Chromium poisoning for prolonged lifetime of electrodes in solid oxide fuel cells - Review

Solid Oxide Fuel Cells (SOFCs) offer low carbon emission and high efficient energy conversion systems. For the wide commercial distribution of this system, one of the technological issues and challenges is prolonged durability: the SOFC systems should have a long lifetime of more than 10 years. The volatile chromium species poisoning is the key degradation factor to overcome at the functional ceramics of air electrode (cathode)/interlayer/electrolyte interfaces in the SOFC system among many degradation factors. This paper reports recent degradation mechanisms, especially on the chromium (Cr) vapors poisoning at the perovskite oxide cathode. The Cr-concentration levels at cathodes were evaluated from the reported data at small cells and practical cell-stacks. The interactions of volatile Cr species and perovskite oxide cathode surface were evaluated by the chemical reaction of cathode materials with Cr-vapors to form SrCrO₄ and the electrochemical induced Cr-vapors reduction (Cr⁶⁺ to Cr³⁺) to form Cr₂O₃ at (La,Sr,Ca)MnO₃-based and (La,Sr)(Co,Fe)O₃-based materials. Recovery mechanism from Cr-poisoning was reanalyzed at the (La,Sr)(Co,Fe)O₃/ceria-based interlayer/YSZ electrolyte interfaces by Cr-cleaning reaction with the evaporation of Cr₂O₃/SrCrO₄ and nano-meter level cation migration/rearrangement effects with phase separation and new phases formation. This paper is covering not only the elucidation of degradation mechanism but also the fundamentals of physical and chemical analyses on perovskite oxide cathode surface and interfaces. An insight for new materials combination for the next-generation SOFCs is also included.     

Materials Development for Advanced Planar Solid Oxide Fuel Cells

High-power density and high durability are the main targets for solid oxide fuel cell (SOFC) development at Forschungszentrum Jülich. Power density has been further increased by variation of the material composition of perovskite-based cathodes (Sr content, Co content, substoichiometry) and by optimization of the diffusion barrier (Gd-substituted ceria) between an electrolyte and a cathode. The application of dense diffusion barrier layers significantly improved the performance. The associated avoidance of SrZrO₃ formation, however, contributed only to a small extent to the improvement of durability of SOFCs with LSCF cathodes. The redox stability of anode-supported SOFCs has been addressed in two ways: (a) conventional Ni/yttria-stabilized zirconia anode substrates have been investigated to explore the limits of re-oxidation and to determine the degree of oxidation at which no damages occur. (b) Alternative anodes and anode substrates are under development, which basically consist of mixed-conducting ceramics. Avoiding the high amount of nickel decreases the probability of failure, but does not automatically lead to redox-stable anodes. The differences in the materials' properties of such ceramics in oxidizing and reducing environment are addressed.     

Fabrication of thin-film gadolinia-doped ceria (GDC) interdiffusion barrier layers for intermediate-temperature solid oxide fuel cells (IT-SOFCs) by chemical solution deposition (CSD)

A dense gadolinia-doped ceria (GDC) interdiffusion barrier layer as thin as 300 nm was successfully fabricated on a rigid anode/electrolyte bilayer substrate using the chemical solution deposition (CSD) process for intermediate temperature solid oxide fuel cells (SOFCs). Drying-related macro-defects were removed by employing drying control chemical additives (DCCA), which effectively relieved drying stresses. The major process flaws caused by the constraining effects of the rigid substrate were completely eliminated by the addition of GDC nanoparticles into the chemical solution, which suppressed the generation of microstructural anisotropy by mitigating the predominant bi-axial substrate constraints. As a consequence, a thin film GDC interlayer was successfully deposited with a high volumetric density, effectively preventing the chemical interaction between the electrolyte and cathode during the fabrication process and subsequent operation. The cell test and microstructural analysis confirmed excellent electrochemical performance and structural and chemical stability. The CSD process presented in this paper is considered to be a promising technology for the practical preparation of GDC thin film barrier layers for intermediate temperature SOFCs based on the film quality, processing costs and potential for large-scale production.     

Effect of transition metal doping on the sintering and electrochemical properties of GDC buffer layer in SOFCs

A dense Ce_0.9Gd_0.1O_2−d (GDC) interlayer is an essential component of the SOFCs to inhibit interfacial elemental diffusion between zirconia-based electrolytes (eg YSZ) and cathodes. However, the characteristic high sintering temperature of GDC (>1400°C) makes it challenging to fabricate an effective highly dense interlayer owing to the formation of more resistive (Zr,Ce)O₂ interfacial solid solutions with YSZ at those temperatures. To fabricate a useful GDC interlayer, we studied the influence of transition metal (TM) (Co, Cu, Fe, Mn, & Zn) doping on the sintering and electrochemical properties of GDC. Dilatometry data showed dramatic drops in the necking and final sintering temperatures for the TM-doped GDCs, improving the densification of the GDC in the order of Fe > Co > Mn > Cu > Zn. However, the electrochemical impedance data showed that among various transition metal dopants, Mn doping resulted in the best electrochemical properties. Anode supported SOFCs with Mn-doped, nano, and commercial-micron GDC interlayers were compared with regard to their performance and stability levels. Although all of the SOFCs showed stable performance, the SOFC with the Mn-doped GDC interlayer showed the highest power density of 1.14 W cm⁻² at 750°C. Hence, Mn-doped GDC is suggested for application as an effective diffusion barrier layer in SOFCs.     

Nano-structured composite cathodes for intermediate-temperature solid oxide fuel cells via an infiltration/impregnation technique

Solid oxide fuel cells (SOFCs) are high temperature energy conversion devices working efficiently and environmental friendly. SOFC requires a functional cathode with high electrocatalytic activity for the electrochemical reduction of oxygen. The electrode is often fabricated at high temperature to achieve good bonding between the electrode and electrolyte. The high temperature not only limits material choice but also results in coarse particles with low electrocatalytic activity. Nano-structured electrodes fabricated at low temperature by an infiltration/impregnation technique have shown many advantages including superior activity and wider range of material choices. The impregnation technique involves depositing nanoparticle catalysts into a pre-sintered electrode backbone. Two basic types of nano-structures are developed since the electrode is usually a composite consists of an electrolyte and an electrocatalyst. One is infiltrating electronically conducting nano-catalyst into a single phase ionic conducting backbone, while the other is infiltrating ionically conducting nanoparticles into a single phase electronically conducting backbone. In addition, nanoparticles of the electrocatalyst, electrolyte and other oxides have also been infiltrated into mixed conducting backbones. These nano-structured cathodes are reviewed here regarding the preparation methods, their electrochemical performance, and stability upon thermal cycling.     

Investigation of LSM-8YSZ cathode within an all ceramic SOFC. Part I: Chemical interactions

This work focuses on a novel, co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. The objective is the understanding of interaction and degradation mechanisms of the cathode and current collector layers within the design during co-sintering. Half cells consisting of silicate mechanical support, lanthanum strontium manganite (LSM) current collector, LSM mixed with 8 mol% yttria-stabilized zirconia (8YSZ) composite cathode and 8YSZ electrolyte were co-sintered at 1150 °C < T < 1250 °C. Crystallographically stable LSM compositions within the design were identified. However, the cathode and silicate/electrolyte interacted by interdiffusion of Zn (gas diffusion) and Mn (solid diffusion), and by the formation of several reaction phases (between silicate and cathode only). Introducing silicate poisoning decreased the electrochemical performance of the cell by around 40%. This is likely due to the formation of the Zn- and Mn-rich phase in the cathode, but may also be caused by a higher ohmic resistance of the current collector.     

氨燃料固体氧化物燃料电池性能研究进展与展望

氨是一种零碳燃料,也是富氢载体,具有较大储运优势。固体氧化物燃料电池(solid oxide fuel cell, SOFC)是一种清洁高效发电装置,在分布式发电、热电联供、储能调峰等领域有广阔应用前景,氨气可直接用作SOFC阳极燃料以实现高效、清洁、低成本发电。首先简介了质子传导型和氧离子传导型氨SOFC的工作原理,电解质、电极材料的选择以及氨气在阳极的分解过程。其次总结了氨SOFC的实验研究现状,以单电池最大功率密度为评价指标,综述了不同电解质/电极材料、电解质厚度、操作温度等因素下两种传导类型的氨SOFC的性能表现,并分析了造成电池性能差异的原因。之后介绍了氨SOFC当前面临的挑战,最后对氨SOFC未来研究方向、热电联供系统的应用进行了展望。     

Synthesis, structural analysis and electrochemical performance of low-copper content La2Ni1−xCuxO4+δ materials as new cathodes for solid oxide fuel cells

In order to enhance the electrochemical performance of solid oxide fuel cells (SOFCs), La₂Ni_1−xCuO_4+δ (x = 0, 0.01, 0.02, 0.05 and 0.1) doped with copper in percentages, varying between 1% and 10%, were prepared following the modified Pechini method. The microstructure and morphology of the samples were analyzed by XRD and SEM. The electrochemical performance was followed by impedance spectroscopy. La₂Ni_0.99Cu_0.01O_4+δ samples showed good electrochemical and physicochemical properties with respect to the undoped material and is potentially a promising cathode. Indeed, doping with such small amounts of copper (1%) into the nickel site led to the formation of pure phases and stabilized the material before and after use at high temperature under air. In contrast, doping with higher amounts of copper (2%, 5% and 10%) led, after heating at 1000 °C for 48 h, to the formation of another phase resulting from the diffusion of copper into the YSZ electrolyte, limiting the interest to these materials as SOFC cathodes.     

Characterizations of impedance responses in an anode-supported solid oxide fuel cell with an air blowing system

Effects of operation parameters on impedance responses are characterized to study electrochemical reactions of an anode-supported solid oxide fuel cell (SOFC) in an air blowing operation. The anode-supported SOFC, which consists of Ni-yttrium stabilized zirconia (YSZ) support/Ni-YSZ anode functional layer/YSZ electrolyte/gadolinium doped ceria (GDC) interlayer/La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ -GDC cathode, is fabricated by a tape casting and co-firing process. To investigate the electrochemical response on impedances, an equivalent circuit is modeled with five elements and fitted by the complex nonlinear least square (CNLS) method. Based on the impedance spectra with the operation parameters, two among five elements are clarified to be concerned with anodic reactions and another two concerned with gas diffusion reactions in electrodes. It is difficult to clarify one among five elements with the results here. The clarified elements may be used to study the effects of materials and processes for SOFC with impedance responses, which will be helpful to improve the performance and reliability.     

Al_2O_3包覆锂电池正极材料LiMn_2O_4的合成及电化学性能研究

研究了在锂离子电池尖晶石Li Mn2O4正极材料上包覆Al2O3来改善材料在循环过程中的容量衰减问题。通过SEM和X射线衍射研究材料的表观形貌和晶体结构。在电化学性能测试中,发现包覆Al2O3可以减少材料与电解液的直接接触,阻止了电解液对尖晶石的侵蚀,最终有效地改进锂电池正极材料Li Mn2O4的电化学性能。     

Formation of chromium containing impurities in (La,Sr)MnO3 solid-oxide-fuel-cell cathodes under stack operating conditions and its effect on performance

In this study, we present an investigation of the chromium-related electrical performance degradation of anode-supported SOFCs with a LSM/YSZ composite cathode. A traditional ferritic interconnect steel with high chromium content is established as the primary chromium source and chromium poisoning of the cathode is carried out at relevant SOFC operating conditions. The prolonged influence of the gaseous chromium species on the cell performance and cathode microstructure under constant current conditions was examined quantitatively. Physical deposition of chromium(III) compounds (mainly spinel-type (Cr,Mn)₃O₄ phases) was observed at the electrochemically active region adjacent to the electrolyte only under realistic constant current conditions. The microstructural degradation associated with the formation of secondary phases correlated directly with the performance degradation, the effective chromium partial pressure and the current density. Furthermore, the influence of the presence of a number of protecting layers on the interconnect steel was evaluated with regard to the cathode poisoning. It was shown that chromium-induced degradation was reduced drastically when an additional manganese reservoir layer and a Cr getter layer were applied.     

Modeling and Optimization of Anode‐Supported Solid Oxide Fuel Cells on Cell Parameters via Artificial Neural Network and Genetic Algorithm

An artificial neural network (ANN) and a genetic algorithm (GA) are employed to model and optimize cell parameters to improve the performance of singular, intermediate‐temperature, solid oxide fuel cells (IT‐SOFCs). The ANN model uses a feed‐forward neural network with an error back‐propagation algorithm. The ANN is trained using experimental data as a black‐box without using physical models. The developed model is able to predict the performance of the SOFC. An optimization algorithm is utilized to select the optimal SOFC parameters. The optimal values of four cell parameters (anode support thickness, anode support porosity, electrolyte thickness, and functional layer cathode thickness) are determined by using the GA under different conditions. The results show that these optimum cell parameters deliver the highest maximum power density under different constraints on the anode support thickness, porosity, and electrolyte thickness.     

晶须/纤维增强3D打印氧化锆多孔陶瓷制备及性能研究

钇稳定氧化锆（YSZ）是一种抗氧化性和耐久性优异的陶瓷,够承受高温,非常适合作热防护材料。采用乳液/泡沫模板法将其制成具有微米级孔的多孔结构,再以氧化铝晶须或氧化锆纤维作为增强相,然后结合直写成型这种3D打印成型技术,又可在毫米级孔尺度上获得设计的自由。由此制备的梯度多孔结构,不仅可以增大材料的比表面积,减小体积密度,更能大大提高多孔YSZ的力学性能。研究增强体的类型、加入量及烧结温度对多孔氧化锆陶瓷微观形貌结构的影响,分析其与抗压强度的相互作用关系。结果表明,氧化铝晶须和氧化锆纤维的加入,均能有效提高多孔氧化锆陶瓷孔的抗压强度,晶须的增强效果更好。氧化锆纤维加入量为4wt%的多孔氧化锆陶瓷孔隙率最高,抗压强度提升最小,为166.6MPa。在1500℃烧结温度下,当氧化锆纤维加入量为8wt%时,抗压强度最大,达到269.36MPa。     

中间相炭微球在锂离子电池负极材料的应用进展

中间相炭微球(MCMB)具有良好锂离子扩散性、导电性和机械稳定性等优势,是目前应用广泛、综合性能优异的锂离子电池负极材料,但较低理论比容量是制约其发展的关键因素。为了获得性能优良的MCMB基锂离子电池负极材料,改性修饰和复合材料已然成为目前研发重点。笔者论述了碳结构、表界面和复合材料等微观结构设计对MCMB负极材料电化学性能的影响。从碳堆积结构类型、有序性、层间距以及球体粒径大小等方面,论述了碳结构微观设计对MCMB电化学性能的影响。发现具有乱层结构的MCMB在充放电过程中内部产生应力较小,且碳结构较稳定,具有优异循环稳定性;内部具有大量微孔或碳层间距较大的MCMB,在充放电过程中可提高锂离子在电极中的迁移速率,并提供更多的储锂空间,一般具有优良的充放电比容量和倍率性能;小粒径MCMB具有较短的锂离子迁移路径和随之增加的比表面积,通常具有较好倍率性能,伴随着可逆比容量和充放电效率的衰减。从表界面碳层改性、包覆和掺杂改性等方面,论述了表界面改性对MCMB电化学性能的影响。表面碳层修饰可增加MCMB与电解液的相容性及其比表面积,提高了与电解液的接触面积及贮锂容量,改善了锂离子电池负极材料的电化学性能;另外,MCMB表面包覆一层无定型碳,可避免其表面与电解液直接接触,减少电化学副反应的产生,提升其可逆比容量。从碳活性物质复合材料、非碳活性物质复合材料等方面,论述了复合材料微观结构设计对MCMB电化学性能的影响。碳活性物质可降低MCMB内部碳层结构的有序性,减少锂离子嵌入过程中的内部应力,提升MCMB循环稳定性。非碳活性物质诱导MCMB生成更加有序的碳层结构,提高MCMB的比表面积,从而改善MCMB表面与电解液分子的接触能力及其嵌锂性能,有利于提升MCMB负极材料可逆比容量、循环性能和倍率性能。MCMB具有高碳层间距和多缺陷位点等结构特征,有利于钠离子自由脱嵌,应用于钠离子电池时具有良好的可逆比容量、循环稳定性和倍率性能。MCMB的不规则定向层状结构经活化等处理具有较高比表面积,可应用于超级电容器电极材料。最后提出在高性能锂离子电池电极材料快速发展的需求下,从微观结构角度设计MCMB纳米复合材料将是MCMB负极材料的研究重点。     

Thermodynamic Analysis of Methane-fueled Solid Oxide Fuel Cells Considering CO Electrochemical Oxidation

abstract Thermodynamic analyses in the literature have shown that solid oxide fuel cells (SOFCs) with proton conducting electrolyte (H-SOFC) exhibited higher performance than SOFC with oxygen ion condu...     

Effect of applied current density on the degradation behavior of anode-supported flat-tubular solid oxide fuel cells

The effects of applied current density on the long-term performance degradation behavior of anode-supported flat-tubular type solid oxide fuel cells (SOFCs) are studied. Durability tests on the anode-supported SOFCs are conducted galvanostatically at 800 °C as a function of applied current density (200, 450, 700 and 1000 mAcm^-2) for the duration of 1000 h. The performance degradation during the long-term test assessed by a voltage loss over time greatly increases with higher applied current density. The combined impedance spectroscopy and post-test characterization results show that the accelerated degradation at high current density is due to enhanced Ni particles coarsening in the anode, the formation of insulating phase between cathode and electrolyte, and evolution of fine particles in the cathode. Systematic degradation analysis conducted in the present study provides profound insight into the electrochemical performance decay of the anode-supported flat-tubular SOFCs.     

实心多孔支撑体全膜化微型固体氧化物燃料电池的制备及性能

提出一种实心多孔支撑体全膜化微型固体氧化物燃料电池(micro solid oxide fuel cell,μSOFC)设计模型.电池用氧化钇部分稳定的氧化锆[(ZrO2)0.97(Y2O3)0.03,partially stabilized zirconia,PSZ]多孔陶瓷作为支撑体,在其上制备NiO-YSZ阳极层,分别采用离心和浸渍两种成膜工艺制备YSZ电解质膜,以La0.8Sr0.2MnO3-YSZ复合材料为阴极,对组装好的单电池进行了电化学性能测试.在850℃和800℃时,离心沉积工艺制备的单电池最大输出功率密度分别为286 mW/cm2和254 mW/cm2,而浸渍涂布法制备单电池的最大输出功率密度则分别达到572 mW/cm2和388 mW/cm2.电化学阻抗谱显示;电极极化是影响电池性能的主要因素.     

Sr2−XLaXMgMoO6 and Sr2−XLaXMgNbO6 for Use as Sulfur‐Tolerant Anodes Without a Buffer Layer

The objective of this effort is to synthesize and characterize a series of lanthanum‐(La) doped Sr₂MgMoO₆ (SMMO) and La‐doped Sr₂MgNbO₆ (SMNO) anode materials which can be used in combination with lanthanum‐containing electrolytes to mitigate the effects of lanthanum poisoning in solid oxide fuel cells (SOFCs). Currently, an La_0.4Ce_0.6O_1.8 (LDC) buffer layer is used with many perovskite‐based anode materials to prevent La diffusion into the anode from the La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) electrolyte which can create a resistive La species that impedes electrochemical performance. The LDC buffer layer, with diminished electronic conductivity, adds an extra level of complexity in the SOFC manufacturing process. Further, this extraneous layer presents an added experimental challenge when assessing anode material performance. Overall electrochemical performance could be improved if the resistive buffer layer could be removed, thereby allowing the anode material to have direct contact with the electrolyte. To accomplish this, a new class of anode materials was synthesized with the goal of balancing “La” chemical potential between these neighboring materials. La‐doped SMMO and SMNO were prepared and studied. It was hypothesized that by incorporating La into the anode, the gradient of chemical activity between the anode and electrolyte would decrease, which would prevent La diffusion. These anode materials were synthesized via a sol–gel methodology and characterized with X‐ray diffraction to assess phase purity. The conductivity of the materials was analyzed in the presence of both H₂ and 100 ppm H₂S/H₂ to determine the stability and performance of these materials during device operation. The stability experiments demonstrated that 40% La‐doped SMNO is stable in all pertinent environments while not reacting with the LSGM electrolyte.     

Electrochemical Performance of a Ni and YSZ Composite Synthesised by Ultrasonic Spray Pyrolysis as an Anode for SOFCs

The electrochemical performance of an anode material for a solid oxide fuel cell (SOFC) depends highly on microstructure in addition to composition. In this study, a NiO–yttria‐stabilised zirconia (NiO–YSZ) composite with a highly dispersed microstructure and large pore volume/surface area has been synthesised by ultrasonic spray pyrolysis (USP) and its electrochemical characteristics has been investigated. For comparison, the electrochemical performance of a conventional NiO–YSZ is also evaluated. The power density of the zirconia electrolyte‐supported SOFC with the synthesised anode is ∼392 mW cm^–2 at 900 °C and that of the SOFC with the conventional NiO–YSZ anode is ∼315 mW cm^–2. The improvement is ∼24%. This result demonstrates that the synthesised NiO–YSZ is a potential alternative anode material for SOFCs fabricated with a zirconia solid electrolyte.     

Lowering the co-sintering temperature of cathode–electrolyte bilayers for micro-tubular solid oxide fuel cells

To prevent undesirable reactions between the cathode and electrolyte materials in cathode-supported solid oxide fuel cells (SOFCs), the co-sintering temperature of these two layers must be lowered. In the present work, we employed different strategies to lower the co-sintering temperature of cathode–electrolyte bilayers for micro-tubular SOFCs by increasing the cathode sintering shrinkage and adding sintering aids to the electrolyte. Strontium-doped lanthanum manganite (LSM) and yttria-stabilized zirconia (YSZ) were used as the cathode and electrolyte materials, respectively. To facilitate densification of the electrolyte layer by controlling the shrinkage of the cathode support, the particle size of the LSM powder was reduced by high-energy ball milling and different amounts of micro-crystalline cellulose pore former were used. Sintering aids, namely NiO and Fe₂O₃, were also added to the YSZ electrolyte to further improve its low-temperature sintering. Our results indicate that with the improvement in the cathode support shrinkage and use of the small amounts of sintering aids, the cathode–electrolyte co-sintering temperature can be reduced to 1250–1300 °C. It was also observed that the presence of the sintering aids helps to reduce the reactivity between the LSM cathode and YSZ electrolyte.