Effect of Current Densities on the Microstructure and Electrochemical Behavior of the Porous β-PbO₂ Electrode

Abstract:

In order to obtain a titanium-based PbO₂ electrode with high electrocatalytic activity and good stability, A porous β-PbO₂ electrode is prepared by electrodepositing on titanium substrate Sn-Sb-RuOx coating. The surface morphology and phase analysis of the porous β-PbO₂ electrode prepared at different current density were investigated by SEM and XRD. Results showed that the current density changes the surface morphology and active surface area of the porous β-PbO₂ electrode. When the current density is 2 A/dm², the surface of the porous β-PbO₂ prepared by electrodeposition has a uniform porous morphology with a pore diameter of 50-200 µm with main crystal phase of β-PbO₂. Influence of current density on the electrochemical activity of the electrode was analyzed using anodic polarization curve, electrochemical impedance spectroscopy and galvanostatic polarization. Results revealed that with the increase of current density, the oxygen evolution potential of the porous β-PbO₂ electrode decreases first and then increases while the exchange current density first increases and then decreases. When the current density is 2 A/dm², the oxygen evolution potential is 2.0075 V(at 0.05 A/cm²) and the maximum exchange current density is 1.77×10^-4 A/cm². According to the electrochemical impedance spectroscopy, when the current density is 2 A/dm², Q_f and Q_dl are the largest, R_f and R_ct are the smallest, and the R_F first increases and then decreases with the current density increases. When the current density is 2 A/dm², the maximum R_F value is 655.7. The results with galvanostatic polarization at current density of 0.05 A/cm² showed that the electrode has a minimum electrode voltage of 2.05 V at a current density of 2 A/dm². Accelerated life experiments were carried out in 2 g/L Cl^- and 150 g/L H₂SO₄ bath at 25 °C, and the porous β-PbO₂ electrode obtained under the current density of 2 A/dm² has the longest life, and the electrode life is 68 h, which is 2.5 times of the PbO₂ electrode obtained under the current density of 4 A/dm².

• Periodical: Materials Science Forum (Volume 956)
• Pages: 21-34
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.956.21
• Online since: June 2019
• Authors: Shi Chuan Wang*, Sheng Chen, Bu Ming Chen, Tai Xiang Huang, Hui Huang, Ya Peng He, Wen Kai Yan, Zhong Cheng Guo, Rui Dong Xu, Hai Tao Yang
• Keywords: Current Density, Electrochemical Behavior, Porous PbO₂, Sn-Sb-RuO_x Interlayer

References

[1] M Zhou, Q Dai, Lecheng Lei, et al. Long Life Modified Lead Dioxide Anode for Organic Wastewater Treatment: Electrochemical Characteristics and Degradation Mechanism. Environmental Science and Technology, 39(2005):363-370.

DOI: 10.1021/es049313a

[2] R Lapuente, F Cases. A voltammetric and FTIR-ATR study of the electropolymerization of phenol on platinum electrodes in carbonate mediumInfluence of sulfide [J]. Journal of Electroanalytical Chemistry, 451(1998):163-171.

DOI: 10.1016/s0022-0728(98)00098-9

[3] R Amadelli, L Samiolo, A B Velichko, et al. Composite PbO2-TiO2 materials deposited from colloidal electrolyte: Electrosynthesis, and physicochemical properties. Electrochimica Acta, 54(2009):5239-5245.

DOI: 10.1016/j.electacta.2009.04.024

[4] Y Dan, H Lu, X Liu, et al. Ti/PbO2+nano-Co3O4 composite electrode material for electrocatalysis of O2 evolution in alkaline solution. International Journal of Hydrogen Energy, 36(2011): 1949-1954.

DOI: 10.1016/j.ijhydene.2010.11.046

[5] Z Zhang. Engineering technology of titanium electrode. Beijing: Metallurgical Industry Press, 2003. (in Chinese).

[6] I Ivanov, Y Stefanov, Z Noncheva, et al. Insoluble anodes used in hydrometallurgy (Part I): Corrosion resistance of lead and lead alloy anodes. Hydrometallurgy, 57(2000):109-124.

DOI: 10.1016/s0304-386x(00)00097-9

[7] Y Lai, L Jiang, J Li, et al. A novel porous Pb-Ag anode for energy-saving in zinc electro-winning(Part I)：Laboratory preparation and Properties. Hydrometallurgy, 102(2010):70-83.

DOI: 10.1016/j.hydromet.2010.02.012

[8] X Ke, D Tang. Structural and electrochemical features of iridium-based oxide coating on titanim. Heat Treatment of Metals, 33(2008):82-84.

[9] Y Shi, H Meng. Electrochemical Behavior of IrO2 Electrodes in the Anodic Electrodeposition of MnO2. Chinese Journal of Chemical Physics, 27(2011):461-467.

[10] H T Yang, H R Liu, Z C Guo, et al. Electrochemical behavior of rolled Pb–0.8%Ag anodes. Hydrometallurgy, 140(2013): 144-150.

DOI: 10.1016/j.hydromet.2013.10.003

[11] Y Zhang, B Chen, Z Guo, et al. Corrosion resistance of electrodeposited Al/Pb-Ag anode during zinc electrowinning. Chinese Journal of Applied Chemistry, 30(2013):458-462.

DOI: 10.3724/sp.j.1095.2013.20264

[12] D Zhou, L Gao. Effect of electrochemical preparation methods on structure and properties of PbO2 anodic layer. Electrochimica Acta, 53(2007):2060-2064.

DOI: 10.1016/j.electacta.2007.09.005

[13] Y Xia, Q Dai, J Chen. Electrochemical degradation of aspirin using a Ni doped PbO2 electrode. Journal of Electroanalytical Chemistry, 744(2015):117-125.

DOI: 10.1016/j.jelechem.2015.01.021

[14] S P Li, Z Hu, H L Cao. Preparation and characterization of neodymium doped Ti-based SnO2/Sb electrocatalytic electrodes. Journal of the Chinese Society of Rare Earths, 26(2008): 291-295.

[15] Y Dong. A Study of Ti/SnO2-Sb/PbO2 Electrode Passivation during the Electrochemical Oxidation. Master's Degree Thesis of Jilin University, China, 2007. (in Chinese).

[16] L Li, Z Huang, X Fan, et al. Preparation and Characterization of a Pd modified Ti/SnO2-Sb anode and its electrochemical degradation of Ni-EDTA, Electrochimica Acta, 231(2017):354-362.

DOI: 10.1016/j.electacta.2017.02.072

[17] H Yang, B Chen, Z Guo, et al. Effects of current density on preparation and performance of Al/conductive coating/a-PbO2-CeO2-TiO2/β-PbO2-MnO2-WC-ZrO2 composite electrode materials. Transactions of Nonferrous Metals Society of China, 24(2014):3394-3404.

DOI: 10.1016/s1003-6326(14)63482-8

[18] R D Xu, L P Huang, J F Zhou, et al. Effects of tungsten carbide on electrochemical properties and microstructural features of Al/Pb-PANI-WC composite inert anodes used in zinc electrowinning. Hydrometallurgy, 22(2012):1693-1700.

DOI: 10.1016/j.hydromet.2012.04.012

[19] Y Lai, Y Li, L Jiang, et al. Electrochemical behaviors of co-deposited Pb/Pb–MnO2, composite anode in sulfuric acid solution-Tafel and EIS investigations. Journal of Electroanalytical Chemistry, 671(2012):16-23.

DOI: 10.1016/j.jelechem.2012.02.011

[20] H Ning, Y Xin, L Xu, et al. Properties of IrO2-Ta2O5 Coated Titanium Anodes Modified with Graphene. Rare Metal Materials and Engineering, 45(2016):946-951.

[21] F Lian, Y Xin, B Ma, et al．Effect of Carbon Nanotubes on Anodic Properties of Ti/Ru-Ir-Sn Oxides. Journal of Electrochemistry, 21(2015):375-381.

[22] J M Hu, H M Meng, J Q Zhang, et al. Degradation mechanism of long service life Ti/Ir-TaO oxide anodes in sulphuric acid. Corrosion Science, 44(2002):1655-1668.

DOI: 10.1016/s0010-938x(01)00165-2

[23] L Xu, Y Xin, J Wang. A comparative study on IrO2-Ta2O5 coated titanium electrodes prepared with different methods. Electrochimica Acta, 54(2009):1820-1825.

DOI: 10.1016/j.electacta.2008.10.004

[24] B Chen, Z Guo, H Huang, et al. Effect of the current density on electrodepositing alpha-lead dioxide coating on aluminum substrate. Acta Metallurgica Sinica (English Letters), 22(2009):373-382.

DOI: 10.1016/s1006-7191(08)60111-8

[25] Débora V. Franco, Leonardo M. Da Silva, Wilson F. Jardim, et al. Influence of the electrolyte composition on the kinetics of the oxygen evolution reaction and ozone production processes.Journal of the Brazilian Chemical Society, 17( 2006):446-757.

DOI: 10.1590/s0103-50532006000400017

[26] V A Alves, L A D Silva, J F C Boodts. Surface characterisation of IrO2/TiO2/CeO2, oxide electrodes and Faradaic impedance investigation of the oxygen evolution reaction from alkaline solution. Electrochimica Acta, 44(1998):1525-1534.

DOI: 10.1016/s0013-4686(98)00276-x

[27] H T Yang, H R Liu, Z C Guo, et al. Electrochemical behavior of rolled Pb–0.8%Ag anodes. Hydrometallurgy, 140(2013):144-150.

DOI: 10.1016/j.hydromet.2013.10.003

[28] U Casellato, S Cattarin, M Musiani. Preparation of porous PbO2, electrodes by electrochemical deposition of composites. Electrochimica Acta, 48(2003):3991-3998.

DOI: 10.1016/s0013-4686(03)00527-9

[29] Junfeng Gui, Liangxing Jiang, Xiaocong Zhong, et al. Effects of Ag and RE contents on electrochemical performance of Pb­Ag­RE alloy anode. The Chinese Journal of Nonferrous Metals, 25(2015):111-118.

[30] Maolan Zhu, Tao Tu, Gensong Zhu, et al. Influence of Gd on properties of Pb based anode for nonferrous electrowinning. The Chinese Journal of Nonferrous Metals, 24(2014):2821-2826.

[31] Xiaocong Zhong, Liangxing Jiang, Xiaojun Lu, et al. Effects of chloride ion on the electrochemical behavior of Pb-Ag-RE alloy anode. Acta Metallurgica Sinica, 3(2015):378-384.

[32] Y H Shi, H M Meng, D B Sun, et al. Effect of SbOx+SnO2 intermediate layer on the properties of Ti-based MnO2 anode. Acta Physico-Chimica Sinica, 23(2007):1553-1559.

[33] Y Zheng, W Su, S Chen, et.al. Ti/SnO2–Sb2O5–RuO2/α-PbO2/β-PbO2 electrodes for pollutants degradation, Chemical Engineering Journal, 174(2011):304-309.

DOI: 10.1016/j.cej.2011.09.035

[34] W Yang, H Wang, F Fu, Preparation and performance of Ti/Sb-SnO2/β-PbO2 electrode modified with rare earth, Rare Metal Materials and Engineering, 39(2010):1215-1218.

[35] Yongchang Huang, Houlong Chen. Study on the anodic reaction of chloring evolution on Ti/β-PbO2 electrode. Chinese Journal of Applied Chemistry, 7(1990):25-29.