改性316L不锈钢表面聚苯胺的制备及电化学性能

doi:10.7503/cjcu20160432

摘要/Abstract

摘要：

采用原位氧化技术调整316L不锈钢(SS316L)基体元素Cr和Ni在界面的浓度和分布, 形成了Ni和Cr富集改性界面. 应用计时电位技术, 通过Cr和Ni改性层催化草酸溶液中的苯胺单体在其表面吸附并聚合, 在SS316L表面沉积了附着力良好的聚苯胺(PANI)膜. 与SS316L相比, 表面富Ni-Cr的SS316L在涂覆PANI膜后, 在80 ℃ 0.5 mol/L H₂SO₄+5 mg/L F^-溶液中阳极和阴极的腐蚀电位分别提高470和500 mV, 维钝电流均下降2~3个数量级; 在模拟质子交换膜燃料电池运行环境中, 经36000 s恒电位极化, 其阳极和阴极的腐蚀电流分别下降约1和2个数量级, 腐蚀速度分别约为6~9 和< 5 μA/cm²; 在1.4 MPa压力下, 聚苯胺膜层与Toray 060碳纸间接触电阻下降约250 mΩ·cm². SS316L表面形成富Ni-Cr改性层并涂覆聚苯胺膜后, 其耐蚀性和导电性均明显优于原始SS316L, 这主要取决于富Ni-Cr改性层的结构、组成和聚苯胺膜的厚度.

关键词: Ni-Cr改性层, 质子交换膜燃料电池, 不锈钢, 聚苯胺, 双极板

Abstract:

Ni-Cr enrichment on stainless steel 316L(SS316L) was achieved by adjusting the concentration and distribution of Cr and Ni on the surface of the SS316L substrate through in situ oxidation processes. Aniline monomers were absorbed and polymerized on the surface of modified SS316L, and a polyaniline(PANI)/Ni-Cr enriched SS316L composite was prepared using chronopotentiometry(CP) technique. Under both reducing(anode simulated) and oxidizing(cathode simulated) conditions of proton exchange membrane fuel cell(PEMFC), the results of potentiodynamic test showed that the PANI coating increased the free corrosion potential of the steel by more than 470 and 500 mV, respectively, with a passivation current density more than 2—3 orders of magnitude lower than that of the bare steel. Under the PEMFC environment, the corrosion currents of the anode and cathod of PANI/Ni-Cr enriched SS316L electrode were decreased by 1 and 2 orders of magnitude, and corrosion rates of the anode and cathode were about 6—9 μA/cm² and <5 μA/cm², respectively. Furthermore, the interface contact resistance between the PANI film and carbon paper was reduced by about 250.0 mΩ·cm² at a compaction pressure of 1.4 MPa. Polyaniline/Ni-Cr enriched SS316L bipolar plate was remarkably more stable in simulated PEMFC environments, and more conducting compared to the bare SS316L.

Key words: Ni-Cr modified layer, Proton exchange membrane fuel cell, Stainless steel, Polyaniline, Bipolar plate

TrendMD:

刘明, 田颖, 傅杰, 徐洪峰. 改性316L不锈钢表面聚苯胺的制备及电化学性能. 高等学校化学学报, 2016, 37(12): 2228.

LIU Ming, TIAN Ying, FU Jie, XU Hongfeng. Preparation and Electrochemical Performance of Polyaniline Film Formed on Acid-activated Stainless Steel 316L^†. Chem. J. Chinese Universities, 2016, 37(12): 2228.

图/表 8

Fig.1 SEM images of the surface of SS316L before(A) and after(B) being activated for 6 h in 0.5 mol/L H2SO4 at 80 ℃.

Fig.2 XRD patterns of SS316L before(A) and after(B) being activated for 6 h in 0.5 mol/L H2SO4 at 80 ℃

Fig.3 EDS spectra and data of SS316L after being activated for 6 h in 0.5 mol/L H2SO4 at 80 ℃

Fig.4 Top-view SEM image of PANI seeds layer(A), top-view(B) and cross-section-view(C) SEM images of PANI coating after secondary growth and the corresponding EDS spectra and data(D, E) (D) Black region in Fig.(B); (E) white sphere region in Fig.(B).

Fig.5 FTIR spectrum of PANI doped with anions derived from oxalic acid

Fig.6 Anodic(A) and cathodic(B) polarization curves for the three samples in 0.5 mol/LH2SO4+5 mg/L F- at 80 ℃ (A) Bubbled with H2, the arrow corresponds to the anode potential in a PEMFC; (B) bubbled with air, the arrow corresponds to the cathode potential in a PEMFC.

Fig.7 Potentiostatic anodic(A) and cathodic(B) polarization curves for untreated SS316L(a) and PANI coated SS316L(b) at -0.1 V(vs. SCE) purged with H2(A) and at 0.6 V(vs. SCE) purged with air(B)

Fig.8 Interfacial contact resistances at different compaction forces a. Untreated SS316L; b. acid activated SS316L; c. PANI coated SS316L.

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