钛基氧化铱电极电沉积制备技术研究进展

doi:10.13208/j.electrochem.200802

摘要/Abstract

摘要：

钛基氧化铱电极作为DSA(dimension stable anode)中的典型电极,广泛应用于各个领域。目前工业生产的钛基氧化铱电极主要由传统热分解法制备,存在成本高昂,工艺繁琐,依赖人工劳动,无法大规模生产等问题,十分有必要探索开发新的制备技术。本文从沉积液配方、基底材料的选择及处理、电沉积方式以及沉积时间等方面系统地讨论了氧化铱电沉积制备技术的研究进展,包括作者课题组所作的一些工作及成果;分析了钛基氧化铱电极电沉积制备技术目前所面临的挑战,并给出一定建议;阐述了其应用前景,展望了其未来发展方向,希望更多的科研人员能投入到相关研究中。

关键词: 钛基氧化铱电极, 电沉积, 工业应用

Abstract:

Titanium-based iridium oxide electrode has been widely used in various fields, such as electrocatalytic oxidation, biomedical applications, hydrometallurgical metal recovery, electro-osmotic dewatering, etc. At present, it is mainly prepared by traditional thermal decomposition method, however, which has high cost, cumbersome process, mainly relying on manual labor and cannot be mass-produced yet. It is, therefore, urgently necessary to explore new preparation technologies by focusing on electrodeposition technology, with technological characteristics such as eco-friendly and sustainable development. This article systematically discusses the research progress in iridium oxide electrodeposition preparation technology from the aspects of deposition solution formulation, base material selection and treatment, electrodeposition method and deposition time, etc. Some works and achievements, made by the author's research group, such as a new electrodeposition recipe of titanium-based iridium oxide electrode and the pretreatment of titanium with anodic oxidation for improving the stability of electrodeposited IrO₂ electrode are also presented. The current challenges faced by the electrodeposition preparation technology of titanium-based iridium oxide electrode, including bad coating quality, weak bonding ability between coating and substrate, lack of the study on the theory about dynamic of electrodeposition and the problem of industrial applications are analyzed. Based upon the aforementioned challenges, some suggestions, for example, utilizing optimization of the electrodeposition, multi-deposition process combination, metal (such as tantalum, lanthanum) co-deposition, are given to solve for the problem of coating quality. The process of electrodeposition by utilizing in-situ electrochemical methods, and combined with COMSOL and other software to simulate the process, and then starting from both electrochemical theory and crystal growth theory, as well as the gradually perfect the theoretical research on electrodeposition of iridium oxide on titanium are summarized. Finally, the application prospects and future development directions are highlighted. It is expected that this brief review would offer critical insights and useful guidelines for developing superior electrodeposition technology of titanium-based iridium oxide electrode.

Key words: IrO₂/Ti electrodes, electrodeposition, industrial applications

吴丹丹, 吴旭. 钛基氧化铱电极电沉积制备技术研究进展[J]. 电化学（中英文）, 2021, 27(1): 35-44.

Dan-Dan Wu, Xu Wu. Research Progress in Electrodeposition Technology of Titanium-Based Iridium Oxide Electrode[J]. Journal of Electrochemistry, 2021, 27(1): 35-44.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200802

https://electrochem.xmu.edu.cn/CN/Y2021/V27/I1/35

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Technology	Introduction	Characteristics
Thermal decomposition	Iridium-containing coating solution is coated on the pretreated titanium substrate by brushing, and then cementation so repeated.	Simple and widely applicated Process is cumbersome, and need manual labour
Sol-gel method	The compound containing high chemically active components is solidified by solution, sol, gel, and then heat-treated to form oxide or other compound solids.	Scale is uniform and crystal grains are fine Preparation process is complicated and raw materials are expensive and harmful.
Magnetron sputtering	Bombarding the target surface with energetic particles in a vacuum to deposit the bombarded particles on the substrate.	Deposition speed is fast, no impurities remain; Process and devices are complicated and high cost.
Laser pulse deposition	A laser is used to bombard an object, and then the bombarded material is deposited on a certain substrate to obtain a thin film or a deposited layer.	Deposition rate is high. The large area can be deposited Film formation is not suitable, and high cost
Electrodeposition	Iridium-containing metal salt ion undergoes oxidation or reduction reaction to deposit on the titanium substrate.	Coating has high cleanliness and homogeneity, high degree of mechanization, and process flow is simple.

Author	Composition of deposition solution	Instruction	Deposition Mechanism
Baur^[18]	IrCl₄、C₂H₅OH、HCl、NaOH	C₂H₅OH： reduction;NaOH：regulate pH	IrCl₄^2-+ C₂H₅OH → Ir(OH₂)₂Cl^- Ir(OH₂)₂Cl^- → Ir₂O₃·xH₂O
Toniolo^[20]	IrCl₄·xH₂O、H₂O₂(30wt.%) Oxalic acid、K₂CO₃	H₂C₂O₄： As complex; K₂CO₃： regulate pH; H₂O₂： improve deposition efficiency	[Ir(C₂O₄) (OH)₄]^2- →IrO₂ + 2CO₂ + 2H₂O + 2e^-
Michel^[21]	IrCl₃、Oxalic acid、K₂CO₃	H₂C₂O₄： As complex; K₂CO₃： regulate pH;	[Ir(C₂O₄) (OH)₄]^3- →[Ir(C₂O₄) (OH)₄]^2- + e^- [Ir(C₂O₄) (OH)₄]^2- → IrO₂ + 2H₂O + 2CO₂ + e^-
Zhang Xing^[22]	(NH₄)₂IrCl₆ (10g/L) Boric acid (40g/L) Sodium malonate	Boric acid： As solvent; Sodium malonate： Improving Stabilization	-

Deposition recipes	Deposition condition
The molo ratio of oxalate and IrCl₃ is 5:1	Potentiostatic techniques: 0.8 V
Adjust pH to 10.2 with K₂CO₃	Temperature: Ambient
Iridium ion concentration: 4 mmol·L^-1	Stirring: Magnetic
The solution was kept at 40 ℃ for 4 d to allow stabilization.	Atmosphere: Air
	Deposition time: 30 min