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

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。     

固体氧化物燃料电池金属连接体防护涂层研究进展

铁素体不锈钢因具有良好的耐腐蚀性、高电导率、高热导率等诸多优异性能,是常用的中低温固体氧化物燃料电池（SOFC）用连接体材料,但是含Cr不锈钢在600～800℃的SOFC工作温度下存在高温氧化带来的界面电阻增大、Cr元素毒化阴极等问题。从连接体材料、防护涂层种类及其制备方法出发,简述了金属连接体材料的选择和Cr毒化阴极机理,重点阐述了活性元素氧化物涂层、稀土钙钛矿涂层以及尖晶石涂层对连接体的保护作用和近些年新的研究进展,并归纳了SOFC金属连接体表面涂层常用的制备方法和特点。介绍了稀土元素氧化物涂层对合金氧化膜的影响机制和应用局限性。总结了La_1–xSr_xCrO₃、La_1–xSr_xCoO₃、La_1–xSr_xMnO₃等常用钙钛矿涂层的优势和不足,并分析了掺杂对钙钛矿涂层性能的影响。重点综述了过渡金属元素掺杂、稀土元素掺杂对Mn-Co、Cu-Mn尖晶石涂层电导率、热膨胀系数匹配性、涂层结合情况等...     

LaCoO3涂层对SUS 430合金连接体中温氧化行为的影响

通过溶胶-凝胶提拉法在SUS 430合金表面施加LaCoO3钙钛矿导电涂层,并研究其对固体氧化物燃料电池(SOFC)金属连接体SUS 430合金中温氧化行为的影响.利用X射线衍射(XRD)、扫描电子显微镜(SEM)以及能谱仪(EDS)对施加涂层合金的氧化物相结构与微观形貌进行表征,并采用"4点法"测量施加涂层合金表面氧化膜的面比电阻(ASR).750 ℃空气中的循环氧化结果表明,施加LaCoO3涂层合金的氧化动力学曲线遵循抛物线规律,氧化速率常数K为4.18×10-15 g2/(cm4·s),比与未施加涂层合金降低了1-2个数量级;LaCoO3涂层有效地抑制了Cr2O3相的形成,减缓了MnCr2O4尖晶石的生长.最终使得SUS 430合金的氧化抗力和氧化后的导电性得到增强.     

固体氧化物燃料电池连接体材料研究进展

固体氧化物燃料电池(SOFC)是高效、洁净、全固态的电化学装置,是发展比较快的能源技术之一.本文总结了SOFC关键组件连接体材料的研究进展,详细论述了近年发展起来的金属连接体材料的研究状况,总结了目前研究比较广泛的Ni基、Fe基、Cr基连接体合金的性能特点和存在的主要问题,最后介绍了经过表面处理的Fe-Cr基合金应作为SOFC金属连接体材料的研究重点.     

空气等离子喷涂板式SOFC连接体保护涂层的性能

在中温平板型固体氧化物燃料电池（ITSOFC）设计中,可以采用金属作为连接材料.Fe-16Cr合金是较为理想的金属连接材料,它存在的主要问题是连接体阴极侧表面的高温氧化和腐蚀,会导致电池性能的迅速降低.本研究采用空气等离子喷涂的方法喷涂了La0.8Sr0.2MnO3-σ（LSM）钙钛矿型保护涂层在金属连接板的表面,并讨论了主要过程参数及其作用效果.研究发现,喷涂后热处理是降低涂层孔隙率的有效方法,经喷涂-热处理后,涂层的孔隙率可降至1%以下.等离子喷涂LSM保护涂层后,Fe-16Cr合金的耐高温氧化性能明显提高,氧化速率降低了76%.     

固体氧化物燃料电池(SOFC)用NiMOCr金属连接体氧化行为研究

金属作为固体氧化物燃料电池(SOFC)连接体材料已成为可能并成为研究热点.本论文对SOFC用NiMoCr合金分别在SOFC阴极和阳极气氛条件下的高温氧化性能作了详细的研究.结果表明:阳极(燃料极)条件下氧化所形成的是MnCr2O4尖晶石;阴极(空气极)条件下氧化所形成的是不含Cr的致密NiMnO4型尖晶石,能有效抑制C...     

固体氧化物燃料电池金属连接体保护膜层研究进展

随着固体氧化物燃料电池(SOFC)的工作温度从1000℃降低到600~800℃,铁素体不锈钢成为SOFC连接体材料的最佳选择,但在高温氧化气氛下,氧化层快速生长以及Cr的毒化问题使得电池堆性能大大降低。目前,主要的解决方式是在基体材料表面涂镀保护膜层和材料改性。前者由于生产简单、成本低成为当前研究热点。本文主要介绍金属连接体保护膜的分类和研究现状,并探讨各膜层材料的优缺点及发展前景。     

铬基合金连接体材料在固体氧化物燃料电池中的应用

主要介绍了固体氧化物燃料电池(SOFC)的铬(Cr)基合金连接体材料的发展现状.Cr基合金具有良好的抗氧化性、耐腐蚀性和导电性能等,是目前连接体材料中的研究热点之一.在SOFC阴极环境中,容易形成氧化层,同时由于Cr的扩散和挥发还可能导致阴极中毒,合金中掺杂稀土元素(Y、La、Ce和Zr)可以抑制Cr2O3层的生成.在阳极环境中,Cr基合金的表现优于阴极.与Al2O3、NiO、MgO和TiO2等相比,Cr2O3基氧化层具有较好的综合性能,其耐高温(1100 ℃)、热膨胀系数(9.6×10-6K-1)和YSZ电解质(10.8×10-6K-1)相近、且具有较好的导电性.目前,Cr基合金的研究重点是氧化物弥散强化(ODS)合金,使用最多的是Cr5Fe1Y2O3,其热膨胀系数为9×10-6K-1～10×10-6K-1(1000 ℃),抗氧化性能较好.     

SOFC连接体用STS444/Y合金的高温导电性能研究

以固体氧化物燃料电池(SOFC)金属连接体为研究对象,分析铁素体不锈钢STS444涂覆稀土元素Y后在750℃下的高温氧化和导电行为。利用辉光放电光谱(GDS)和二次离子质谱(SIMS)技术研究了主要元素(Fe,Cr,Mn,Si)和稀土元素Y对氧化膜生长和高温导电性能的影响。结果表明,Y元素的活性元素效应使STS444/Y合金可以显著改善其抗氧化性和高温导电性,可作为SOFC金属连接体的候选材料。     

涂层在固体氧化物燃料电池金属连接体中的应用

固体氧化物燃料电池工作温度的降低,使铁素体不锈钢用作连接体成为了可能。这类连接体具有热导率高、导电性能好、热膨胀性匹配等优点,但也存在一些问题,如高价Cr的挥发以及抗氧化性弱等。涂层可以改善铁素体不锈钢的相关性能。本文综述了稀土氧化物涂层、钙钛矿涂层以及尖晶石涂层的涂层类型和涂覆方法,比较了在金属连接体中的应用效果。     

Indirect evaluation of the long-term oxidation properties of Al−21Ti−23Cr and Al−37Ti−12Cr coating materials for TiAl alloy

The most pertinent coating materials in the Al−Ti−Cr alloy system to improve the high temperature oxidation resistance of a TiAl alloy, with respect to oxidation properties, resistance to thermal stress, and chemical compatibility, are the two-phase alloys of Al−21Ti−23Cr (L1₂+Cr₂Al) and Al−37Ti−12Cr (γ+TiAlCr). In this study, cyclic oxidation tests at 1000 °C and 1200 °C were performed for the specimens coated with both materials of 10 im thickness. Furthermore, breakaway oxidation caused by the formation of a rutile TiO₂ scale was observed, though both bulk alloys showed very stable oxidation behavior. This phenomenon was resulted from the depleted Al content in the coating layer due to Al₂O₃ oxide growth and interdiffusion with the substrate. Considering the decrease of Al content due to oxide growth, the Al−21Ti−23Cr coating with the initial higher Al content was more effective for long-term oxidation protection of the TiAl alloy. On the other hand, when the Al content changes due to the interdiffusion with the substrate, the Al−37Ti−12Cr coating with a smaller compositional gradient with the TiAl substrate was more effective than the Al−21Ti−23Cr coating. Cyclic oxidation tests at 1000 °C and 1200 °C confirmed that for the longer lifetime of coating materials the initial Al content was more important than the smaller compositional gradient with the substrate. Consequently, the Al−21Ti−23Cr coating was considered as more effective one for the long-term oxidation resistance of TiAl alloys.     

Conductivity and Oxidation Behavior of Fe-16Cr Alloy as Solid Oxide Fuel Cell Interconnect Under Long-Stability and Thermal Cycles

Conductivity and oxidation behavior of Fe-16Cr alloy were investigated under long-term stability operation at 750℃ and thermal cycles from room temperature to 750℃.The results showed that the area specific resistance (ASR) of Fe-16Cr alloy increased over time and reached about 56.29 mΩcm ~(2 )after 40,000 h of long-term stability operation at 750℃ by theoretical calculation.The ASR of Fe-16Cr remained about 11 mΩcm ~(2 )after 52 thermal cycles from room temperature to750℃.The analysis of structure showed that the oxidized phase on the surface of Fe-16Cr was mainly composed of Cr _(2 )O _3and Fe Cr _(2 )O _(4 )spinel phase under long-term stability operation at 750℃.While the Cr _(2 )O _(3 )phase was mainly observed on the surface of Fe-16Cr alloy after 52 thermal cycles,the oxidation rates of Fe-16Cr alloy were 0.0142μm h~(-1 )and 0.06μm cycle~(-1 )under long-term stability operation and under thermal cycle,respectively.The property of Fe-16Cr alloy with 2.6 mm thickness met the lifespan requirement of interconnect for solid oxide fuel cell (SOFC) stacks.The Cr element all diff used onto oxidation surface,indicating that it was necessary to spray a coating on the surface to avoid poisoning cell cathode of SOFCs.Two 2-cell stacks were assembled and tested to verify the properties of Fe-16Cr alloy as SOFC interconnect under long-term stability operation and thermal cycle condition.     

Fe-Cr-Mn合金在湿润环境中的氧化行为研究

研究比较了Fe-13Cr-xMn(x=0.5,1,2) 系列合金在干燥和湿润空气中800 ℃下的氧化行为。结果表明,在干燥气氛中合金表现出良好的抗氧化性能,当Mn含量低于1%时有助于合金表面生成阻碍Cr挥发的 (Mn,Cr)₃O₄尖晶石相;而当Mn含量达到2%,合金表面则会产生Mn₂O₃,从而影响合金的抗高温氧化性能。在含水蒸气气氛中,合金发生了失稳态氧化,表面生成了大量氧化物,合金的氧化速率随Mn含量的增大而减小,主要原因是Mn含量增加导致膜层中形成 (Mn,Cr)₃O₄尖晶石相,从而有效阻碍了水气环境中Cr的挥发,尤其Fe-13Cr-2Mn合金在氧化初期12 h内并没有发生加速腐蚀,Fe-Cr-Mn合金的加速氧化是由表面氧化铬膜与水蒸气发生反应所致。通过SEM,XRD等分析手段深入探讨了合金加速氧化机制以及Mn效应。     

A new austenitic alumina forming alloy: an aluminium‐coated FeNi32Cr20

The FeCrAl alloys owe their low oxidation rate to the formation of a slow growing α‐aluminium oxide scale. Therefore they are used, for example, as a substrate material in metal‐supported automotive catalytic converters. Increasing exhaust gas temperatures mean that, in addition to the oxidation properties, high temperature mechanical properties should also be improved. Compared to the ferritic FeCrAl alloys, austenitic alloys possess the required high mechanical strength at higher temperatures. However for most commercially available materials the oxidation resistance is not sufficient due to a low aluminium content. High aluminium contents are avoided in austenitic alloys, since they cause severe workability problems, even at aluminium contents, which are below the necessary amount to get a pure alumina scale. The newly developed material Nicrofer 3220 PAl (coated FeNiCrAl) consists of an austenitic FeNi32Cr20 alloy coated with aluminium on both sides. It combines the outstanding oxidation resistance of an alumina forming FeCrAl alloy with the advantage of the high temperature strength of an austenitic alloy. Additionally the oxidation is even lower than the oxidation of the commercial grade Aluchrom YHf (FeCr20Al6)—conventional homogenous FeCrAl. Aluminium coated FeNiCrAl can easily be formed into its final shape. Prior to service, an in situ heat treatment is recommended in order to optimize the properties.     

锆合金包壳表面涂层研究进展

耐事故燃料是一种满足反应堆更多安全裕量设计要求的新型燃料元件。锆合金表面涂层研究是耐事故燃料包壳发展的一个主要方向,致力于解决高温条件下锆水严重反应的问题。该包壳具有经济性好,易于实现商业化等优点。重点阐述了锆合金包壳表面涂层制备技术和一些应用性能的研究进展,制备技术包括涂层方法、涂层厚度和涂层成分等,应用性能主要包括高温氧化和辐照性能。详细分析了锆合金表面涂层研究需要考虑的四个关键问题,即涂层材料选择、涂层工艺选择、涂层质量表征以及涂层锆包壳关键应用性能研究。涂层材料既要满足耐高温氧化性能,又要满足堆内正常运行的相关性能要求;涂层工艺应能制备出结合力好且致密的薄膜,并考虑锆包壳管涂层过程的可实现性;针对锆包壳特殊的应用环境,涂层质量表征重点关注涂层的附着力和膜致密度;涂层包壳关键应用性能主要考虑高温氧化、腐蚀、抗热冲击和腐蚀性能。综合已有研究结果,指出MAX相和金属Cr是两种有应用前景的锆包壳涂层材料,电弧离子镀技术作为锆包壳涂层工艺有一定的发展潜力。     

Thermal stability and oxidation resistance of TiCrAlYO coatings on SS430 for solid oxide fuel cell interconnect applications

Chromia-forming ferritic stainless steels are being considered for interconnect applications in planar solid oxide fuel cell (SOFC) stacks because of their low cost and physical properties. At high temperatures, ferritic steels lack environmental stability in the SOFC operating environment, and gradually degrade the cell stack performance. In this study, an effective, dense and well adherent TiCrAlYO coating was deposited on an SS430 alloy using the filtered arc deposition technique. High-energy ion backscattering was used to characterize the composition and the thermal stability of the coatings. The chromium volatility of the coated steel plates at 800 °C was also measured using ion beam analysis. Significant reductions in oxidation rates as well as reduced Cr volatility were observed for the coated alloys.     

高温海洋环境下过渡金属基合金的腐蚀与防护研究进展

综述了高温海洋腐蚀环境的类型,以及各类合金在不同环境下的腐蚀失效机理。重点考察了Fe、Ti、Ni基合金内部的主要元素在高温下的扩散行为,及其与侵蚀性离子之间的交互作用。从盐雾腐蚀以及熔融热腐蚀2个角度,讨论了化学/电化学反应发生的可能性。基于氧化腐蚀过程中复合氧化膜的形成过程,总结了氧化膜与侵蚀性离子以及杂质气体的再作用机理,明确了保护性氧化膜和非保护性氧化膜的类型。从合金化的角度,揭示了Cr、Al等元素对防腐性能提升的关键作用,指出了材料计算在高温海洋环境的潜在应用价值。最后归纳了高温海洋环境下的涂层防护手段和材料体系,其中结构稳定性和界面反应问题是涂层材料研究的重点。在未来研究方向上,指出应该重点关注腐蚀过程中活性元素的交互作用以及钝化膜的形成机理,筛选有效防护元素。利用氧化、盐雾等多种腐蚀条件,依托构效关系进行涂层优化,形成系统的海洋高温涂层防护方案。高熵合金涂层作为新兴体系在高温防护上的应用具有研究价值。     

Mo含量对FeCoCrNiMox高熵合金等离子喷焊层组织与性能的影响

目的 研究不同Mo元素添加量对FeCoCrNiMox(x=0、0.5、1、1.5)高熵合金等离子喷焊层组织和性能的影响,以期望获得一种高硬度、耐腐蚀的喷焊层,用于改善传统工模具表面防护与使用寿命的问题。方法 采用等离子喷焊技术在Q235A低碳钢表面制备了不同Mo含量的高熵合金喷焊层,通过X射线衍射仪(XRD)、光学显微镜(OM)、扫描电子显微镜(SEM)、能量色散X射线光谱仪(EDS)表征其微观组织与相结构,借助显微硬度计和电化学工作站对喷焊层的硬度和耐腐蚀性能进行测试。结果 随着Mo含量x从0逐渐增加到1.5,喷焊层的晶界胞状枝晶组织(枝晶内为白色富Mo相,枝晶间为灰色富Fe、Ni相)逐渐增加,合金微观组织变得细小;喷焊层的硬度由204.4HV0.2增加至706.8HV0.2;喷焊层在3.5%NaCl溶液中呈现出明显的钝化行为,腐蚀电位由?0.753 V增大到?0.412 V,腐蚀电流密度由1.23×10^?4 A/cm²减小到3.80×10^?6 A/cm²,点蚀电位由?0.642 V增大到?0.371 V,具有优异的耐腐蚀性能。结论 所设计的FeCoCrNiMox合金及相应的等离子喷焊工艺,满足对喷焊层高耐磨以及耐腐蚀性的要求,有望应用于传统工模具的表面防护与修复。     

Development of Re‐based diffusion barrier coatings on nickel based superalloys

A diffusion barrier type coating with a duplex layer structure, an inner σ‐(Re, W, Cr, Ni) as a diffusion barrier and outer Ni‐aluminide as an Al reservoir, was formed on a Nickel based, single crystal, superalloy (TMS‐82 +) and on Hastelloy X. Oxidation properties of both the alloys with or without the diffusion barrier coating were investigated in air under thermal cycling between room temperature and 1423 K for up to 360 ks. The inner σ layer with a composition (at%) of (35–40) Re, (15–20) W, (15–25) Cr and (15–25) Ni was produced by electrodeposition of Ni‐70Re and Ni‐20W films from aqueous solutions followed by Cr‐pack cementation at temperatures between 1473 and 1573 K, and the outer Ni‐aluminides of β‐(Ni,Cr)Al + γ′‐(Ni,Cr)₃Al was formed by electrodeposition of a Ni film, followed by Al pack cementation. After the 360 ks oxidation it was found that the structure and composition of both σ layer and alloy substrate were retained with little change. Furthermore, there was little Al in the σ layer. It could be concluded that the Re‐based alloys such as σ (Re(W),Cr,Ni) are very promising candidates as a diffusion barrier between the outer Al‐reservoir layer and alloy substrate at temperature of 1423 K. It was found that the Re(W)‐Cr‐Ni acts as a diffusion barrier for both inward diffusion of Al and outward diffusion of alloying elements in the alloy substrate.