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模拟PEMFC环境下纳米晶ZrC涂层钛合金双极板的性能研究
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南京航空航天大学材料科学与技术学院,Nanjing University of Aeronautics and Astronautics

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TM911.4

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国家自然科学基金(51374130)和航空科学基金(2013ZE52058)资助项目


The Properties of ZrC Nanocrystalline Coating Prepared on Ti Alloy Bipolar Plates in Simulated PEMFC Environments
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School of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics,

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    摘要:

    本文采用双阴极等离子溅射沉积技术,在Ti-6A1-4V合金双极板表面制备了纳米晶ZrC涂层。通过多种实验表征手段(包括X射线衍射仪(XRD),扫描电子显微镜(SEM)和透射电镜(TEM)对该涂层的微观组织特征进行观察与分析。采用电化学工作站对比研究了改性前后钛合金双极板在不同温度下模拟质子交换膜燃料电池(PEMFC)环境中(0.5 mol L-1 H2SO4 2 mg L-1 HF)的耐腐蚀性能。此外,通过测量了钛合金双极板改性前后的接触角和接触电阻,研究纳米晶ZrC涂层对Ti-6A1-4V合金双极板的疏水性能和导电性能的影响。结果表明:所制备涂层的外层呈柱状结构的、其平均晶粒尺寸为12 nm的纳米晶ZrC沉积层,内层为沉积层与钛合金基体间互扩散所形成的扩散层。在模拟PEMFC阴/阳极环境中,纳米晶ZrC涂层动电位极化曲线的腐蚀电位明显高于Ti-6A1-4V合金,其腐蚀电流密度较Ti-6A1-4V合金下降了约4个数量级。恒电位极化曲线表明,在 0.6 V阴极工作电极电位下,纳米晶ZrC涂层具有较快的成膜速率以及较高的钝化膜稳定性;而在-0.1 V阳极工作电极电位下,纳米晶ZrC涂层则呈现出阴极保护特征。在PEMFC工作温度范围内,开路电位和电化学阻抗谱测试结果表明:随着溶液温度的升高,双极板材料的耐腐蚀性能逐渐降低。且纳米晶ZrC涂层的温度腐蚀敏感性明显小于Ti-6A1-4V合金。此外,纳米晶ZrC涂层显著降低了Ti-6A1-4V合金的表面能和界面接触电阻,提高了Ti-6A1-4V合金的表面疏水性能和导电性能。Ti-6A1-4V合金双极板改性前后表面接触角分别为92.8 °、58.8 °。且1.4 MPa的压紧力下,纳米晶ZrC涂层和Ti-6A1-4V合金的界面接触电阻分别为12 mΩ/cm-2、87 mΩ/cm-2。

    Abstract:

    In the present study, ZrC nanocrystalline coating was synthesized on Ti-6A1-4V alloy as bipolar plates for PEMFC by a double glow discharge plasma technique. The microstructure of as-prepared ZrC coating was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). Electrochemical measurements were carried out on a CHI604D electrochemical workstation in the simulated PEMFC anodic and cathodic environments. The hydrophilicity and interfacial contact resistance of the ZrC nanocrystalline coating were also evaluated. The microstructure of as-prepared ZrC coating consists of deposited layer and diffusion layer. The 10 μm thick deposited layer shows a dense columnar microstructure, composed of equiaxed grains with an average grain size of ~12 nm, whereas the 4 μm thick diffusion layer with the gradient distribution of alloying elements offers a smooth transition of mechanical properties, which is beneficial to improve the adhesion strength of the ZrC coating on the Ti-6A1-4V substrate. The Ecorr of the as-deposited ZrC nanocrystalline coating is obviously higher than that of Ti-6A1-4V alloy in a simuiated PEMFC environment. At applied cathode ( 0.6 V) potential for PEMFC, ZrC nanocrystalline coating is in passive region, and the passive current density is four orders of magnitude lower than that of Ti-6A1-4V alloy. At applied anode (-0.1 V) potentia, ZrC nanocrystalline coating exhibits the characteristic of cathodic protection. The results of OCP and EIS showed that the higher the temperature, the worse the corrosion resistance of bipolar plates. And the temperature corrosion susceptibility of ZrC nanocrystalline coating is obviously lower than Ti-6A1-4V alloy. Moreover, ZrC nanocrystalline coating can effectively improve conductivity and hydrophobic nature of Ti-6A1-4V alloy bipolar plate.

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钱阳,徐江.模拟PEMFC环境下纳米晶ZrC涂层钛合金双极板的性能研究[J].稀有金属材料与工程,2017,46(4):1033~1042.[QIAN Yang, Xu Jiang. The Properties of ZrC Nanocrystalline Coating Prepared on Ti Alloy Bipolar Plates in Simulated PEMFC Environments[J]. Rare Metal Materials and Engineering,2017,46(4):1033~1042.]
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  • 收稿日期:2014-12-14
  • 最后修改日期:2015-03-18
  • 录用日期:2015-06-11
  • 在线发布日期: 2017-08-04
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