electrolyte detection technology, and from the perspective of engineering applications, in-situ online detection of electrolyte is also required. The activity and distribution of the electrode affect the energy density and polarization of the all-vanadium flow battery, and the hydrogen precipitation of the negative electrode also affects the activity of the electrode, which requires further investigation of the reaction kinetics of the negative electrode. Based on the above, this thesis investigates the online detection of electrolyte, transmembrane transport kinetics, and the reaction kinetics and distribution of vanadium ion reaction and hydrogen precipitation side reactions at the anode electrode of an all-vanadium flow battery, starting from the anode electrolyte and electrode materials. The main contents are as follows:An on-line electrolyte spectroscopic monitoring platform was developed for the online detection of SOC and volume of negative electrolyte of all-vanadium flow battery. A series of absorbance values of negative electrolyte standard samples were prepared and tested, and the relationship between absorbance and V2+ and V3+ concentrations of negative electrolyte at 605 nm and 640 nm were obtained. The online detection of the negative electrolyte SOC of an all-vanadium flow battery was achieved by coupling two equations and further investigating the changes in vanadium ions in the negative electrolyte of an all-vanadium flow battery during 200 charge/discharge cycles. The results show that H3O+ and vanadium ions are transported from positive to negative electrode during charging, and from negative to positive electrode during discharging, showing a continuous reduction of vanadium ions and volume in the negative electrolyte, where the electrolyte imbalance is mainly divided into a rapid imbalance phase (1-10 cycles), a transition phase (10-70 cycles) and a smooth imbalance phase (after 70 cycles).An insitu electrode detection system based on total reflection sensing detection was developed and used to detect the distribution of vanadium ion reactions and hydrogen precipitation side reactions on the electrode surface when graphite loaded with Bi is used as the anode electrode of an all-vanadium flow battery. It is found that large amount of hydrogen precipitation causes Bi shedding, which has less effect on the activity of vanadium ion reaction at the anode, but causes the distribution of vanadium ion reaction at the electrode surface to become uneven and reversible; large amount of hydrogen precipitation also greatly increases the onset potential of hydrogen precipitation, and causes the distribution of hydrogen precipitation side reaction activity to become uneven, which is beneficial to suppress the occurrence of hydrogen precipitation side reaction at the anode electrode material.