Effect of Hydrogen Pre-charging for Ti-substrate on Microstructure and Electrochemical Properties of Ti/RuO2-IrO2-TiO2 Anode

doi:10.11902/1005.4537.2024.410

Journal of Chinese Society for Corrosion and protection

2025, Vol. 45

Issue (5): 1277-1288 DOI: 10.11902/1005.4537.2024.410

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Effect of Hydrogen Pre-charging for Ti-substrate on Microstructure and Electrochemical Properties of Ti/RuO₂-IrO₂-TiO₂ Anode

LIU Penghe¹^,², XUE Lili¹, XU Likun²(

), XIN Yonglei², GUO Mingshuai², ZHOU Shuai², DUAN Tigang²

1 College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
2 National Key Laboratory of Marine Corrosion and Protection, Luoyang Ship Material Research Institute, Qingdao 266237, China

Cite this article:

LIU Penghe, XUE Lili, XU Likun, XIN Yonglei, GUO Mingshuai, ZHOU Shuai, DUAN Tigang. Effect of Hydrogen Pre-charging for Ti-substrate on Microstructure and Electrochemical Properties of Ti/RuO₂-IrO₂-TiO₂ Anode. Journal of Chinese Society for Corrosion and protection, 2025, 45(5): 1277-1288.

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Abstract

The anode of oxides-coated Ti-substrate plays an important role in the electro-chlorination system for biofouling prevention in seawater. The surface condition of Ti-substrate affects the performance of the anode. Herein, the effect of hydrogen pre-charging for the Ti-substrate on the microstructure and electrochemical properties of Ti/RuO₂-IrO₂-TiO₂ anode was studied using surface analysis methods like SEM, XRD, and electrochemical techniques such as CV, EIS, potentiodynamic polarization measurement, and accelerated life test. The results show that a surface layer composed of hydrides of TiH_1.5 and TiH₂ is formed on the surface of Ti-substrate after being charged with hydrogen, which reduces the corrosion resistance of Ti substrate. As the current density for hydrogen charging increases, the oxide anode presents more large cracks while the porosity of the oxide coating increased, which enhances the electrochemically active surface area and electrocatalytic activity of the oxide anode for chlorine evolution reaction, but lowers the electrochemical stability of the anode. When the charging current density rises to 500 mA/cm², on the contrary, the electrochemical activity of the oxide anode is decreased somewhat while the stability of the anode is improved to some extent.

Key words: titanium substrate hydrogen charging oxide anode microstructure electrochemical properties

Received: 25 December 2024 32134.14.1005.4537.2024.410

ZTFLH:

TG174

Fund: Exchange Projects at the 10th Regular Session of Scientific and Technological Cooperation Committee of China and Croatia (10-2)(10-2)

Corresponding Authors: XU Likun, E-mail: xulk@sunrui.net

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	LIU Penghe
	XUE Lili
	XU Likun
	XIN Yonglei
	GUO Mingshuai
	ZHOU Shuai
	DUAN Tigang

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https://www.jcscp.org/EN/10.11902/1005.4537.2024.410 OR https://www.jcscp.org/EN/Y2025/V45/I5/1277

Fig.1 Surface morphologies of titanium substrates with acid etching before (a, b) and after hydrogen charging for 4 h in sulfuric acid solution at the current densities of 50 (c, d), 100 (e, f), 250 (g, h) and 500 (i, j) mA/cm²

Fig.2 XRD spectra of titanium substrates with acid etching before and after hydrogen charging at different cathode current densities in sulfuric acid solution

Fig.3 Nyquist (a), Bode phase angle (b) and Bode modulus (c) diagrams of titanium substrates before and after hydrogen charging at different cathode current densities in 3.5%NaCl solution, and corresponding equivalent circuit diagram (d)

Table 1 Fitting parameters of EIS of titanium substrates uncharged and charged with hydrogen at different cathode current densities

Fig.4 Potentiodynamic polarization curves of titanium substrates uncharged and charged with hydrogen at different cathode current densities

Fig.5 Surface morphologies of RuO₂-IrO₂-TiO₂ anodes prepared on acid-etched titanium substrates uncharged (a) and charged with hydrogen at the cathode current densities 50 (b), 100 (c), 250 (d) and 500 (e) mA/cm²

Fig.6 XRD patterns of RuO₂-IrO₂-TiO₂ anodes prepared on titanium substrates uncharged and charged with hydrogen at different cathode current densities

Fig.7 Nyquist diagrams recorded in 3.5%NaCl solution at 1.20 V (vs. SCE) for RuO₂-IrO₂-TiO₂ anodes prepared on titanium substrates without and with hydrogen charging at different current densities (a), and equivalent circuit diagram (b)

Table 2 Fitting parameters of EIS of the oxide anodes on titanium substrates uncharged and charged with hydrogen at different current densities

Fig.8 Cyclic voltametric curves recorded in 3.5%NaCl solution at different scanning rates for the oxide anodes on titanium substrates uncharged (a) and charged with hydrogen at the current densities of 50 (b), 100 (c), 250 (d) and 500 (e) mA/cm², and variations of the current density at 0.7 V (vs. SCE) with scanning rate (f)

I / mA·cm^-2	q $t o t a l *$ / mC·cm^-2	q $o u t e r *$ / mC·cm^-2	q $i n n e r *$ / mC·cm^-2	ε
Uncharged	16.65	9.30	7.35	0.44
50	20.91	9.81	11.10	0.53
100	30.34	12.12	18.22	0.60
250	35.42	13.05	22.37	0.63
500	27.87	12.97	14.90	0.53

Table 3 Voltammetric charge parameters and porosities of the oxide anodes on titanium substrates uncharged and charged with hydrogen at different current densities

Table 4 Double-layer capacitances and morphological factors of the oxide anodes on titanium substrates uncharged and charged with hydrogen at different current densities

Fig.9 Potentiodynamic polarization curves measured in 3.5%NaCl solution for the oxide anodes on titanium substrates uncharged and charged with hydrogen at different current densities

Fig.10 Cell voltage vs. time curves recorded during accelerated life tests in 1 mol/L sulfuric acid solution at 1 A/cm² for the oxide anodes prepared on titanium substrates uncharged and charged with hydrogen at different current densities

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