赫亮亮,张香云,刘太楷,谢迎春,褚欣.基于形貌控制的多孔涂层沉积机制及其碱式电解水性能研究[J].表面技术,2024,53(24):206-215.
HE Liangliang,ZHANG Xiangyun,LIU Taikai,XIE Yingchun,CHU Xin.Deposition Mechanism of Porous Coatings and Its Alkaline Water Electrolysis Performance Based on Morphology Control[J].Surface Technology,2024,53(24):206-215 |
| 基于形貌控制的多孔涂层沉积机制及其碱式电解水性能研究 |
| Deposition Mechanism of Porous Coatings and Its Alkaline Water Electrolysis Performance Based on Morphology Control |
| 投稿时间：2023-12-21 修订日期：2024-05-25 |
| DOI：10.16490/j.cnki.issn.1001-3660.2024.24.019 |
| 中文关键词: 电解水 冷喷涂 造孔剂 NiAl 多孔电极 电化学阻抗谱 |
| 英文关键词:water electrolysis cold spraying pore former NiAl porous electrode electrochemical impedance spectroscopy |
| 基金项目:冷喷涂先进功能涂层专项资金项目(2020B0101330001);航空发动机及燃气轮机基础科学中心项目(P2022-B-IV-011-001);广东省科学院发展专项资金项目(2022GDASZH-2022010203-003);中法政府间科技合作项目国家重点研发计划(2023YFE0108000);广东特支计划项目(2019BT02C629);国家自然科学基金(52061024);兰州理工大学红柳优秀青年人才支持计划(52161027) |
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| Author | Institution |
| HE Liangliang | School of Materials Science and Engineering, Lanzhou University of Science and Technology, Lanzhou 730050, China;National Engineering Laboratory of Surface Engineering Technology for Modern Materials, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510650, China |
| ZHANG Xiangyun | School of Materials Science and Engineering, Lanzhou University of Science and Technology, Lanzhou 730050, China |
| LIU Taikai | National Engineering Laboratory of Surface Engineering Technology for Modern Materials, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510650, China |
| XIE Yingchun | National Engineering Laboratory of Surface Engineering Technology for Modern Materials, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510650, China |
| CHU Xin | National Engineering Laboratory of Surface Engineering Technology for Modern Materials, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510650, China |
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| 中文摘要: |
| 目的 探索冷喷涂工艺中造孔剂形貌对涂层沉积机制、多孔镍电极结构和电解水析氢性能的影响。方法 采用冷喷涂工艺将不同形貌的造孔剂粉末沉积为涂层，经化学腐蚀造孔后，得到可供测试的多孔镍电极。通过SEM/EDS、XPS、XRD对样品微观形貌、元素价态等物性进行表征，并通过线性扫描伏安法(LSV)、循环扫描伏安法(CV)和电化学阻抗谱(EIS)等电化学方法研究样品的析氢性能。结果 由于片状Al粉末在喷涂过程中受气体影响较大，不易沉积在涂层中;因此球形Al造孔效果明显优于片状Al，得到的涂层孔隙更多，比表面积更大，表现出更优异的电解性能，同时两组样品析氢反应步骤都是Heyrovsky步骤。在电流密度为100 mA/cm2和250 mA/cm2时，NsA样品的过电位分别为0.32 V和0.42 V，而NfA样品的过电位则分别为0.4 V和0.5 V。结论 球形Al表面氧化物的阻抗和孔隙度的阻抗要小于片状Al，电荷转移能力明显较强，双电层的电容有所增加，显示出较大的活性表面积。因此，球形Al造孔效果明显优于片状Al，所得到的涂层电解析氢性能更强。 |
| 英文摘要: |
| The work aims to explore the effect of pore former morphologies on the deposition mechanism of Ni coatings, structures of porous Ni electrodes and hydrogen evolution performance of alkaline water electrolysis. By applying cold spraying technology, Ni powder and Al powder (the pore former) were deposited on perforated Ni sheets to obtain coatings. The obtained coatings were chemically etched to remove the pore former, then leaving numerous pores in the coatings which were used for further test. By performing SEM/EDS, XPS, XRD, the micro morphology, element state and other properties were characterized and analyzed. Furthermore, LSV, CV, EIS tests were carried out to estimate the HER performance of the obtain porous coatings. Nickel powder and aluminum powder were blended in a volume ratio of 3∶1. Coatings obtained with special Al powder were noted as NsA, and coatings prepared with flake Al powder were marked as NfA. Both NsA and NfA were immersed in a 30wt% KOH solution at room temperature for 24 h to successfully obtain two groups of porous coatings. The morphology of the coating before and after corrosion was analyzed by scanning electron microscopy (SEM). The valence state of elements and phase composition of the coatings were analyzed by EDS, XPS and XRD. The hydrogen evolution performance of the samples was studied through electrochemical tests including linear sweep voltammetry (LSV), cyclic sweep voltammetry, and electrochemical impedance spectroscopy (EIS), etc. The results showed that since the flake Al particles were greatly affected by spray gas, the flight state was extremely unstable, and only a small amount of flake Al powder was deposited as coating. Meanwhile, the spherical Al particle was able to maintain a stable flight state and achieve a high enough velocity to form coating upon the substrate. Consequently, the Al content of the sprayed coatings was high, resulting in more pores and larger specific surface area than that of the flake one. Therefore, the pore forming effect of spherical Al was significantly better than that of flaky Al. At the same time, the hydrogen evolution reaction of both coatings was dominated by the Herovsky step. At current densities of −100 mA/cm2 and −250 mA/cm2, the HER overpotentials of NsA samples were 0.32 V and 0.42 V, respectively, while the overpotentials of NfA samples were 0.4 V and 0.5 V, respectively. The maximum phase angle of sample NsA was 24°, and its corresponding characteristic frequency was 50 Hz. The maximum phase angle of the sample NfA was 30°, and its corresponding characteristic frequency was 1 000 Hz. Therefore, the surface of NfA coatings was rougher and more porous than that of NsA coatings. The difference in electrolysis performance between NsA and NfA samples mainly came from their difference of microstructure. The flake powder resulted in smaller and less pores in the coatings while the spherical powder caused more and larger pores to the coating, assuring sufficient contact between the catalyst and the electrolyte. Therefore, it can be considered that the pore forming effect of spherical Al is significantly better than that of flake Al, and the resulting coating has better electrochemical hydrogen evolution performance. |
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