目的 304不锈钢（304SS）双极板在质子交换膜燃料电池的酸性湿热环境下易被腐蚀破坏,从而影响燃料电池堆的稳定功率输出,在不锈钢双极板表面制备耐蚀导电涂层是解决这一问题的有效途径。方法 采用直流磁控溅射技术在304SS不锈钢表面高温沉积Cr/a-C涂层,采用SEM、EDS、XPS和拉曼光谱对Cr/a-C涂层的微观结构及组成进行表征,通过在0.1 mol/L H2SO4溶液环境中进行动/恒电位极化、电化学阻抗谱和循环伏安法评价涂层的耐腐蚀性能。结果 涂层均致密完好。在550 ℃、650 ℃、750 ℃温度下沉积涂层的腐蚀电流密度分别为3.17×10-7 A/cm2、2.87×10-7 A/cm2和1.55×10-8 A/cm2。750 ℃沉积的Cr/a-C涂层表现出最佳的耐腐蚀性能,其在0.6 V(vs.SCE)恒电位极化10 h后电流密度为2.16×10-8 A/cm2,在溶液中腐蚀1 000 h后,仍保持较高的电荷转移电阻（Rct,3.12×106 Ω/cm2）,在150次的循环伏安实验后,具有最低的峰值电流密度（1.43×10-6 A/cm2）和转移电荷量（3.76 mC/cm2）。结论 在750 ℃的高温下Cr过渡层与a-C界面处发生扩散,形成扩散结构有效减少了涂层界面缺陷,提高了涂层与基体结合力,进而提升了涂层的抗腐蚀性能。
Abstract
304 stainless steel (304SS) is a highly promising material for proton exchange membrane fuel cell bipolar plates. To enhance the corrosion resistance of 304 stainless steel bipolar plates in the cathode environment of proton exchange membrane fuel cells, a Cr/a-C coating was deposited on the surface of the 304SS substrate with direct current magnetron sputtering technology at high temperatures. The microstructure and composition of the coating were characterized through scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The corrosion resistance of the coating in the cathode corrosion environment of a proton exchange membrane fuel cell (PEMFC) was evaluated with a series of electrochemical testing methods, including dynamic polarization testing, constant potential polarization testing, impedance spectroscopy experiments, and cyclic voltammetry. The results showed that the prepared coatings had tight interface contact with no pores or voids, and were firmly bonded to the substrate. The composite coating (304SS/Cr/C-750) deposited at 750 ℃ exhibited significant interdiffusion of components between the metallic Cr layer and the amorphous carbon layer. Through Tafel fitting of the dynamic potential polarization curve, it was found that the corrosion current density of the 304SS/Cr/C-750 coating was only 1.55×10-8 A/cm2, which was four orders of magnitude lower than that of the substrate, significantly enhancing the corrosion resistance of the substrate. After 10 hours of constant potential polarization at an applied potential of 0.6 V vs. SCE, the final current density stabilized at 2.16×10-8 A/cm2, meeting the 2025 target (DOE25) set by the U.S. Department of Energy. In a 1 000-hour impedance spectroscopy experiment, the coating maintained a high charge transfer resistance (Rct) value, with the final Rct value reaching 3.12×106 Ω/cm2, which was four orders of magnitude higher than the substrate (352.1 Ω·cm2), demonstrating exceptional long-term corrosion barrier performance. The diffusion coefficient in the equivalent circuit fitting of the coating varied between 0.83 and 0.87, indicating that the coating surface did not undergo significant changes. After undergoing 150 cycles of cyclic voltammetry testing, 304SS/Cr/C-750 exhibited the lowest peak current density (1.43×10-6 A/cm2) and the lowest transferred charge quantity (3.76 mC/cm2), demonstrating its optimal electrochemical stability under dynamic operating conditions. The excellent corrosion resistance of 304SS/Cr/C-750 stems from the Cr/C interdiffusion "interlocking" structure formed at 750 ℃: it significantly enhances the interfacial bonding strength between the coating and the substrate and drastically reduces porosity, effectively blocking the penetration pathways of corrosive media (H+, SO42-, etc.). Additionally, the high sp³ carbon content enhances the hardness and chemical inertness of the coating, while the low porosity and dense structure significantly impede ion and electron transport, thereby increasing membrane resistance. As a result, the coating maintains stable passivation in harsh acidic environments, effectively protecting the 304SS substrate from corrosion. In a simulated PEMFC cathode environment, the coating exhibits extremely low corrosion rates, excellent passivation stability, outstanding long-term impedance characteristics, and good dynamic load durability, fully meeting the application requirements for high-performance PEMFC bipolar plates.
关键词
质子交换膜燃料电池 /
金属双极板 /
磁控溅射 /
非晶碳涂层 /
电化学测试 /
腐蚀性能
Key words
PEMFC /
metal bipolar plate /
magnetron sputtering /
amorphous carbon coating /
electrochemical testing /
corrosion resistance
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基金
国家自然科学基金（52171066, 52175129）
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