氧气对聚苯胺/316L不锈钢体系耐腐蚀性能的影响
|
摘要
为了防止不锈钢双极板在质子交换膜燃料电池(PEMFC)工作环境下发生腐蚀,在由0.1 mol/L苯胺单体与0.2 mol/L H_2SO_4组成的水溶液中采用循环伏安法在316L不锈钢(SS)表面电化学合成了导电聚苯胺(PANI)薄膜。采用傅里叶变换红外光谱(FT-IR)分析了PANI的化学结构,采用扫描电镜(SEM)观察了表面形貌,发现所合成的PANI具有苯-醌交替的中间氧化态结构,PANI膜呈现纤维状形貌特征。采用极化曲线和电化学阻抗谱(EIS)对比研究了在0.2 mol/L H_2SO_4中氧气对PANI/316L SS和无涂层316L SS耐腐蚀性能的影响。结果表明,氧气促进了PANI/316L SS界面处保护性氧化膜的形成,使PANI/316L SS体系的耐腐蚀性能提高。
In order to prevent stainless steel bipolar plates from corrosion under PEMFC(proton exchange membrane fuel cell) working environment, electrosynthesis was performed on the surface of 316L stainless steel(SS) in an aqueous solution composed of 0.1 mol/L aniline and 0.2 mol/L H_2SO_4 by cyclic voltammetry. The chemical structure of polyaniline(PANI)was analyzed by Fourier-transform infrared spectroscopy(FT-IR). The surface morphology was observed by scanning electron microscopy(SEM). It was found that the synthesized polyaniline was in an alternating benzene–quinone intermediate oxidation state, and the PANI film showed a fibrous morphology. The effect of oxygen on corrosion resistance of PANI/316L SS and uncoated 316 L SS in 0.2 mol/L H_2SO_4 was studied by polarization curve measurement and electrochemical impedance spectroscopy(EIS). The results showed that oxygen promoted the formation of protective oxide film at the interface of PANI/316L SS, which improved the corrosion resistance of PANI/316L SS system.
In order to prevent stainless steel bipolar plates from corrosion under PEMFC(proton exchange membrane fuel cell) working environment, electrosynthesis was performed on the surface of 316L stainless steel(SS) in an aqueous solution composed of 0.1 mol/L aniline and 0.2 mol/L H_2SO_4 by cyclic voltammetry. The chemical structure of polyaniline(PANI)was analyzed by Fourier-transform infrared spectroscopy(FT-IR). The surface morphology was observed by scanning electron microscopy(SEM). It was found that the synthesized polyaniline was in an alternating benzene–quinone intermediate oxidation state, and the PANI film showed a fibrous morphology. The effect of oxygen on corrosion resistance of PANI/316L SS and uncoated 316 L SS in 0.2 mol/L H_2SO_4 was studied by polarization curve measurement and electrochemical impedance spectroscopy(EIS). The results showed that oxygen promoted the formation of protective oxide film at the interface of PANI/316L SS, which improved the corrosion resistance of PANI/316L SS system.
引文
[1]BROUZGOU A,SONG S Q,TSIAKARAS P.Low and non-platinum electrocatalysts for PEMFCs:current status,challenges and prospects[J].Applied Catalysis B:Environmental,2012,127:371-388.
[2]MEHTA V,COOPER J S.Review and analysis of PEM fuel cell design and manufacturing[J].Journal of Power Sources,2003,114(1):32-53.
[3]付宇,侯明,邵志刚,等.PEMFC金属双极板研究进展[J].电源技术,2008,32(9):631-635.
[4]MELE C,BOZZINI B.Electrodeposition of a Au-Dy2O3 composite solid oxide fuel cell catalyst from eutectic urea/choline chloride ionic liquid[J].Energies,2012,5(12):5363-5371.
[5]DE LAS HERAS N,ROBERTS E P L,LANGTON R,et al.A review of metal separator plate materials suitable for automotive PEM fuel cells[J].Energy&Environmental Science,2009,2(2):206-214.
[6]LAVIGNE O,ALEMANY-DUMOUT C,NORMAND B,et al.Cerium insertion in 316L passive film:effect on conductivity and corrosion resistance performances of metallic bipolar plates for PEM fuel cell application[J].Surface and Coatings Technology,2010,205(7):1870-1877.
[7]JEON J W,MA Y G,MIKE J F,et al.Oxidatively stable polyaniline:polyacid electrodes for electrochemical energy storage[J].Physical Chemistry Chemical Physics,2013,15(24):9654-9662.
[8]LE D P,YOO Y H,KIM J G,et al.Corrosion characteristics of polyaniline-coated 316L stainless steel in sulphuric acid containing fluoride[J].Corrosion Science,2009,51(2):330-338.
[9]YANG Y,GUO L J,LIU H T.Corrosion characteristics of SS316L as bipolar plate material in PEMFC cathode environments with different acidities[J].International Journal of Hydrogen Energy,2011,36(2):1654-1663.
[10]DE BRUIJN F.The current status of fuel cell technology for mobile and stationary applications[J].Green Chemistry,2005,7(3):132-150.
[11]ANTUNES R A,OLIVEIRA M C L,ETT G,et al.Corrosion of metal bipolar plates for PEM fuel cells:a review[J].International Journal of Hydrogen Energy,2010,35(8):3632-3647.
[12]CHO E A,JEON U S,HONG S A,et al.Performance of a 1 kW-class PEMFC stack using TiN-coated 316 stainless steel bipolar plates[J].Journal of Power Sources,2005,142(1/2):177-183.
[13]LI M C,LUO S Z,ZENG C L,et al.Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments[J].Corrosion Science,2004,46(6):1369-1380.
[14]JOSEPH S,MCCLURE J C,CHIANELLI R,et al.Conducting polymer-coated stainless steel bipolar plates for proton exchange membrane fuel cells(PEMFC)[J].International Journal of Hydrogen Energy,2005,30(12):1339-1344.
[15]REN Y J,CHEN J,ZENG C L.Corrosion protection of type 304 stainless steel bipolar plates of proton-exchange membrane fuel cells by doped polyaniline coating[J].Journal of Power Sources,2010,195(7):1914-1919.
[16]LI P P,DING X N,YANG Z Y,et al.Electrochemical synthesis and characterization of polyaniline-coated PEMFC metal bipolar plates with improved corrosion resistance[J].Ionics,2018,24(4):1129-1137.
[17]DEBERRY D W.Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive coating[J].Journal of the Electrochemical Society,1985,132(5):1022-1026.
[18]JAFARZADEH S,THORMANN E,R?NNEVALL T,et al.Toward homogeneous nanostructured polyaniline/resin blends[J].ACS Applied Materials&Interfaces,2011,3(5):1681-1691.
[19]JAFARZADEH S,CLAESSON P M,SUNDELL P E,et al.Nanoscale electrical and mechanical characteristics of conductive polyaniline network in polymer composite films[J].ACS Applied Materials&Interfaces,2014,6(21):19168-19175.
[20]JOUBERT M,BOUHADID M,BéGUéD,et al.Conducting polyaniline composite:from syntheses in waterborne systems to chemical sensor devices[J].Polymer,2010,51(8):1716-1722.
[21]HAN M G,SPERRY J,GUPTA A,et al.Polyaniline coated poly(butyl methacrylate)core-shell particles:roll-to-roll printing of templated electrically conductive structures[J].Journal of Materials Chemistry,2007,17(14):1347-1352.
[22]LEE I S,CHO M S,CHOI H J.Preparation of polyaniline coated poly(methyl methacrylate)microsphere by graft polymerization and its electrorheology[J].Polymer,2005,46(4):1317-1321.
[23]CHEN W C,WEN T C,HU C C,et al.Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy[J].Electrochimica Acta,2002,47(8):1305-1315.
[24]李芝华,李珺杰,卢健体.银/聚苯胺纳米复合材料的制备及电化学性能[J].高分子材料科学与工程,2014,30(7):168-172.
[25]PAWAR P,GAIKAWAD A B,PATIL P P.Electrochemical synthesis of corrosion protective polyaniline coatings on mild steel from aqueous salicylate medium[J].Science and Technology of Advanced Materials,2006,7(7):732-744.
[26]GAO Y Z,SYED J A,LU H B,et al.Anti-corrosive performance of electropolymerized phosphomolybdic acid doped PANI coating on 304SS[J].Applied Surface Science,2016,360(Part A):389-397.
[27]GRGUR B N,GVOZDENOVI?M M,MI?KOVI?-STANKOVI?V B,et al.Corrosion behavior and thermal stability of electrodeposited PANI/epoxy coating system on mild steel in sodium chloride solution[J].Progress in Organic Coatings,2006,56(2/3):214-219.
[28]刘明,傅杰,徐洪峰,等.聚苯胺复合材料制备及在模拟PEMFC环境下的电化学行为[J].大连交通大学学报,2016,37(5):103-108.
[29]LACO J I I,VILLOTA F C,MESTRES F L.Corrosion protection of carbon steel with thermoplastic coatings and alkyd resins containing polyaniline as conductive polymer[J].Progress in Organic Coatings,2005,52(2):151-160.
[30]赖延清,卢海,张治安,等.聚苯胺纳米纤维的界面聚合法合成及电化学电容行为[J].中南大学学报(自然科学版),2007,38(6):1110-1114.
[31]CHEN W C,WEN T C,HU C C,et al.Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy[J].Electrochimica Acta,2002,47(8):1305-1315.
[32]李谋成,曾潮流,林海潮,等.不锈钢在含24SO-稀HCl中的电化学腐蚀行为[J].腐蚀科学与防护技术,2002,14(3):132-135.
[33]孙毅,钟发春,舒远杰,等.聚苯胺的腐蚀防护机理及其在金属防腐中的应用[J].材料导报,2009,23(13):65-68.
[34]FAHLMAN M,JASTY S,EPSTEIN A J.Corrosion protection of iron/steel by emeraldine base polyaniline:an X-ray photoelectron spectroscopy study[J].Synthetic Metals,1997,85(1/2/3):1323-1326.
[2]MEHTA V,COOPER J S.Review and analysis of PEM fuel cell design and manufacturing[J].Journal of Power Sources,2003,114(1):32-53.
[3]付宇,侯明,邵志刚,等.PEMFC金属双极板研究进展[J].电源技术,2008,32(9):631-635.
[4]MELE C,BOZZINI B.Electrodeposition of a Au-Dy2O3 composite solid oxide fuel cell catalyst from eutectic urea/choline chloride ionic liquid[J].Energies,2012,5(12):5363-5371.
[5]DE LAS HERAS N,ROBERTS E P L,LANGTON R,et al.A review of metal separator plate materials suitable for automotive PEM fuel cells[J].Energy&Environmental Science,2009,2(2):206-214.
[6]LAVIGNE O,ALEMANY-DUMOUT C,NORMAND B,et al.Cerium insertion in 316L passive film:effect on conductivity and corrosion resistance performances of metallic bipolar plates for PEM fuel cell application[J].Surface and Coatings Technology,2010,205(7):1870-1877.
[7]JEON J W,MA Y G,MIKE J F,et al.Oxidatively stable polyaniline:polyacid electrodes for electrochemical energy storage[J].Physical Chemistry Chemical Physics,2013,15(24):9654-9662.
[8]LE D P,YOO Y H,KIM J G,et al.Corrosion characteristics of polyaniline-coated 316L stainless steel in sulphuric acid containing fluoride[J].Corrosion Science,2009,51(2):330-338.
[9]YANG Y,GUO L J,LIU H T.Corrosion characteristics of SS316L as bipolar plate material in PEMFC cathode environments with different acidities[J].International Journal of Hydrogen Energy,2011,36(2):1654-1663.
[10]DE BRUIJN F.The current status of fuel cell technology for mobile and stationary applications[J].Green Chemistry,2005,7(3):132-150.
[11]ANTUNES R A,OLIVEIRA M C L,ETT G,et al.Corrosion of metal bipolar plates for PEM fuel cells:a review[J].International Journal of Hydrogen Energy,2010,35(8):3632-3647.
[12]CHO E A,JEON U S,HONG S A,et al.Performance of a 1 kW-class PEMFC stack using TiN-coated 316 stainless steel bipolar plates[J].Journal of Power Sources,2005,142(1/2):177-183.
[13]LI M C,LUO S Z,ZENG C L,et al.Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments[J].Corrosion Science,2004,46(6):1369-1380.
[14]JOSEPH S,MCCLURE J C,CHIANELLI R,et al.Conducting polymer-coated stainless steel bipolar plates for proton exchange membrane fuel cells(PEMFC)[J].International Journal of Hydrogen Energy,2005,30(12):1339-1344.
[15]REN Y J,CHEN J,ZENG C L.Corrosion protection of type 304 stainless steel bipolar plates of proton-exchange membrane fuel cells by doped polyaniline coating[J].Journal of Power Sources,2010,195(7):1914-1919.
[16]LI P P,DING X N,YANG Z Y,et al.Electrochemical synthesis and characterization of polyaniline-coated PEMFC metal bipolar plates with improved corrosion resistance[J].Ionics,2018,24(4):1129-1137.
[17]DEBERRY D W.Modification of the electrochemical and corrosion behavior of stainless steels with an electroactive coating[J].Journal of the Electrochemical Society,1985,132(5):1022-1026.
[18]JAFARZADEH S,THORMANN E,R?NNEVALL T,et al.Toward homogeneous nanostructured polyaniline/resin blends[J].ACS Applied Materials&Interfaces,2011,3(5):1681-1691.
[19]JAFARZADEH S,CLAESSON P M,SUNDELL P E,et al.Nanoscale electrical and mechanical characteristics of conductive polyaniline network in polymer composite films[J].ACS Applied Materials&Interfaces,2014,6(21):19168-19175.
[20]JOUBERT M,BOUHADID M,BéGUéD,et al.Conducting polyaniline composite:from syntheses in waterborne systems to chemical sensor devices[J].Polymer,2010,51(8):1716-1722.
[21]HAN M G,SPERRY J,GUPTA A,et al.Polyaniline coated poly(butyl methacrylate)core-shell particles:roll-to-roll printing of templated electrically conductive structures[J].Journal of Materials Chemistry,2007,17(14):1347-1352.
[22]LEE I S,CHO M S,CHOI H J.Preparation of polyaniline coated poly(methyl methacrylate)microsphere by graft polymerization and its electrorheology[J].Polymer,2005,46(4):1317-1321.
[23]CHEN W C,WEN T C,HU C C,et al.Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy[J].Electrochimica Acta,2002,47(8):1305-1315.
[24]李芝华,李珺杰,卢健体.银/聚苯胺纳米复合材料的制备及电化学性能[J].高分子材料科学与工程,2014,30(7):168-172.
[25]PAWAR P,GAIKAWAD A B,PATIL P P.Electrochemical synthesis of corrosion protective polyaniline coatings on mild steel from aqueous salicylate medium[J].Science and Technology of Advanced Materials,2006,7(7):732-744.
[26]GAO Y Z,SYED J A,LU H B,et al.Anti-corrosive performance of electropolymerized phosphomolybdic acid doped PANI coating on 304SS[J].Applied Surface Science,2016,360(Part A):389-397.
[27]GRGUR B N,GVOZDENOVI?M M,MI?KOVI?-STANKOVI?V B,et al.Corrosion behavior and thermal stability of electrodeposited PANI/epoxy coating system on mild steel in sodium chloride solution[J].Progress in Organic Coatings,2006,56(2/3):214-219.
[28]刘明,傅杰,徐洪峰,等.聚苯胺复合材料制备及在模拟PEMFC环境下的电化学行为[J].大连交通大学学报,2016,37(5):103-108.
[29]LACO J I I,VILLOTA F C,MESTRES F L.Corrosion protection of carbon steel with thermoplastic coatings and alkyd resins containing polyaniline as conductive polymer[J].Progress in Organic Coatings,2005,52(2):151-160.
[30]赖延清,卢海,张治安,等.聚苯胺纳米纤维的界面聚合法合成及电化学电容行为[J].中南大学学报(自然科学版),2007,38(6):1110-1114.
[31]CHEN W C,WEN T C,HU C C,et al.Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy[J].Electrochimica Acta,2002,47(8):1305-1315.
[32]李谋成,曾潮流,林海潮,等.不锈钢在含24SO-稀HCl中的电化学腐蚀行为[J].腐蚀科学与防护技术,2002,14(3):132-135.
[33]孙毅,钟发春,舒远杰,等.聚苯胺的腐蚀防护机理及其在金属防腐中的应用[J].材料导报,2009,23(13):65-68.
[34]FAHLMAN M,JASTY S,EPSTEIN A J.Corrosion protection of iron/steel by emeraldine base polyaniline:an X-ray photoelectron spectroscopy study[J].Synthetic Metals,1997,85(1/2/3):1323-1326.