杨佳宇,周婉秋,刘晓安,辛士刚,康艳红,孙秋菊.阳极反应气氛氢气对聚苯胺/不锈钢耐蚀性的影响[J].表面技术,2022,51(2):295-305.
YANG Jia-yu,ZHOU Wan-qiu,LIU Xiao-an,XIN Shi-gang,KANG Yan-hong,SUN Qiu-ju.Effects of Hydrogen of Anode Reaction Atmosphere on Corrosion Resistance of Polyaniline/Stainless Steel[J].Surface Technology,2022,51(2):295-305 |
| 阳极反应气氛氢气对聚苯胺/不锈钢耐蚀性的影响 |
| Effects of Hydrogen of Anode Reaction Atmosphere on Corrosion Resistance of Polyaniline/Stainless Steel |
| 投稿时间：2020-12-04 修订日期：2021-08-30 |
| DOI：10.16490/j.cnki.issn.1001-3660.2022.02.029 |
| 中文关键词: 聚苯胺 不锈钢双极板 离子液体 循环伏安 氢气 耐蚀性 |
| 英文关键词:polyaniline stainless steel bipolar plate ionic liquid cyclic voltammetry hydrogen corrosion resistance |
| 基金项目:辽宁省教育厅重点实验室基础研究项目(LZ2015066) |
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| Author | Institution |
| YANG Jia-yu | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
| ZHOU Wan-qiu | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
| LIU Xiao-an | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
| XIN Shi-gang | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
| KANG Yan-hong | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
| SUN Qiu-ju | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
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| 中文摘要: |
| 目的 为了提高双极板在质子交换膜燃料电池(PEMFC)工作环境下的耐蚀性。方法 在1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM][DEP])离子液体中，在316 L不锈钢(SS)基体上电聚合聚苯胺(PANI)膜。用红外光谱(FTIR)、拉曼光谱(Raman)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)进行微观结构表征。通入氢气(H2)模拟阳极反应气氛，控制电位为−0.1 V(vs. SCE)，模拟阳极工作电位，采用开路电位(OCP)、电化学阻抗谱(EIS)和极化曲线研究H2对PANI/316 L SS双极板腐蚀性能的影响。结果 FTIR显示有苯环、醌环、P==O和—COOH伸缩振动，Raman显示有掺杂态半醌自由基C—N+.伸缩振动，XPS表明PANI 膜含有C、N、O和P等元素。极化曲线腐蚀电流密度按照H2>N2>O2(DO)依次增大，EIS容抗弧半径按照H2<N2<O2 O2(DO)依次减小。H2环境使PANI/316 L SS体系OCP下降0.06 V，电荷转移电阻(Rct)值下降55 Ω/cm2，自腐蚀电位下降0.3 V左右。结论 PANI具有中间氧化态结构， (CH3CH2)2PO4−和HOOC—COO−作为“对阴离子”在PANI中发生共掺杂。在PEMFC阳极工作电位下，H2对PANI/316 L SS耐蚀性有显著影响，H2使PANI膜发生还原，—N+==与—N+H—的和与总N原子含量的比值(N+/N值)下降1.4%，导致PANI分子链中的“对阴离子”发生脱掺杂，PANI/316 L SS体系耐蚀性下降。 |
| 英文摘要: |
| The work aims to improve the corrosion resistance of bipolar plates in the working environment of proton exchange membrane fuel cell (PEMFC). Polyaniline (PANI) films were electropolymerized on 316 L stainless steel (SS) matrix in 1-ethyl3-methylimidazole diethyl phosphate ([EMIM][DEP]) ionic liquid. The microstructure was characterized by infrared spectroscopy (FTIR), Raman spectroscopy (Raman), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Hydrogen (H2) was injected to simulate the anode reaction atmosphere, and the potential was controlled at −0.1 V(vs. SCE) to simulate the anode working potential. Open circuit potential (OCP), EIS and polarization curves were used to study the effect of H2 on the corrosion performance of bipolar plates. The results indicated that FTIR showed benzene ring, quinone ring, P==O and —COOH stretching vibration, Raman showed doped semi-quinone radical C—N+ stretching vibration, and XPS showed that PANI film contained C, N, O and P elements. The corrosion current density of the polarization curve increased in order of H2>N2>O2(DO), and the radius of the EIS capacitive reactance arc decreased in order of H2<N2<O2(DO). The H2 environment caused the OCP of PANI/316 L SS system to drop by 0.06 V, the charge transfer resistance (Rct) value to drop by 55 Ω/cm2, and the self-corrosion potential to drop by about 0.3 V. It is concluded that PANI has an intermediate oxidation state structure. (CH3CH2)2PO4− and HOOC—COO−are co-doped in PANI as “counter anions”. Under the PEMFC anode working potential, H2 has significant effect on the corrosion resistance of PANI/316 L SS. H2 results in the reduction of PANI and the ratio of the sum of —N+== and —N+H— to the total N atom content (N+/N value) decreases by 1.4%, which leads to the de-doping of the “counter anions” in the PANI molecular chains, and the decrease of the corrosion resistance of PANI/316 L SS system. |
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