李荣斌,黄从发,周滔,张如林.氮气流量对VNbMoTaWNx薄膜作为PEMFC不锈钢双极板改性层性能的影响[J].表面技术,2024,53(6):90-98.
LI Rongbin,HUANG Congfa,ZHOU Tao,ZHANG Rulin.Effect of Nitrogen Flow Rate on the Performance of VNbMoTaWNx Film as Modified Layer of Stainless Steel Bipolar Plates for PEMFC[J].Surface Technology,2024,53(6):90-98
氮气流量对VNbMoTaWNx薄膜作为PEMFC不锈钢双极板改性层性能的影响
Effect of Nitrogen Flow Rate on the Performance of VNbMoTaWNx Film as Modified Layer of Stainless Steel Bipolar Plates for PEMFC
投稿时间:2023-03-24  修订日期:2023-05-10
DOI:10.16490/j.cnki.issn.1001-3660.2024.06.008
中文关键词:  质子交换膜燃料电池  双极板  高熵合金薄膜  耐腐蚀性  接触电阻
英文关键词:proton exchange membrane fuel cell  bipolar plates  high entropy alloy films  corrosion resistance  contact resistance
基金项目:上海市地方院校能力建设项目(21010500900);国家自然科学基金联合基金重点项目(U23A20607)
作者单位
李荣斌 上海理工大学 材料与化学学院,上海 200093;上海电机学院 材料学院,上海 201306 
黄从发 上海理工大学 材料与化学学院,上海 200093 
周滔 上海电机学院 材料学院,上海 201306 
张如林 上海电机学院 材料学院,上海 201306 
AuthorInstitution
LI Rongbin School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China;School of Materials, Shanghai Dianji University, Shanghai 201306, China 
HUANG Congfa School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China 
ZHOU Tao School of Materials, Shanghai Dianji University, Shanghai 201306, China 
ZHANG Rulin School of Materials, Shanghai Dianji University, Shanghai 201306, China 
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中文摘要:
      目的 降低SS316L表面的接触电阻,提高耐腐蚀性能。方法 采用非平衡场磁控溅射离子镀技术在SS316L不锈钢表面制备VNbMoTaW和不同氮气流量的VNbMoTaWNx薄膜。使用场发射扫描电镜、XRD衍射仪、XPS光电子能谱仪、电化学工作站、接触电阻测试装置,研究了改性涂层的组成和结构对接触电阻和耐腐蚀性能的影响。结果 扫描电子显微镜结果表明,所有薄膜表面致密且连续、与基体结合良好。随着氮气流量的增加,氮化物相逐渐增多、柱状晶结构减少、薄膜更加致密紧凑。XRD结果表明,未通氮气的高熵合金薄膜具有高熵合金体心立方结构,并沿(110)晶面方向生长。随着氮气流量的增加,氮化物相逐渐增多,薄膜晶体结构开始从体心立方结构转变为面心立方结构。结合XPS分析结果可知,VNbMoTaWNx薄膜表面主要由金属氮化物和少量高熵合金BCC相组成,并且随着氮气流量的增加,金属氮化物相逐渐增多。与单层VNbMoTaW薄膜相比,VNbMoTaWNx薄膜具有更好的耐腐蚀性和导电性能。氮流量为12 mL/min的高熵合金氮化物薄膜具有最优异的综合性能。表面改性后的薄膜接触电阻大幅度降低,在1.4 MPa的压力下,与碳纸的接触电阻仅为12.2 mΩ.cm2,接近美国能源部(DOE)的技术目标。由动电位极化曲线测得VNbMoTaWNx-12 mL/min在模拟PEMFC阴极环境下的腐蚀电流密度为0.040 μA/cm2,与SS316L基体相比,薄膜的耐腐蚀性得到了很大提升。在0.6 V恒电位模拟阴极环境下,VNbMoTaWNx-12 mL/min的电流密度稳定在1.01 μA/cm2,接近美国能源部1 μA/cm2的目标。结论 VNbMoTaW和不同氮气流量的VNbMoTaWNx薄膜能显著提高SS316L基体的耐腐蚀性和导电性能。
英文摘要:
      The work aims to reduce the contact resistance on the surface of SS316L and improve its corrosion resistance. VNbMoTaW and VNbMoTaWNx films with different nitrogen flow rates were prepared on SS316L stainless steel by closed field unbalanced magnetron sputter ion plating. The field-emission scanning electron microscopy, XRD diffractometer, XPS photoelectron spectroscopy, electrochemical workstation, and contact resistance testing device were used to study the effects of modified layer composition and structure on contact resistance and corrosion resistance. The scanning electron microscopy results showed that all film surfaces were dense and continuous, with good adhesion to the substrate. With the increase of nitrogen flow rate, the columnar crystal structure decreased, and the film became more dense and compact. The XRD results indicated that the high entropy alloy film without nitrogen flow rate had a high entropy alloy body centered cubic structure and grew along the (110) crystal plane direction. With the increase of nitrogen flow rate, the nitride phase gradually increased, and the film crystal structure began to transition from a body centered cubic structure to a face centered cubic structure. Combined with XPS analysis, the surface of VNbMoTaWNx film was mainly composed of metal nitrides and a small amount of high entropy alloy BCC phase, and with the increase of nitrogen flow rate, the metal nitrides phase gradually increased. Compared to single-layer VNbMoTaW films, VNbMoTaWNx films had better corrosion resistance and conductivity. The high entropy alloy nitride film with a nitrogen flow rate of 12 mL/min had the most excellent comprehensive performance. The contact resistance of the film after surface modification was greatly reduced. Under the pressure of 1.4 MPa, the contact resistance with carbon paper was only 12.2 mΩ.cm2, which was close to the technical goal of the United States Department of Energy (DOE). Under the simulated PEMFC environment, the corrosion current density of VNbMoTaWNx-12 mL/min in the cathode environment was 0.040 μA/cm2 measured by the potentiodynamic polarization curve. Compared to the SS316L substrate, the corrosion resistance of the film was greatly improved. Under a 0.6 V constant potential simulated cathode environment, the current density of VNbMoTaWNx-12 mL/min remained stable at 1.01 μA/cm2, close to the goal of 1 μA/cm2 of the United States Department of Energy. Both VNbMoTaW and VNbMoTaWNx films with different nitrogen flow rates can significantly improve the corrosion resistance and conductivity of SS316L substrate.
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