用于燃料电池双极板的不锈钢成分优化

doi:10.11900/0412.1961.2020.00131

金属学报

2021, Vol. 57

Issue (5): 651-664 DOI: 10.11900/0412.1961.2020.00131

研究论文

本期目录 | 过刊浏览

用于燃料电池双极板的不锈钢成分优化

黄一川¹, 王清¹, 张爽², 董闯¹^,²(

), 吴爱民¹, 林国强¹

^1.大连理工大学三束材料改性教育部重点实验室大连 116024
^2.大连交通大学材料科学与工程学院大连 116028

Optimization of Stainless Steel Composition for Fuel Cell Bipolar Plates

HUANG Yichuan¹, WANG Qing¹, ZHANG Shuang², DONG Chuang¹^,²(

), WU Aimin¹, LIN Guoqiang¹

^1.Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024, China
^2.School of Materials Science and Engineering, Dalian Jiaotong University, Dalian 116028, China

引用本文:

黄一川, 王清, 张爽, 董闯, 吴爱民, 林国强. 用于燃料电池双极板的不锈钢成分优化[J]. 金属学报, 2021, 57(5): 651-664.
Yichuan HUANG, Qing WANG, Shuang ZHANG, Chuang DONG, Aimin WU, Guoqiang LIN. Optimization of Stainless Steel Composition for Fuel Cell Bipolar Plates[J]. Acta Metall Sin, 2021, 57(5): 651-664.

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摘要:

利用团簇式方法，通过对Fe-Cr-Ni合金进行成分精修，在保持合金良好耐蚀性的同时，提升不锈钢的导电性。首先，解析316L不锈钢的成分，获得其Fe-Cr-Ni基础成分的理想团簇式[Ni-Fe₁₁Ni₁]Cr₃，进而，固定Cr₃，将Ni含量(质量分数)从6.63%变到32.74%，得到符合团簇成分通式[Ni-Fe_13-_xNi_x_-1]Cr₃ = Fe_13-_xNi_xCr₃ (x = 1~5)的合金成分。利用真空电弧熔炼并铜模浇注成直径10 mm试棒，随后进行固溶及水淬处理。实验结果表明，在模拟双极板服役环境(0.5 mol/L H₂SO₄ + 2 × 10^-6 HF)下，随着Ni含量提高，在酸钝化后，自腐蚀电流密度由14.39 μA/cm²降低至1.10 μA/cm²，在电化学氮化后，由1.03 μA/cm²降低至0.29 μA/cm²。这些数据均优于参照合金316L不锈钢(分别为7.51和0.47 μA/cm²)，甚至低于0.5 μA/cm²的目前产业目标。在0.064 MPa压力下接触电阻逐渐减小(酸钝化后，从1.16 Ω·cm²减至0.98 Ω·cm²，电化学氮化后，从1.07 Ω·cm²减至1.03 Ω·cm²)，优于316L不锈钢的1.1 Ω·cm²。上述实验结果表明，Ni含量的持续添加能够提升合金作为双极板的使役性能，最佳的不锈钢成分配方为 [Ni-Fe₁₀Ni₂]Cr₃，可以作为替代316L的新型不锈钢。电化学氮化处理方法在提升合金耐蚀性的同时，保持了相当高的接触电阻，是较好的不锈钢双极板表面处理方法。

关键词 ：不锈钢, 双极板, 酸钝化, 电化学氮化, 耐蚀性, 界面接触电阻, 钝化膜

Abstract：

316 stainless steel is the first choice for bipolar plate material in fuel cells; however, it suffers from passivation-induced corrosion and conductivity deficiencies. In this work, Fe-Cr-Ni alloy was refined using the cluster-plus-glue-atom model to obtain stainless steels with balanced corrosion and electrical performances. For austenite 316L stainless steel, the unit is described as a 16-atom cluster formula [Ni-Fe₁₁Ni₁]Cr₃. By fixing the three atoms of a glue, Cr₃ is required to achieve sufficient corrosion resistance, and new compositions with varying Ni contents are designed following [Ni-Fe_13-_xNi_x_-1]Cr₃ = Fe_13-_xNi_xCr₃ (x = 1-5). The designed alloys were arc melted at least five times, copper-mold suction casted into 10-mm cylindrical rods under an argon atmosphere, homogenized at 1150^oC for 2 h, and water quenched. Under the simulated bipolar plate service environment (0.5 mol/L H₂SO₄ + 2 × 10^-6 HF aqueous solution), as the Ni content increases, the self-corrosion current density decreases to 1.10 and 0.29 μA/cm² after acid passivation and electrochemical nitridation, respectively. These values are well below compared to the commercial 316L stainless steel (7.51 and 0.47 μA/cm²) and close to the current industry target (0.5 μA/cm²) for bipolar plates. At the same time, the contact electrical resistance (under 0.064 MPa pressure) decreases to 0.98 and 1.03 Ω·cm² after acid passivation and electrochemical nitridation, respectively, which is superior to the 316L stainless steel (1.1 Ω·cm²). Thus, optimal alloy composition [Ni-Fe₁₀Ni₂]Cr₃ can be used as the right substrate material of the bipolar plate instead of the 316L stainless steel. The electrochemical nitridation method is the proper surface treatment method for stainless steel bipolar plates, and this method improves the alloy's corrosion resistance while maintaining the same level of contact resistance.

Key words： stainless steel bipolar plate acid passivation electrochemical nitridation corrosion resistance interfacial contact resistance passivation film

收稿日期: 2020-04-27

ZTFLH:

TM911.4

基金资助:国家重点研发计划项目(2016YFB0701401)

作者简介: 黄一川，男，1996年生，硕士生

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图1 奥氏体相结构中的立方八面体团簇构型

表1 基于团簇式[Ni-Fe13-xNix-1]Cr3设计的不锈钢成分，以及参照合金316L的成分式及团簇式 (mass fraction / %)

图2 Schaeffler组织图及本工作涉及的合金位置

图3 经固溶加水淬处理后设计合金的XRD谱

图4 [Ni-Fe13-xNix-1]Cr3合金经固溶加水淬处理后显微组织的OM像(a) [Ni-Fe12]Cr3 (b) [Ni-Fe11.5Ni0.5]Cr3 (c) [Ni-Fe11Ni]Cr3 (d) [Ni-Fe10.5Ni1.5]Cr3(e) [Ni-Fe10Ni2]Cr3 (f) [Ni-Fe9Ni3]Cr3 (g) [Ni-Fe8Ni4]Cr3

图5 设计合金及316L不锈钢的硬度随Ni当量的变化情况

图6 钝化处理前后的设计合金及参照合金开路电位-时间曲线

图7 设计合金与316L不锈钢经酸钝化处理前后在0.5 mol/L H2SO4 + 2 × 10-6 HF水溶液中的动电位极化曲线

表2 酸钝化处理前后合金的自腐蚀电位(Ecorr)和自腐蚀电流密度(icorr)

图8 合金酸钝化处理后的自腐蚀电位与自腐蚀电流密度随Ni当量的变化情况

图9 酸钝化后合金的Mott-Schottky曲线

图10 酸钝化后载流子浓度随Ni当量的变化情况

表3 酸钝化后设计合金的载流子浓度(施主和受主载流子浓度Nd和Na分别拟合自图9的②和③区)

表4 酸钝化后合金的空间电荷层厚度(δsc)

图11 电化学氮化前后合金开路电位-时间曲线

图12 设计合金与316L不锈钢经电化学氮化处理前后在0.5 mol/L H2SO4 + 2 × 10-6 HF水溶液中的动电位极化曲线

表5 电化学氮化前后合金的自腐蚀电位和自腐蚀电流密度

图13 电化学氮化处理后合金的自腐蚀电位与自腐蚀电流密度随Ni当量的变化情况

图14 电化学氮化后合金的Mott-Schottky曲线

表6 电化学氮化后合金的载流子浓度

表7 电化学氮化后合金空间电荷层厚度

表8 酸钝化和电化学氮化后设计合金的界面接触电阻

图15 酸钝化后设计合金界面接触电阻随Ni当量的变化情况

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