利用EQCM研究铅电极在硫酸和硫酸钠溶液中的反应机理

doi:10.13208/j.electrochem.150126

电化学（中英文） ›› 2015, Vol. 21 ›› Issue (4): 362-367. doi: 10.13208/j.electrochem.150126

利用EQCM研究铅电极在硫酸和硫酸钠溶液中的反应机理

邹献平¹，康宗轩¹，黄毓岚¹，舒东^1,2,3*，钟雅云¹，郝俊南¹，廖雨清¹

1. 华南师范大学化学与环境学院，广东广州 510006；2. 广州市能源转化与储能材料重点实验室，广东广州 510006；3. 电化学储能材料与技术教育部工程研究中心，广东广州 510006

收稿日期:2015-01-26 修回日期:2015-04-09 出版日期:2015-08-28 发布日期:2015-08-28
通讯作者: 舒东 E-mail:dshu@scnu.edu.cn
基金资助:
国家自然科学基金（No. 21273085）、广州市科技计划项目（No. 2012J4300147）和广东省自然科学基金（No. S2011010003416）资助

Reaction Mechanisms Study of Pb Electrodes in Sulfuric Acid and Sodium Sulfate Solutions by EQCM

ZOU Xian-ping¹, KANG Zong-xuan¹, HUANG Yu-lan¹, SHU Dong^1,2,3*, ZHONG Ya-yun¹, HAO Jun-nan¹, LIAO Yu-qing¹

1. School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China; 2. Guangzhou Laboratory of Materials for Energy Conversion and Storage, Guangzhou 510006, China; 3. Engineering Research Center of Electrochemical Materials and Technology on Energy Storage, Ministry of Education, Guangzhou 510006, China

Received:2015-01-26 Revised:2015-04-09 Published:2015-08-28 Online:2015-08-28
Contact: SHU Dong E-mail:dshu@scnu.edu.cn

摘要/Abstract

摘要： 使用电化学线性扫描伏安(LSV)、循环伏安(CV)和电化学石英晶体微天平(EQCM)方法研究了硫酸和硫酸钠溶液中铅电极表面的反应过程. 伏安曲线和电极表面质量变化结果分析表明，从-1.0 V到-0.4 V正向扫描时，铅在硫酸溶液中生成两种氧化产物，在-0.87 V时生成硫酸铅，在-0.73 V时生成PbO·PbSO₄，然后PbO·PbSO₄转化成硫酸铅，而铅在硫酸钠中的氧化产物只有硫酸铅. 因此，酸性溶液是PbO·PbSO₄形成的必要条件，这进一步揭示了铅酸电池的负极放电机理，也为铅酸电池负极反应过程提供了新的研究方法.

关键词: 铅酸电池, 电化学石英晶体微天平, 循环伏安, 铅电极

Abstract: Surface reaction processes of Pb electrodes were investigated in H₂SO₄ and Na₂SO₄ solutions by LSV, CV and EQCM. The results in the voltammogram and the mass change curve of the Pb electrode indicated that the oxide products of lead included PbSO4 and PbO·PbSO₄ in sulfuric acid solution with a positive-going potential scan from -1.0 V to -0.4 V and then PbO·PbSO₄transformed into PbSO₄. However, the oxide product of lead was only PbSO₄ in sodium sulfate solution. The experimental results revealed that the acid solution is necessary for the formation of PbO·PbSO₄ and the negative discharge mechanism of lead-acid batteries was suggested. This study had also provided a new research method for the negative plates of lead-acid battery.

Key words: lead-acid battery, electrochemical quartz crystal microbalances, cyclic voltammetry, Pb electrode

中图分类号:

O646

邹献平, 康宗轩, 黄毓岚, 舒东, 钟雅云, 郝俊南, 廖雨清. 利用EQCM研究铅电极在硫酸和硫酸钠溶液中的反应机理[J]. 电化学（中英文）, 2015, 21(4): 362-367.

ZOU Xian-ping, KANG Zong-xuan, HUANG Yu-lan, SHU Dong, ZHONG Ya-yun, HAO Jun-nan, LIAO Yu-qing. Reaction Mechanisms Study of Pb Electrodes in Sulfuric Acid and Sodium Sulfate Solutions by EQCM[J]. Journal of Electrochemistry, 2015, 21(4): 362-367.

参考文献

[1] Li H, Liu H P, Wang Q M, et al. Effects of covalently bonded siloxane on the electrochemical and physical behavior of GEL-VRLA battery[J]. Electrochimica Acta, 2010, 56(2): 663-666.
[2] Xiang J Y, Ding P, Zhang H, et al. Benefical effects of activated carbon additives on the performance of negative lead-acid battery electrode for high-rate partial-state-of-charge operation[J]. Journal of Power Sources, 2013, 241(1): 150-158.
[3] Saravanan M, Ganesan M, Ambalavanan S. A modified lead-acid negative electrode for high-rate partial-state-of-charge applications batteries and energy storage[J]. Journal of Electrochemical Society, 2012, 159(4): A452-A458.
[4] Gandhi K S. Role of electrical resistance of electrodes in modeling of discharging and charging of flooded lead-acid batteries[J]. Journal of Power Sources, 2015, 277: 124-130.
[5] Swogger S W, Everill P, Dubey D P, et al. Discrete carbon nanotubes increase lead acid battery charge acceptance and performance[J]. Journal of Power Sources, 2014, 261: 55-63.
[6] Shanmugasundharam L, Ramasamy M. Influence of some nanostructured materials additives on the performance of lead acid battery negative electrodes[J]. Electrochimica Acta, 2014, 144(20): 147-153.
[7] Shapira R, Nessim G D, Zimrin T, et al. Towards promising electrochemical technology for load leveling application: Extending cycle life of lead acid batteries by the use of carbon nano-tubes (CNTs)[J]. Energy ＆Environmental Science, 2013, 6(2): 587-594.
[8] Kumar S M, Ambalavanan S, Mayavan S. Effects of graphene and carbon nanotubes on the negative active materials of lead acid batteries operating under high-rate partial-state of charge operation[J]. RSC Advances, 2014, 4(69): 36517-36521.
[9] Pavlov D, Rogachev T, Nikolov P, et al. Mechanism of action of electrochemically active carbons on the processes that take place at the negative plates of lead-acid batteries[J]. Journal of Power Sources, 2009, 191(1): 58-75.
[10] Saravanan M, Ganesan M, Ambalavanan S. An in situ generated carbon as integrated conductive additive for hierarchical negative plate of lead-acid battery[J]. Journal of Power Sources, 2014, 251: 20-29.
[11] Pavlov D, Nikolov P. Capacitive carbon and electrochemical lead electrode systems at the negative plates of lead-acid batteries and elementary processes on cycling[J]. Journal of Power Sources, 2013, 242: 380-399.
[12] Zhao L, Chen B S, Wang D L. Effects of electrochemically active carbon and indium oxide in negative lpates on cycle performance of valve-regulated lead-acid batteries during high-rate partial-state of charge operation[J]. Journal of Power Sources, 2013, 231: 34-38.
[13] Ellen E, Daniel B, Alexander B, et al. Carbon blacks for the extension of the cycle life in flooded lead acid batteries for micro-hybrid applications[J]. Journal of Power Sources, 2013, 239: 483-489.
[14] Pavlov D, Nikolov P. Lead-carbon electrode with inhibitor of sulfation for lead-acid batteries operating in the HRPSoC duty batteries and energy storage[J]. Journal of Electrochemical Society, 2012, 159(8): A1215-A1225.
[15] Krivik P, Baca P, Tonar K, et al. Improving the negative lead-acid battery electrodes by using extra additives[J]. ECS Transactions, 2012, 40(1): 145-152.
[16] Wang L Z(王力臻), Zhang K Q(张凯庆), Zhang L S(张林森), et al. Effect of carbon material on electrochemical characteristic of negative electrodes of lead-acid battery[J]. Chinese Journal of Power Sources(电源技术), 2012, 36(9): 1325-1329.
[17] Long L(龙璐), Shi L Y(施利勇), Zhu J(朱健), et al. Effects of carbon material to the performance of ultra-battery[J]. Battery Bimonthly(电池), 2014, 44(3): 147-149.
[18] Mech K, Zabinski P, Kowalik R. Analysis of Rhodium electrodeposition from Chloride solutions[J]. Journal of Electrochemical Society, 2014, 161: D458-D461.
[19] Mitsuhiro S, Takahiro T, Kazuaki T, et al. EQCM investigation on electrodeposition and charge stroge behavior of birnessite-Type MnO2[J]. ECS Transactions, 2013, 50(43): 85-92.
[20] Chen G L(陈国良), Lin H(林珩), Zheng X H(郑杏红), et al. Oxidation of n-propyl alcohol on Pt and Sb, S modified Pt electrodes using CV＆EQCM[J]. Acta Physico-Chimica Sinica(物理化学学报), 2002, 18(2): 147-151.
[21] Lin H(林珩), Chen S P(陈声培), Lin J M(林进妹), et al. An EQCM study of water adsorption and oxidation on Pt electrodes in sulfate acid solution[J]. Journal of Electrochemistry(电化学), 2003, 9(1): 47-53.
[22] Gao J C(高继超), Qi L(齐力), Wang H Y(王宏宇). EQCM studies on the effect of anti-freezing additives on the storage behavior of ions at activates carbon electrodes in NaClO4 aqueous solutions[J]. Chemical Journal of Chinese Universities(高等学校化学学报), 2014, 35(3): 608-612.
[23] Maiara O S, Vitor L M, Roberto M T, et al. An EQCM-D study of the influence of chloride on the lead anodic oxidation[J]. Electrochimica Acta, 2012, 78(1): 347-352.
[24] Peng X L(彭谢兰), Xie Q J(谢青季), Kang Q(康青), et al. Study on the electrodeposition of hydroxides in hydrated perchlorate + organic solvent systems using EQCM[J]. Acta Physico-Chimica Sinica(物理化学学报), 2006, 22(11): 1361-1366.
[25] Pech D, Brousse T, Bélanger D, et al. EQCM study of electrodeposited PbO2: Investigation of the gel formation and discharge mechanisms[J]. Electrochimica Acta, 2009, 54(28): 7382-7388.
[26] Bruckenstein S, Shay M. Experimental aspects of use of the quartz crystal microbalance in solution[J]. Electrochimica Acta, 1985, 30(10): 1295-1300.
[27] Chang W, Krishnan R. In situ charaterzation of lead carrosion layers by combined voltammetry, coulometry, and electrochemical quartz crystal[J]. Journal of Electrochemical Society, 1993, 140(8): L128-L130.

利用EQCM研究铅电极在硫酸和硫酸钠溶液中的反应机理

Reaction Mechanisms Study of Pb Electrodes in Sulfuric Acid and Sodium Sulfate Solutions by EQCM

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

[1]	王昊, 曹晓舟, 薛向欣. 锑在氯化胆碱-乙二醇低共熔溶剂中的电沉积研究[J]. 电化学（中英文）, 2022, 28(4): 2103071-.
[2]	蔡雪凡, 孙升. 多孔电极电池的循环伏安法模拟[J]. 电化学（中英文）, 2021, 27(6): 646-657.
[3]	孙齐, 韩严和, 付晓璐. 改性钛基PbO₂电极的制备及其对COD的快速检测[J]. 电化学（中英文）, 2021, 27(5): 558-569.
[4]	邢逸飞, 李娜, 温晓芳, 韩宏彦, 崔敏, 张聪, 任聚杰, 籍雪平. 基于取代型多酸复合材料的多巴胺电化学检测[J]. 电化学（中英文）, 2020, 26(6): 890-899.
[5]	杨裕生. 电化学储能研究22年回顾[J]. 电化学（中英文）, 2020, 26(4): 443-463.
[6]	韩平, 冯海涛, 董亚萍, 田森, 张波, 李武. 氢氧化钠水溶液体系中金属铬的电化学氧化过程[J]. 电化学（中英文）, 2020, 26(3): 413-421.
[7]	郭佳瑶, 陈煅, 张杰, 詹东平. 法拉第吸脱附偶联过程循环伏安行为的有限元分析[J]. 电化学（中英文）, 2020, 26(2): 281-288.
[8]	凌云, 汤儆, 刘国坤, 宗铖. 暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程[J]. 电化学（中英文）, 2019, 25(6): 731-739.
[9]	李明雪, 史杭, 刘佳, 张檬, 周剑章, 吴德印, 田中群. 金电极上偶氮腺嘌呤的电化学行为研究[J]. 电化学（中英文）, 2019, 25(6): 651-659.
[10]	M. Rostom Ali, S Sankar Saha, Md Ziaur Rahman. 共晶基离子液体的钴电化学沉积[J]. 电化学（中英文）, 2018, 24(5): 546-554.
[11]	董鹏飞，李娜，赵海燕，崔敏，张聪，任聚杰，藉雪平. Keggin 型磷钨酸盐修饰碳糊电极传感多巴胺的研究[J]. 电化学（中英文）, 2018, 24(5): 555-562.
[12]	黄帅帅，刘诚，金磊，杨防祖，田中群，周绍民. 玻碳电极表面复合配位银电结晶机理研究[J]. 电化学（中英文）, 2018, 24(4): 344-350.
[13]	秦建新，林峰，刘文平，陈超，任孟德. 酸性溶液中Fe²⁺ /Fe³⁺相互转换对电极还原行为的影响[J]. 电化学（中英文）, 2017, 23(6): 702-707.
[14]	M. Rostom Ali, R. K. Biswas, Md. Golam Zakaria. 海沙钛铁矿在硫酸溶液中的电化学溶解研究[J]. 电化学（中英文）, 2017, 23(4): 420-428.
[15]	黄先杰，闫慧，黄帅帅，杨防祖，田中群，周绍民. 玻碳电极表面因瓦合金的电化学成核机理[J]. 电化学（中英文）, 2017, 23(1): 7-12.