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Investigation on Improvement for Electrodes of Full Sediment Lead-acid Flow Battery

Author: HanXiaoYan
Tutor: ZhangShengTao
School: Chongqing University
Course: Applied Chemistry
Keywords: Liquid flow battery based on deposition reaction Lead methanesulfonate Electrode modification
CLC: TM912
Type: Master's thesis
Year: 2009
Downloads: 185
Quote: 0
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Abstract


The use of chemical power source for energy storage will not be restricted by geographical conditions, and hopefully realize the large-scale energy storage. Therefore, it has significant economic value. The redox flow battery is a kind of large-scale energy storage system, which is mainly developed for power load leveling and peak load reduction. In addition, the redox flow battery can be combined with photovoltaic cell and wind turbine generator. Pletcher et al. had proposed a new kind of lead–acid flow battery system- full sediment lead-acid flow battery. This system differs from traditional lead acid battery in that the electrolyte is aqueous methanesulfonic acid and lead (II) is highly soluble in this acid. It also differs from all reported flow batteries in that it requires only a single electrolyte and hence no separator is required and this will reduce the cost of the batteries significantly. However, the research on this redox flow battery system is still at the starting stage, and there are still a lot of problems remained to be studied.In this paper, kinetics behavior of the PbO2/ Pb(Ⅱ) couple has been studied. According to the anodic polarization curve of rotating glass carbon disc electrode in 0.01mol·L-1 Pb(CH3SO3)2 + 0.5mol·L-1 CH3SO3H, the kinetic parameters of Pb(Ⅱ)→PbO2 reaction were obtained: The equilibrium electrode potential Ee 0q=1.32V vs. SCE, the charge transfer resistance Rc t=3016.21 ?·cm2; exchange current density i 0=1.7026×10-5A·cm-2 obtained by means of the Tafel straight-line extrapolation, charge transfer coefficientβ=0.1378.The cyclic voltammetry behavior of PbO2/Pb(Ⅱ) couple on Pt electrode has been studied experimentally. The results of experiment show that the reversibility for the conversion between PbO2and Pb(Ⅱ) is very poor. And the significant overpotential associated with PbO2/Pb(Ⅱ) couple can cause the major energy loss in this storage system. The kinetics of the Pb(Ⅱ) /Pb couple are rapid, and there is no significant overpotential during the deposition and dissolution of lead.The cyclic voltammetry behavior of PbO2/Pb(Ⅱ) couple on graphite rod, graphite felt and graphite powder-acetylene black composite electrodes has been studied experimentally. It has been found experimentally that the electrode materials tested show good electro-catalytic activity for PbO2/Pb(Ⅱ) redox reaction. Under the same experimental conditions, the deposition amount of PbO2 on the electrode materials tested were in sequence of graphite felt electrode > graphite powder-acetylene black composite electrode > graphite rod electrode. With the increment of the CV cycle number, the reduction peak potential shifts negatively on the electrode materials tested, and the order of the negative shift magnitude of reduction peak potential are graphite felt electrode > graphite powder-acetylene black composite electrode > graphite rod electrode. Oil of vitriol & heat treatments were used to pretreat the electrode materials. Cyclic voltammetry test showed that acid treatment has little improvement effect on the electro-catalytic performance of the graphite rod electrode. However, the PbO2→Pb(Ⅱ) reaction overpotential on graphite felt electrode decreased after the acid treatment.The charge-discharge performance of the PbO2/ Pb(Ⅱ) couple on graphite and graphite felt electrodes have been studied by using constant-current charge/discharge technology. At a current density of 10 mA·cm-2, the coulombic efficiency of the charge-discharge cycle on graphite electrode is typically 73.73%, and the energy efficiency is 58.06%; However, when the current density increased to 50 mA·cm-2, the battery had a poor charge-discharge performance. Therefore, graphite has the potential to be developed as the positive electrode material, but it is not suitable for high current charge-discharge. Compare with the graphite electrode, the vitriol-treaded graphite felt is suitable for high current charge-discharge. When the current density increased to 50 mA·cm-2, the coulombic efficiency of the charge-discharge cycle on graphite felt electrode is still > 80%, and the energy efficiency is 60%. So, graphite felt can be the suitable electrode material for the positive electrode reaction.

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CLC: > Industrial Technology > Electrotechnical > Independent power supply technology (direct power) > Battery
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