Isothermal models for anode-supported tubular solid oxide fuel cells

Modeling of solid oxide fuel cells (SOFCs) has gained considerable significance in recent years. A detailed phenomenological model for SOFC can be used to understand performance limitations, optimization, in situ diagnostics and control. In this paper, we study the transport and various electrochemical phenomena in an anode-supported tubular SOFC using a steady-state model. In particular, we discuss the importance of modeling different phenomena vis-a-vis their impact on the prediction capability of the model. It is observed that even a reasonably simple model can be sufficiently predictive in a particular operating range. As the operating range of the cell is increased, the predictive capability of a model validated in a narrow range cannot be guarantied. It has also been observed that neglecting momentum conservation in the model for a tubular SOFC can affect the predictive capability of the model at higher overpotentials. An extensively validated model is used to study the percentage conversion of oxygen and oxygen concentration profile within a cell at different operating conditions. All of the simulation studies are supported by experimental data that spans a wide range of operation in terms of the DC polarization, reactant flow rates and operating temperatures.     

Effect of yttrium-stabilized bismuth bilayer electrolyte thickness on the electrochemical performance of anode-supported solid oxide fuel cells

Lowering operating temperature and optimizing electrolyte thickness, while maintaining the same high efficiencies are the main considerations in fabricating solid oxide fuel cells (SOFCs). In this study, the effect of yttrium-stabilized bismuth bilayer electrolyte thickness on the electrical performance was investigated. The yttrium-stabilized bismuth bilayer electrolyte was coated on the nickel–samarium-doped composite anode/samarium-doped ceria electrolyte substrate with varying bilayer electrolyte thicknesses (1.5, 3.5, 5.5, and 7.5 μm) via dip-coating technique. Electrochemical performance analysis revealed that the bilayer electrolyte with 5.5 μm thickness exhibited high open circuit voltage, current and power densities of 1.068 V, 259.5 mA/cm² and 86 mW/cm², respectively at 600 °C. Moreover, electrochemical impedance spectroscopy analysis also exhibited low total polarization resistance (4.64 Ωcm²) at 600 °C for the single SOFC with 5.5 μm thick yttrium-stabilized bismuth bilayer electrolyte. These findings confirm that the yttrium-stabilized bismuth bilayer electrolyte contributes to oxygen reduction reaction and successfully blocks electronic conduction in Sm_0.2Ce_0.8O_1.9 electrolyte materials. This study has successfully produced an Y_0.25Bi_0.75O_1.5/Sm_0.2Ce_0.8O_1.9 bilayer system with an extremely low total polarization resistance for low-temperature SOFCs.     

Slip casting combined with colloidal spray coating in fabrication of tubular anode-supported solid oxide fuel cells

A simple and cost-effective slip casting technique was successfully developed to fabricate NiO–YSZ anode substrates for tubular anode-supported single SOFCs. An YSZ electrolyte film was coated on the anode substrates by colloidal spray coating technique. A single cell, NiO–YSZ/YSZ (20 μm)/LSM–YSZ, using the tubular anode supports with YSZ coating, was assembled and tested to demonstrate the feasibility of the techniques applied. Using humidified hydrogen (75 ml/min) as fuel and ambient air as oxidant, the maximum power densities of the cell were 760 mW/cm² and 907 mW/cm² at 800 °C and 850 °C, respectively. The observed OCV was closed to the theoretical value and the SEM results revealed that the microstructure of the anode fabricated by slip casting is porous while the electrolyte film coated by colloidal spray coating is dense.     

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.     

A medium entropy cathode with enhanced chromium resistance for solid oxide fuel cells

Perovskite type SrCo_0.9Ta_0.1O_3-δ (SCT91) cathode exhibits high activity for oxygen reduction reactions, but the instability in Cr-containing atmosphere restricts its application in intermediate temperature solid oxide fuel cells (IT-SOFCs). In this study, a B-site medium-entropy SrCo_0.5Fe_0.2Ti_0.1Ta_0.1Nb_0.1O_3-δ (SCFTTN52111) cathode is proposed and investigated as a potential Cr-tolerance cathode. The electrochemical activity of pristine SCT91 cathode degrades rapidly in the presence of volatile chromium species. In contrast, SCFTTN52111 performs very stable. Chromium vapors prefer to react with segregated SrO species rather than Co₃O₄ precipitates_. Significant secondary phases of SrCrO₄ and Co₃O₄ are detected on SCT91 electrode, while only trace by-products are found on medium-entropy cathode. The better Cr tolerance is closely related to the enhanced structural stability by medium-entropy engineering and reduced surface Sr segregations. This work sheds light on the development of robust cathodes for IT-SOFCs through rational design of configuration entropy.     

Performance of an anode-supported tubular solid oxide fuel cell (SOFC) under pressurized conditions

An anode-supported tubular solid oxide fuel cell (SOFC) with a 15-μm thick YSZ electrolyte and an active area of 100 cm² was successfully fabricated by co-firing process, and the cell performance was measured under both atmospheric and pressurized conditions. The experimental results showed that the cell performance was significantly improved under the pressurized condition. When the pressure was increased from 1 to 6 atm, the maximum power density increased from 135.0 to 159.0 mW cm⁻² at 650 °C, and from 266.7 to 306.0 mW cm⁻² at 800 °C. The maximum power density at 800 °C and 4 atm was decreased from 334.8 to 273.9 mW cm⁻² when increasing the fuel utilization from 10% to 90%. Under the test condition of 70% fuel utilization, 800 °C and 4 atm, the cell could run stably at 0.7 V and 350 mA cm⁻² for 50 h, almost without any performance loss.     

Inert substrate-supported microtubular solid oxide fuel cells based on highly porous ceramic by low-temperature co-sintering

Inert substrate-supported microtubular solid oxide fuel cells (MT-SOFCs) are attractive due to their advantages, including high reduction–oxidation (redox) cycling stability and thermal cycling tolerance. A method involving sequential dip-coating, leaching, and co-sintering was developed and applied to fabricate inert substrate-supported MT-SOFCs through acid leaching nickel from the conventional Ni–yttria-stabilized zirconia (YSZ) anode. A thin current collector was deposited onto the support surface to minimize the current collection losses by collecting current from the entire surface area of the anode. A dense electrolyte could be obtained at a co-sintering temperature of 1250?°C. The produced MT-SOFC with the configuration of porous zirconia support/Ni–Scandia-stabilized zirconia (SSZ) anode current collector/Ni-SSZ anode/SSZ electrolyte/strontium-doped lanthanum manganite (LSM)-SSZ cathode/LSM cathode current collector was evaluated by electrochemical characterization tests. The inert substrate-supported MT-SOFC exhibited the maximum power densities of 616, 542, 440, and 300?mW?cm^?2 at 800, 750, 700, and 650?°C, respectively using dry hydrogen and air. In addition, the thermal cycling stability of the MT-SOFC was evaluated. The cell survived from thermal cycling tests and came out intact after 50 thermal cycles between 700?°C and 400?°C during an operation time of 50?h.     

BSCF/GDC as a refined cathode to the single-chamber solid oxide fuel cell based on a LAMOX electrolyte

In an effort to build the solid oxide fuel cell for intermediate temperature operations, the oxide ion conductor member of LAMOX family appears to be an ideal candidate for electrolyte since its parent crystal La₂Mo₂O₉ shows a monoclinic-cubic phase transition around 580 °C. Nonetheless, members of the LAMOX family are much less refractory than the conventional electrode compositions which are targeted to coordinate with the electrolyte of yttrium stabilized zirconia. In this work, we study the viability of a cathode composite of Ba_0.5Sr₀₅Co_0.8Fe_0.2O₃ (BSCF) and gadolinium doped ceria (GDC) to match the electrolyte La_1.8Dy_0.2Mo₂O₉ (LDM). Severe interfacial reactions between BSCF and LDM require a ceria-based diffusion barrier between them. The iron-doped GDC barrier of high sinterability is a convenient choice to block the unwanted reactions, allowing us to devise a BSCF/GDC composite cathode of gradient GDC content to relieve thermal stresses. The cell, operated in a mixed reactant chamber with flowing methane/air, functions properly at operation temperature 625–700 °C. Its maximum power output is recorded at 675 °C, since the BSCF crystal begins to degrade at 700 °C under the methane/air atmosphere.     

Development of LSM/YSZ composite cathode for anode-supported solid oxide fuel cells

This paper presents the effect of (La,Sr)MnO₃ (LSM) stoichiometry on the polarization behaviour of LSM/Y₂O₃-ZrO₂ (YSZ) composite cathodes. The composite cathode made of A-site deficient (La_0.85Sr_0.15)_0.9MnO₃ (LSM-B) showed much lower electrode interfacial resistance and overpotential losses than that made of stoichiometric (La_0.85Sr_0.15)_1.0MnO₃ (LSM-A). The much poorer performance of the latter is believed to be due to the formation of resistive substances such as La₂Zr₂O₇/SrZrO₃ between LSM and YSZ phases in the composite electrode. A slight A-site deficiency (∼0.1) was effective in inhibiting the formation of these resistive substances. A power density of ∼1 W cm⁻² at 800 °C was achieved with an anode-supported cell using an LSM-B/YSZ composite cathode. In addition, the effects of cathodic current treatment and electrolyte surface grinding on the performance of composite cathodes were also studied.     

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.     

Sr and Fe co-doped Ba2In2O5 as a new proton-conductor-derived cathode for proton-conducting solid oxide fuel cells

BaSrInFeO₅ (BSIF), a new cathode material for proton-conducting solid oxide fuel cells (SOFCs), is designed based on the modification of the Ba₂In₂O₅ proton conductor with Sr and Fe cations. Compared with the Ba₂In₂O₅ proton conductor tailored with only Fe cations (Ba₂InFeO₅, BIF), doping Sr can improve the chemical stability and also benefit the formation of oxygen vacancies. The proton mobility is also improved with Sr-doping, which is confirmed by first-principles calculations and experimental studies. An H-SOFC using the BSIF cathode generates a relatively high peak power density of 1192 mW cm^-2 at 700 ^oC, which is superior to many cells in previous reports. First-principles calculations find that the cathode oxygen reduction reaction (ORR) energy barrier for BSIF is significantly lower than that for BIF. Although Ba₂In₂O₅ is less studied, the derived cathode materials can still present decent performance, probably offering new material selections for H-SOFCs.     

Optimization of a ScCeSZ/GDC bi-layer electrolyte fabrication process for intermediate temperature solid oxide fuel cells

Cost-effective wet ceramic coating techniques for fabricating ScCeSZ/GDC bi-layer electrolyte anode-supported button cells were investigated in this study. Aqueous ceramic slurries were prepared by ball milling and then used for Ni/ScCeSZ half cell fabrication by tape casting and spin coating. Prepared cells were tested at operating temperature between 700 and 800°C with a fuel composition of hydrogen:nitrogen 3:1 and air at the cathode. The cell with a spin coated GDC film showed the maximum power density of 1.142, 1.012, 0.813 W?cm^?2 at 800, 750, and 700°C, respectively. It was also able to produce power output around 0.7 W?cm^?2 for 500 h at 750°C, which confirms the cell operational stability. More importantly, the GDC film prepared by spin coating effectively avoided the formation of the (Zr,Ce)O₂^?based solid solution at the ceria/zirconia interface compared with the other cells with the co-casted and sintered GDC film.     

Development of La(CrCoFeNi)O3 system perovskites as interconnect and cathode materials for solid oxide fuel cells

The purpose of this research is to develop interconnect and cathode materials for use in solid oxide fuel cells (SOFCs) which demonstrate desired properties of outstanding sintering properties, high electrical conductivity, and excellent chemical stability at high temperatures. Five different perovskite oxides of lanthanum in combination with chromium, iron, cobalt and nickel oxides powders, i.e. LaCr_0.7Co_0.1Fe_0.1Ni_0.1O₃(LCr7CFN), LaCo_0.7Cr_0.1Fe_0.1 Ni_0.1O₃(LCo7CFN), LaFe_0.7Cr_0.1Co_0.1Ni_0.1O₃(LFe7CCN), LaNi_0.7Cr_0.1Co_0.1Fe_0.1O₃(LNi7CCF), and LaCr_0.25Co_0.25Fe_0.25Ni_0.25O₃(LCCFN), were synthesized through the Pechini method. XRD results show that all materials are in single phase, either rhombohedral or orthorhombic crystal structure. The resulting powders were able to be sintered to a high relative density at a temperature of 1400 °C for 2 h in air. The electrical conductivity of the sintered sample was measured and evaluated from 300 °C to 800 °C. The LCCFN sample appears to have the best combination of sintering property (approximate 94% relative density) and electrical conductivity (88.13 Scm⁻¹ at 800 °C).     

阳极支撑微管式固体氧化物燃料电池的研究进展

近些年来,微管式固体氧化物燃料电池(SOFC)由于其具有密封简单、体积能量密度高、抗热震性好、启动时间快等优点备受关注。本文主要介绍了微管式SOFC的优势,并重点概述了阳极支撑型微管式SOFC的制备方法、研究现状和未来的发展方向。分别对采用塑性挤出法和相转化法制备的阳极支撑微管式SOFC的技术进展进行了综述。介绍了阳极支撑微管式SOFC电池堆的设计理念,并对未来微管式SOFC的发展方向进行了展望。     

Enhancing the performance of traditional La2NiO4+x cathode for proton-conducting solid oxide fuel cells with Zn-doping

A Zn-doping strategy was employed to modify the Ruddlesden-Popper (R–P) structure oxide La₂NiO_4+x to improve hydration and proton diffusion ability. First-principles calculations indicated the formation of interstitial oxygen instead of oxygen vacancy is favorable for Zn-modified and Zn-free La₂NiO_4+x. The doping of Zn significantly lowered the hydration energy for La₂NiO_4+x and decreased the proton migration barrier. The electrical conductivity relaxation confirmed that the Zn-modified La₂NiO_4+x sample had a higher proton diffusion rate than the Zn-free sample. Furthermore, the Zn-doping strategy did not alter the thermal expansion behavior of the material, and both Zn-modified and Zn-free La₂NiO_4+x samples showed a similar thermal expansion coefficient value, which was also close with the electrolyte materials. As a result, the Zn-modified La₂NiO_4+x exhibited suitability as the cathode for proton-conducting solid oxide fuel cells (H–SOFCs). An H–SOFC using the Zn-modified La₂NiO_4+x showed a relatively high peak power density of 1070 mW cm^-2 at 700 °C, significantly larger than that La₂NiO_4+x-based H–SOFCs reported previously.     

Direct-methane anode-supported solid oxide fuel cells fabricated by aqueous gel-casting

Direct methane Solid Oxide Fuel Cells (SOFCs) operated under catalytic partial oxidation (CPOX) conditions are investigated, focusing on the processing of the anode support and the anode deactivation caused by carbon deposition. Anode-supported SOFCs based on gadolinium-doped ceria (GDC) electrolyte, and NiO-GDC anode support were fabricated by the gel-casting method. Suitable aqueous slurries formulations of NiO–GDC were prepared, starting NiO-GDC nanocomposite powders, agarose as gelling agent and rice starch as pore former. Electrochemical and mechanical tests evidenced that the support of 550 ± 50 µm thickness and 10 wt% pore former is a good candidate for direct-methane SOFCs. The cells operating under stoichiometric conditions of CPOX reached a performance of 0.64 W·cm^?2 at 650 ºC, a very close value to that measured under humidified hydrogen (0.71 W·cm^?2). The best electrochemical stability of the cell is achieved at a CH₄/O₂ ratio of 2.5, showing no evidence of carbon deposition and reducing nickel re-oxidation significantly.     

Controlling cation migration and inter-diffusion across cathode/interlayer/electrolyte interfaces of solid oxide fuel cells: A review

Solid oxide fuel cells (SOFCs) have attracted great interest as an alternative potential way to become the most efficient and cleanest electrochemical energy conversion system. The commercialization of SOFC technology is hindered by the degradation of component materials. The durable and high performing cathode materials is of immense importance in the durability improvement of SOFCs. Cobaltite type perovskite-based oxides have shown remarkable results but cation migration and formation of the insulating phases within and near the interface between cathode and electrolyte is often observed, which impacts greatly on the electrochemical performance and durability. Therefore, the reaction barrier layer (interlayer) typically made of doped ceria is required between cathode and electrolyte. The stability of this layer due to cations cross-migration between cathode and electrolyte and interdiffusion with electrolyte during fabrication and operation is presently one of the foremost issues (motivation) in the SOFC industry. The chemical and structural disparity associated with the cations migration and interdiffusion could affect the stability and functionality of different layers of SOFC. Understanding the formation of secondary phases and their evolution during the operating lifespan is thought-provoking because of the complexity of the system and the occurrence of numerous other processes simultaneously. In this review paper, the recent progress and advancement in this extent are presented, emphasizing the key driving forces, kinetics, analysis techniques at the micro- and nano-scale levels, and cations migration in extensively studied perovskite-based materials. An insightful understanding of the interdiffusion phenomenon taking place in the cathode/electrolyte/interlayer of SOFCs and control measures are then highlighted which is important to achieve the rational design of highly efficient SOFC with outstanding stable performance.     

Telescopic projective Adams multiscale modeling of electrochemical reactions in tubular solid oxide fuel cells

In order to predict the electrochemical performance of Solid Oxide Fuel Cells (SOFCs), a telescopic projective Adams (TPA) multiscale simulation method is proposed in this work. This method is constructed on the basis of the equation-free method (EFM). A lattice Boltzmann model is used as the fine-scale simulator of the proposed method. The electrochemical reaction-diffusion process was simulated by the TPA and the lattice Boltzmann method (LBM). The results of the two methods were found to be in good agreement, and the TPA method can give accurate results with lower computational costs. The electrochemical reactions were also simulated based on the TPA method. The results were consistent with the experimental data, indicating that the proposed TPA method is an effective tool to simulate the electrochemical reactions of SOFCs. Also, the proposed method is suggested to be helpful in multiscale modeling of other energy systems.     

Review of perovskite-structure related cathode materials for solid oxide fuel cells

In this article, different perovskite-structure related materials are reviewed, which could be potential candidates for cathode materials in solid oxide fuel cells. Solid oxide fuel cells provide an alternative, environmentally viable and efficient option to conventional electricity-producing devices. Different properties are required for the materials to qualify as a cathode for solid oxide fuel cells. Therefore, the analysis and review are done based on the process parameters and their effect on the electrical conductivity, electrochemical properties, the coefficient of thermal expansion and mechanical properties of different cathode materials. Fracture toughness and hardness have been the focus while analysing the mechanical properties. The selection of the initial composition, dopants and their valence plays a vital role in deciding the properties mentioned above of cathode materials. The prospective cathode materials classified as cobalt-based and cobalt-free are further bifurcated based on the A-site elements of the perovskite (ABO₃) structure. Also given in this article is the summary of the latest development on the cathode materials. As observed from the properties studied, cobalt-based materials tend to have higher conductivity than cobalt-free materials. While cobalt-free compositions are cost-effective and have a comparable coefficient of thermal expansion with other components of solid oxide fuel cells. The last section of the article gives the future scope of the research.     

Low-temperature constrained sintering of YSZ electrolyte with Bi2O3 sintering sacrificial layer for anode-supported solid oxide fuel cells

Solid oxide fuel cells (SOFCs) have strong potential for next-generation energy conversion systems. However, their high processing temperature due to multi-layer ceramic components has been a major challenge for commercialization. In particular, the constrained sintering effect due to the rigid substrate in the fabrication process is a main reason to increase the sintering temperature of ceramic electrolyte. Herein, we develop a bi-layer sintering method composed of a Bi₂O₃ sintering sacrificial layer and YSZ main electrolyte layer to effectively lower the sintering temperature of the YSZ electrolyte even under the constrained sintering conditions. The Bi₂O₃ sintering functional layer applied on the YSZ electrolyte is designed to facilitate the densification of YSZ electrolyte at the significantly lowered sintering temperature and is removed after the sintering process to prevent the detrimental effects of residual sintering aids. Subsequent sublimation of Bi₂O₃ was confirmed after the sintering process and a dense YSZ monolayer was formed as a result of the sintering functional layer-assisted sintering process. The sintering behavior of the Bi₂O₃/YSZ bi-layer system was systematically analyzed, and material properties including the microstructure, crystallinity, and ionic conductivity were analyzed. The developed bi-layer sintered YSZ electrolyte was employed to fabricate anode-supported SOFCs, and a cell performance comparable to a conventional high temperature sintered (1400 °C) YSZ electrolyte was successfully demonstrated with significantly reduced sintering temperature (<1200 °C).