EFFECTS OF CHLORIDE ION ON THE ELECTRO- CHEMICAL BEHAVIOR OF Pb-Ag-RE ALLOY ANODE

doi:10.11900/0412.1961.2014.00548

Acta Metall Sin

2015, Vol. 51

Issue (3): 378-384 DOI: 10.11900/0412.1961.2014.00548

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EFFECTS OF CHLORIDE ION ON THE ELECTRO- CHEMICAL BEHAVIOR OF Pb-Ag-RE ALLOY ANODE

ZHONG Xiaocong, JIANG Liangxing(

), LÜ Xiaojun, LAI Yanqing, LI Jie, LIU Yexiang

School of Metallurgy and Environment, Central South University, Changsha 410083

Cite this article:

ZHONG Xiaocong, JIANG Liangxing, LÜ Xiaojun, LAI Yanqing, LI Jie, LIU Yexiang. EFFECTS OF CHLORIDE ION ON THE ELECTRO- CHEMICAL BEHAVIOR OF Pb-Ag-RE ALLOY ANODE. Acta Metall Sin, 2015, 51(3): 378-384.

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Abstract

Corrosion and oxygen evolution behavior of Pb-Ag-RE alloy anode has been comparatively investigated in H₂SO₄ solution without Cl^- and with 500 mg/L Cl^- by galvonostataic polarization, SEM, XRD, EIS and Tafel scanning. The results show that anodic layer on Pb-Ag-RE anode formed in electrolyte with Cl^- exhibits ‘volcanic vent'-like holes, and the metallic substrate in this electrolyte shows obvious localized corrosion feature with large numbers of corrosion pits. In addition, the presence of Cl^- decreases the amount of PbO₂ on the surface of anodic layer. It also inhibits the formation and adsorption of oxygen evolution intermediates, and further enhances the charge transfer resistance of oxygen evolution reaction. Therefore, Cl^- is detrimental to the corrosion resistance and oxygen evolution reactivity of Pb-Ag-RE alloy anode. Consequently, the Cl^- concentration in electrolyte should be reduced as low as possible during industrial operation.

Key words: Pb-Ag-RE alloy lead-based anode electrowinning chloride ion localized corrosion oxygen evolution reaction

ZTFLH:	TF813
	O646

Fund: Supported by National Natural Science Foundation of China (Nos.51204208 and 51374240), Natural Science Foundation of Hunan Province (No.13JJ1003), China Postdoctoral Science Foundation (No.2013M540638) and Fundamental Research Funds for the Central Universities of Central South University (No.2014zzts028)

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	Xiaocong ZHONG
	Liangxing JIANG
	Xiaojun LÜ
	Yanqing LAI
	Jie LI
	Yexiang LIU

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https://www.ams.org.cn/EN/10.11900/0412.1961.2014.00548 OR https://www.ams.org.cn/EN/Y2015/V51/I3/378

图6

Fig.1 Anodic potential variation of Pb-Ag-RE anode during galvanostatic polarization in H₂SO₄ solution without Cl^- and with 500 mg/L Cl^-

Fig.2 SEM images of anodic layers on Pb-Ag-RE anode obtained through 72 h galvanostatic polarization in H₂SO₄ solution without Cl^- (a) and with 500 mg/L Cl^- (b)

Fig.3 XRD patterns of anodic layers on Pb-Ag-RE anode formed through 72 h galvanostatic polarization in H₂SO₄ solution without Cl^- and with 500 mg/L Cl^-

Fig.4 Variation of Pb²⁺ concentration in electrolyte during 72 h galvanostatic polarization in H₂SO₄ solution without Cl^- and with 500 mg/L Cl^-

Fig.5 Corrosion morphologies of the substrate of Pb-Ag-RE anode after 72 h galvanostatic polarization in H₂SO₄ solution without Cl? (a) and with 500 mg/LCl? (b)

Impedance parameters determined by fitting the EIS data shown in Fig.6

所示EIS数据拟合后获得的阻抗参数

Electrolyte	L	R_u	Q	C_dl	n	R_ct	χ²
	10^-⁷ H?cm²	Ω?cm²	10^-² F?cm^-²	10^-² F?cm^-²		Ω?cm²
Without Cl^?	1.01	0.593	6.90	5.42	0.919	1.88	3.58×10^?4
500 mg/L Cl^?	1.11	0.633	6.64	5.06	0.911	2.26	6.61×10^?4

Impedance parameters determined by fitting the EIS data shown in Fig.6

Fig.6 EIS of Pb-Ag-RE anode after 72 h galvanostatic polarization in H₂SO₄ solution without Cl ? and with 500 mg/L Cl? (Bias potential is 1.38 V in electrolyte without Cl? and 1.36 V in electrolyte with 500 mg/L Cl?) and electrical equivalent circuits (inset) used to fit the impedance data (L—inductance, Ru—uncompensated resistance, CPE—constant phase element, Rct—charge transfer resistance)

Fig.7 Tafel curves of Pb-Ag-RE anode after 72 h galvanostatic polarization in H₂SO₄ solution without Cl? and with 500 mg/LCl? (i—current density)

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