固体氧化物燃料电池(SOFC)合金连接体耐高温氧化导电防护涂层
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摘要
降低固体氧化物燃料电池(SOFC)工作温度,可使用高电导、高热导、高强度的合金作为连接体。其中含Cr的铁素体不锈钢合金,具有与SOFC其他部件材料匹配的热膨胀系数,此外还有易于加工及成本低廉等优点,成为中低温板式SOFC连接体材料应用与研究的重点。但这类合金表面高温氧化所带来的界面电阻变化,及Cr挥发进而在阴极沉积所带来的诸多问题,成为影响板式SOFC长期稳定的关键因素,因此必须进行有效的表面处理。从SOFC合金连接体引起的电堆性能衰减机理出发,阐明了降低或防止阴极Cr中毒的几类方法,论述了合金连接体涂层的必要性。结合笔者开发设计的尖晶石粉末还原法在合金连接体表面制备纳米微结构Mn_(0.9)Y_(0.1)Co_2O_4(MYC)防护涂层方面的工作,综述了国内外SOFC合金连接体涂层材料及涂层制备方法的研究进展。对各类涂层材料及涂层制备方法优缺点进行比较的同时,重点介绍了电导率高、实用性较强的钙钛矿结构及尖晶石结构涂层材料。最后展望了合金连接体涂层的发展前景。
The alloy with high conductivity, thermal conductance and strength can be used as the interconnect to reduce the temperature of solid oxide fuel cell(SOFC). The chromium-containing ferritic stainless steels are selected as the leading candidate alloys in the application and study of interconnects for intermediate and low temperature SOFC due to thermal coefficient of expansion matching with the component material of SOFC, easy processing, low cost, etc.. However, issues caused from both interface resistance change induced from surface high-temperature oxidation, and the Cr volatilization and deposition to the cathode, have become the major reasons to influence the long-term stability of SOFC. Therefore, effective surface treatment must be carried out. Based on the degradation mechanism induced from alloy interconnect of SOFC stack, the work illustrates several methods to reduce or prevent cathode Cr poisoning and summarizes that it is necessary to prepare a protective coating on the surface of interconnect alloy. In combination with the previous study by the authors about the Mn_(0.9)Y_(0.1)Co_2O_4(MYC) protective coating of nanostructure on alloy interconnect prepared by the spinel powders reduction technique, the domestic and overseas development of coating materials and fabrication methods for SOFC alloy interconnect are elaborately reviewed. For comparison of the advantages and disadvantages of all kinds of coating materials and coating preparation methods, the perovskite structure and spinel structure materials are highlighted due to high electrical conductivity and practical application ability. Finally, the outlook of alloy interconnect coating is outlined.
The alloy with high conductivity, thermal conductance and strength can be used as the interconnect to reduce the temperature of solid oxide fuel cell(SOFC). The chromium-containing ferritic stainless steels are selected as the leading candidate alloys in the application and study of interconnects for intermediate and low temperature SOFC due to thermal coefficient of expansion matching with the component material of SOFC, easy processing, low cost, etc.. However, issues caused from both interface resistance change induced from surface high-temperature oxidation, and the Cr volatilization and deposition to the cathode, have become the major reasons to influence the long-term stability of SOFC. Therefore, effective surface treatment must be carried out. Based on the degradation mechanism induced from alloy interconnect of SOFC stack, the work illustrates several methods to reduce or prevent cathode Cr poisoning and summarizes that it is necessary to prepare a protective coating on the surface of interconnect alloy. In combination with the previous study by the authors about the Mn_(0.9)Y_(0.1)Co_2O_4(MYC) protective coating of nanostructure on alloy interconnect prepared by the spinel powders reduction technique, the domestic and overseas development of coating materials and fabrication methods for SOFC alloy interconnect are elaborately reviewed. For comparison of the advantages and disadvantages of all kinds of coating materials and coating preparation methods, the perovskite structure and spinel structure materials are highlighted due to high electrical conductivity and practical application ability. Finally, the outlook of alloy interconnect coating is outlined.
引文
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[3]衣宝廉.燃料电池-原理·技术·应用[M].北京:化学工业出版社,2003.YI Bao-lian.Fuel cell-principle,technology,application[M].Beijing:Chemical Industry Press,2003.
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[7]辛显双,朱庆山.固体氧化物燃料电池(SOFC)电池稳定性分析[J].化学进展,2009,21(1):227-234.XIN Xian-shuang,ZHU Qing-shan.Analyses of solid oxide fuel cells(SOFCs)stability[J].Progress in chemistry,2009,21(1):227-234.
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[9]XIN X S,LYU Z,ZHU Q S,et al.Fabrication of dense YSZ electrolyte membranes by a modified dry-pressing using nanocrystalline powders[J].Journal of materials chemistry,2007,17:1627-1630.
[10]NGUYEN Q M.Ceramic fuel cells[J].Journal of the European ceramic society,1993,76:563-588.
[11]TIMURKUTLUK B,CIGDEM T,MAT M D,et al.Areview on cell/stack designs for high performance solid oxide fuel cells[J].Renewable and sustainable energy reviews,2016,56:1101-1121.
[12]SINGHAL S C.Advance in solid oxide fuel cells technology[J].Solid state ionics,2000,135:305-313.
[13]BADWAL S P S,FOGER K.Solid oxide electrolyte fuel cell review[J].Ceramics international,1996,22:257-265.
[14]ZHU W Z,DEEVI S C.Development of interconnect materials for solid oxide fuel cells[J].Materials science&engineering,2003,A348:227-243.
[15]SHAIGAN N,QU W,IVEY D G,et al.A review of recent progress in coatings,surface modifications and alloy developments for solid oxide fuel cell ferritic stainless steel interconnects[J].Journal of power sources,2010,195:1529-1542.
[16]FALK-WINDISCH H,SATTARI M,SVENSSON J E,et al.Chromium vaporization from mechanically deformed pre-coated interconnects in solid oxide fuel cells[J].Journal of power sources,2015,297:217-223.
[17]SHAIGAN N Q W,LVEY D G,CHEN C.A review of recent progress in coatings,surface modifications and alloy developments for solid oxide fuel cell ferritic stainless steel interconnects[J].Journal of power sources,2010,195:1529-1542.
[18]FONTANA S,AMENDOLA R,CHEVALIER S,et al.Metallic interconnects for SOFC:Characterization of corrosion resistance and conductivity evaluation at operating temperature of differently coated alloys[J].Journal of power sources,2007,171:652-662.
[19]PARK M,SHIN J S,LEE S,et al.Thermal degradation mechanism of ferritic alloy(Crofer 22 APU)[J].Corrosion science,2018,134:17-22.
[20]ALNEGREN P,SATTARI M,SVENSSON J E,et al.Temperature dependence of corrosion of ferritic stainless steel in dual atmosphere at 600~800℃[J].Journal of power sources,2018,392:129-138.
[21]HILPERT K,DAS D,MILLER M,et al.Chromium vapor species over solid oxide fuel cell interconnect materials and their potential for degradation processes[J].Journal of the electrochemical society,1996,143:3642-3647.
[22]MOSBAEK R R,HJELM J,BARFOD R,et al.Electrochemical characterization and degradation analysis of large SOFC stacks by impedance spectroscopy[J].Fuel cells,2013,13(4):605-611.
[23]ROEHRENS D,NEUMANN A,BEEZ A,et al.Formation of chromium containing impurities in(La,Sr)MnO3solid-oxide-fuel-cell cathodes under stack operating conditions and its effect on performance[J].Ceramics international,2016,42:9467-9474.
[24]六价铬[EB/OL].http://baike.haosou.com/doc/30235-31519.html,2007-03-16/2018-08-24.Hexavalent chromium[EB/OL].http://baike.haosou.com/doc/30235-31519.html,2007-03-16/2018-08-24.
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[26]GAI L L,LIU Y,XIN X S,et al.Promising cermets of TiN-Ni for intermediate temperature solid oxide fuel cell interconnects application[J].Journal of power sources,2017,359:166-172.
[27]QI Q,LIU Y,WANG L J,et al.The oxidation resistance optimization of titanium carbide/hastelloy(Ni-based alloy)composites applied for intermediate-temperature solid oxide fuel cell interconnects[J].Journal of power sources,2017,359:626-633.
[28]XIONG C Y,LI W L,XIAO J H,et al.Improved chromium-poisoning on lanthanum strontium manganite cathode in presence of a newly developed iron-chromium based interconnect alloy for solid oxide fuel cells[J].International journal of hydrogen energy,2015,40:13957-13963.
[29]FUJITA K,HASHIMOTO T,OGASAWARA K,et al.Relationship between electrochemical properties of SOFCcathode and composition of oxide layer formed on metallic interconnects[J].Journal of power sources,2004,131(1-2):270-277.
[30]STANISLOWSKI M,FROIZHEIM J,NIEWOLAK L,et al.Reduction of chromium vaporization from SOFC interconnectors by highly effective coatings[J].Journal of power sources,2007,164(2):578-589.
[31]TU H Y,STIMMING U.Advances,aging mechanisms and lifetime in solid-oxide fuel cells[J].Journal of power sources,2004,127(1-2):284-293.
[32]LAU G Y,TUCKER M C,JACOBSON C P,et al.Chromium transport by solid state diffusion on solid oxide fuel cell cathode[J].Journal of power sources,2010,195:7540-7547.
[33]PAULSON S C,BIRSS V I.Chromium poisoning of LSM-YSZ SOFC cathodes I detailed study of the distribution of chromium species at a porous,single-phase cathode[J].Journal of the electrochemical society,2004,151(11):A1961-A1968.
[34]JIANG S P,ZHEN Y D,ZHANG S.Interaction between Fe-Cr metallic interconnect and(La,Sr)MnO3/YSZ composite cathode of solid oxide fuel cells[J].Journal of the electrochemical society,2006,153(8):A1511-A1517.
[35]YOKOKAWA H,HORITA T,SAKAI N,et al.Thermodynamic considerations on Cr poisoning in SOFC cathodes[J].Solid state ionics,2006,177(35-36):3193-3198.
[36]HILPERT K,DAS D,MILLER M,et al.Chromium vapor species over solid oxide fuel cell interconnect materials and their potential for degradation processes[J].Journal of the electrochemical society,1996,143(11):3642-3647.
[37]JIANG S P,ZHEN Y D.Mechanism of Cr deposition and its application in the development of Cr-tolerant cathodes of solid oxide fuel cells[J].Solid state ionics,2008,179(27-32):1459-1464.
[38]FERGUS J W.Effect of cathode and electrolyte transport properties on chromium poisoning in solid oxide fuel cells[J].International journal of hydrogen energy,2007,32(16):3664-3671.
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