李宛静,周婉秋,辛士刚,苏桂田,康艳红,孙秋菊.阴极气体O2对石墨烯/聚苯胺/不锈钢双极板耐蚀性的影响[J].表面技术,2023,52(5):163-174.
LI Wan-jing,ZHOU Wan-qiu,XIN Shi-gang,SU Gui-tian,KANG Yan-hong,SUN Qiu-ju.Effect of Cathode Gas Oxygen on Corrosion Resistance of Graphene/Polyaniline/Stainless Steel Bipolar Plates[J].Surface Technology,2023,52(5):163-174 |
| 阴极气体O2对石墨烯/聚苯胺/不锈钢双极板耐蚀性的影响 |
| Effect of Cathode Gas Oxygen on Corrosion Resistance of Graphene/Polyaniline/Stainless Steel Bipolar Plates |
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| DOI：10.16490/j.cnki.issn.1001-3660.2023.05.016 |
| 中文关键词: 石墨烯 聚苯胺 不锈钢双极板 O2 离子液体 耐蚀性 |
| 英文关键词:graphene polyaniline stainless steel bipolar plates oxygen ionic liquid corrosion resistance |
| 基金项目:辽宁省教育厅重点实验室基础研究项目(LZ 2015066) |
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| Author | Institution |
| LI Wan-jing | 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 |
| XIN Shi-gang | College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China |
| SU Gui-tian | 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 提高质子交换膜燃料电池(PEMFC)双极板的耐腐蚀性能。方法 采用循环伏安法(CV)在316L不锈钢(SS)基材上制备还原氧化石墨烯(rGO)/聚苯胺(PANI)层-层复合双极板。用透射电镜(TEM)和扫描电镜(SEM)进行形貌观察，用红外光谱(FTIR)和拉曼光谱(Raman)确定官能团结构，用紫外可见光谱(UV-vis)确定分子共轭状态，用X射线光电子能谱(XPS)确定化学成分和键合状态。在模拟PEMFC阴极工作环境下研究rGO/PANI/316L SS层-层复合双极板的耐腐蚀性能，向体系中通入氧气(O2)，测量开路电位(OCP)、电化学阻抗谱(EIS)和极化曲线评价双极板的抗腐蚀性能。结果 在离子液体1-乙基-3-甲基咪唑硫酸甲酯中，通过电聚合能够获得厚度为53 μm的PANI膜层，在pH=4的0.03 mol/L K2SO4溶液中还原氧化石墨烯(GO)，在PANI上获得厚度为10 μm的rGO膜层。PANI呈中间氧化态，sp2杂化的rGO和PANI之间的相互作用使得共轭效应增强。连续致密的rGO覆盖在多孔的PANI上提高了双极板的耐蚀性。氧气对rGO/PANI/316L SS的耐蚀性有显著影响，不同氧含量条件下，腐蚀电流密度按照N2 > O2(DO) > O2依次降低。结论 氧气有助于在膜/基界面形成保护性的钝化膜，提升了rGO/PANI/316L SS双极板的耐蚀性。 |
| 英文摘要: |
| Stainless steel is one of the most concerned proton exchange membrane fuel cell (PEMFC) bipolar plate materials with low cost, good machinability and excellent electrical and thermal conductivity. However, it is easy to suffer corrosion in acidic working environment of PEMFC. It is necessary to modify the surface of stainless steel (SS) bipolar plate to improve its corrosion resistance. The results show that the corrosion resistance of polyaniline (PANI) monolayer films synthesized by electrochemistry in aqueous solution system is still inadequate, and the corrosive medium can still penetrate into the metal surface through the polymer film to corrode it. In this paper, polyaniline film was synthesized on the surface of 316L stainless steel bipolar plate in ionic liquid, and then graphene oxide was reduced by electrochemical deposition to form rGO/polyaniline layer-layer composite coating to improve the corrosion resistance of bipolar plate. 316L stainless steel plate of 30 mm×10 mm×1 mm was used as the base, and polished with sandpaper. After cleaning with acetone, pickling and water washing, it was blow-dried for later use. Polyaniline thin films were prepared on 316L stainless steel substrate by cyclic voltammetry (CV). The scanning potential ranged from ‒0.8 V to 2 V, the scanning speed was 0.05 V/s, and the cycle was 10 cycles. Then 0.15 mL GO was dropped onto the surface of PANI, and electrochemical reduction was carried out by cyclic voltammetry. The scanning voltage range was from ‒1.6 V to 0.6 V, the scanning speed was 0.02 V/s, and the cycle was 6 cycles. The rGO/PANI layer by layer composite bipolar plate was obtained. The morphology was observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), the structure of functional groups was determined by infrared spectroscopy (FTIR) and Raman spectroscopy (Raman), the conjugation state was determined by UV-vis spectroscopy (UV-VIS), and the chemical composition and bonding state were determined by X-ray photoelectron spectroscopy (XPS). The corrosion resistance of rGO/PANI/316L SS layer-layer composite bipolar plate was studied under the simulated working environment of PEMFC cathode (Oxygen (O2), +0.6 V, 0.2 mol/L H2SO4 aqueous solution). Oxygen was introduced into the system. Open-circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and polarization curves were measured to evaluate the corrosion resistance of bipolar plates. In the ionic liquid 1-ethyl-3-methylimidazolium methyl sulfate, PANI film with thickness of 53 μm was obtained by electropolymerization. GO was reduced in 0.03 mol/L K2SO4 solution with pH=4, and rGO film with thickness of 10 μm was obtained on PANI. The rGO film was like a layer of light yarn covering the surface of PANI, and the coral-like shape of PANI under the film could be vaguely seen through the rGO film. PANI had an intermediate oxidation state. The interaction between sp2 hybrid rGO and PANI enhanced the conjugation effect. The continuous dense rGO covering the porous PANI improved the corrosion resistance of the bipolar plate. In the rGO/PANI/316L SS system, the corrosion current densities of O2, O2(DO) and N2 were 2.89×10‒6 A/cm2, 3.84×10‒6 A/cm2 and 8.13×10‒6 A/cm2 respectively. In the PANI/316L SS system, the corrosion current densities of O2, O2(DO) and N2 were 2.30×10‒5 A/cm2, 1.39×10‒5 A/cm2 and 1.25×10‒5 A/cm2 respectively. The corrosion current density of rGO/PANI/316L SS system was one order of magnitude lower than that of PANI/316L SS system, indicating that the corrosion resistance of rGO/PANI composite coating was further improved. The corrosion current density of rGO/PANI/316L SS was the lowest in O2. Oxygen had a significant effect on the corrosion resistance of rGO/PANI/316L SS. Oxygen contributes to the formation of a protective passivation film at the membrane/substrate interface, which improves the corrosion resistance of rGO/PANI/316L SS bipolar plates and has a good development prospect in the future. |
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