The influence of activated carbon as an additive in anode materials for low temperature solid oxide fuel cells

The effects of activated carbon (AC) as an additive in multi-oxide nano composite LiNiCuZn–O for application as anode in solid oxide fuel cell (SOFC) is reported. The composite was synthesized using solid state reactions method with varying content of AC in range 0.1%–0.9% for use as anode in the cell. The cell was composed of the synthesized composite as anode, LiNiCuZn–O as cathode and Samaria doped ceria (SDC) as electrolyte. The prepared composites were characterized for morphology and crystal structure by scanning electron microscope (SEM) and x-ray diffraction (XRD) respectively. Furthermore, the crystallite sizes of LiNiCuZn–O and LiNiCuZn–O with AC as an additive have been found in the range from 50 nm to 70 nm. The prepared composite materials were observed porous and the porosity of the sample having 0.5% additive was found highest. The conductivity and power density of the SOFC were studied at temperature of 600 °C. The maximum value of conductivity was found as 4.79 S/cm for the composite containing 0.5% AC as measured by using 4-probe method. The maximum value of power density of the fuel cell with anode comprising of 0.5% AC along with the mentioned cathode and the electrolyte was 455 mW/cm². Therefore, out of the compositions studied, the composite comprising of LiNiCuZn–O with 0.5% AC offered best performance for anode in the cell. This oxide composite is reported as a potential candidate for use as anode in low temperature SOFCs.     

Fabrication of one-step co-fired proton-conducting solid oxide fuel cells with the assistance of microwave sintering

A microwave sintering technique is reported for fabricating co-sintered proton-conducting solid oxide fuel cells. With this method, high-quality ceramic electrolyte membranes can be prepared at 1100?°C, thus enabling the fabrication of entire cells in a single step. The microwave sintering method not only enhances electrolyte densification but also improves the cathode/electrolyte interface, which is critical for improving fuel cell performance. The power output of the co-sintered cell prepared under the microwave conditions (up to 449?mW?cm^?2 at 700?°C) was significantly higher than that of the cell fabricated using the traditional co-sintering method (approximately 292?mW?cm^?2 at the same temperature). Electrochemical analysis revealed that the enhanced electrolyte density and the improved cathode/electrolyte interface achieved by using the microwave sintering technique decrease both the ohmic resistance and the polarisation resistance of the cell, leading to good fuel cell performance.     

Nanostructured engineering of nickel cermet anode for solid oxide fuel cell using inkjet printing

A single-step wet-chemical synthesis of NiO-SDC (Sm³⁺ doped ceria) colloidal ink for the inkjet printing (IJP) of nanostructured anodic layers with enhanced catalytic activity for solid oxide fuel cells (SOFCs) is developed and characterized. Dynamic light scattering, scanning electron microscope, and Raman spectroscopy revealed stable nanoparticles with the main size of 11.85 nm within the ink solution. Rheology parameters were analyzed, and the anode was printed. Porous post-sintered Ni-cermet layer, with a thickness of 15?25 μm contained near-spherical nanoparticles of 40?80 nm, was obtained. X-ray diffraction confirmed the phase composition of the cermet layer. Electrical impedance spectroscopy demonstrated a significant reduction, by more than 80 %, in the area-specific resistance of the IJP half-cell in comparison with the Screen-printed half-cell. The microstructure engineering using IJP provides fabrication of the cermet NiO-SDC layer with a conjugated structure, which ultimately enhances the catalytic activity of the SOFC.     

Characterization of core-shell structured Ni@GDC anode materials synthesized by ultrasonic spray pyrolysis for solid oxide fuel cells

Core-shell structured NiO@GDC powders with NiO cores and GDC shells were synthesized by ultrasonic spray pyrolysis (USP) with a four-zone furnace. The morphology of the as-synthesized powders can be modified by controlling parameters such as the precursor pH, carrier gas flow rate, and zone temperature. At high carrier gas flow rates, the as-synthesized core-shell structured NiO@GDC powders have raisin-like morphology with a rough surface; this is due to fast gas exhaustion and insufficient particle ordering. The core-shell structured Ni@GDC anode showed considerable electrochemical performance enhancement compared to the conventionally-mixed Ni-GDC anode. The polarization resistance (R_p) of conventionally-mixed Ni-GDC anodes increases gradually as a function of the operation time. Alternatively, the core-shell structured Ni@GDC anode synthesized by USP does not exhibit any significant performance degradation, even after 500 h of operation. This is the case because the rigid GDC ceramic shell in the core-shell structured Ni@GDC may restrain Ni aggregation.     

Fabrication and characterization of a Ni-YSZ anode support using high-frequency induction heated sintering (HFIHS)

Ni-YSZ cermet anode supports solid oxide fuel cells (SOFCs) were fabricated by high-frequency induction heated sintering (HFIHS) under 60 MPa pressure with powders synthesized by the glycine nitrate process (GNP) as well as mechanically mixed commercial powders. The HFIHS method created a uniformly porous microstructure without abnormal grain growth compared to the conventional sintering method. Samples sintered by HFIHS show higher strength and electrical conductivity than conventionally sintered samples, even though they have similar porosity.     

Oscillation of electrical current during direct methane oxidation over Ni-added LSCF–GDC anode of solid oxide fuel cells

Solid oxide fuel cells are studied under direct methane feeding with 10–70% CH₄. When either La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)–Ce_0.9Gd_0.1O_1.95 (GDC) or Ni-added LSCF–GDC composite is used as the anode, the oscillations of the electrical current and the formation rates of CO and CO₂ occur. The oscillation of the electrical current can be explained by a mechanism of periodic oxidation–reduction of the bulk lattice of the anode, with the determining factor being the build-up of the concentration of the oxygen vacancies to a certain extent. As the methane concentration increases, the current density increases and becomes larger with Ni addition. Higher methane concentration leads to higher possibility to induce the oscillation, to start it earlier, and to result in a larger amplitude. Ni addition inhibites the occurrence of the oscillation of the electrical current but promotes that of the CO₂ formation rate.     

Three phase boundaries and electrochemically active zones of lanthanum strontium vanadate–yttria-stabilized zirconia anodes in solid oxide fuel cells

Electrochemical reactions in solid oxide fuel cells take place around three-phase boundaries (TPBs). The electrochemically active zones (EAZs) are generated in three-dimensions around the TPBs of on-running SOFCs. This work discusses the behaviours of TPBs and EAZs via a case study on lanthanum strontium vanadate (LSV)–yttria-stabilized zirconia (YSZ) composite anode. A percolating binary particle aggregate, based on geometric random loose packing model and traditional sintering theory, is constructed to represent the LSV–YSZ anode. The TPB lengths of LSV–YSZ anodes are evaluated from the coordination numbers and sintering necks of the particles in the particle aggregate. Empirical interrelations among TPBs, EAZs, active electrode thickness, in-depth penetration of electrocatalysts of polarized LSV–YSZ anode are established.     

Review of composite cathodes for intermediate-temperature solid oxide fuel cell applications

A composite cathode exhibits low activation polarisation by spreading its electrochemically active area within its volume. Composite cathodes enable the development of high-performance electrodes for solid oxide fuel cells (SOFCs) at intermediate temperatures (600 °C – 800 °C) because of their significant role in determining the kinetics of oxygen reduction reaction (ORR). Few anions O²⁻ are transferred through the electrolyte component when the ORR is low, thereby lowering the reaction with cation H⁺ from an anode side to transfer electrons along the outer circuit to the cathode side to participate in ORR. The resistance to the ORR at the cathode is minimised, thereby contributing to performance degradation and efficiency loss in existing SOFCs, especially at intermediate temperatures. The suitability and compatibility of the cathode and electrolyte are crucial in the development of cathodes and electrochemical reactions. The intercomponent compatibility is important to ensure the robustness and durability of SOFCs, especially at an operating temperature around 800 °C, at which the components experience extreme thermal and mechanical stresses. Composite cathodes are used to improve cathode performance. These composite cathodes help enhance the properties of mixed electronic–ionic conductors and the intercomponent compatibility. Herein, we reviewed historical data of composite-cathode development for SOFCs, including its basic principle and criteria. The overall performance of as-synthesised composite cathodes in terms of microstructure, electrochemical reaction and intercomponent compatibility is briefly discussed.     

Synthesis and densification of lanthanum silicate apatite electrolyte for intermediate temperature solid oxide fuel cell via co-precipitation method

Lanthanum silicate apatite (LSA, La_9.33+xSi₆O_26+1.5x, x = 0–0.67) has been widely investigated as a promising electrolyte material for intermediate temperature solid oxide fuel cell (SOFC). In this work, a facile and low-cost co-precipitation method is used to synthesize LSA precursor powders. The well dispersed nanopowders (ca. 70 nm) with pure hexagonal LSA phase are obtained by calcining the precursor at 900 °C. Impurity of La₂SiO₅, caused by the different precipitation productivities of La(NO₃)₃ and TEOS, can be eliminated through lowering the La/Si ratio in the starting mixtures. The dispersant (PEG200) plays a crucial role in co-precipitation processes, which can effectively mitigate the agglomeration and therefore significantly improve the sinterability of the nanoparticles. Dense LSA ceramic with relative density of 98% is obtained after sintering at 1550 °C, which exhibits a conductivity of 0.13 mS cm⁻¹ at 500 °C.     

Fabrication of glass ceramic sealants with ceramic fiber filler for solid oxide fuel cells

In this study, ceramic fibers are used as a filler material for glass ceramic sealant in solid oxide fuel cells to improve the thermal cycle behavior. Beside the bare glass ceramic sealant for comparison, multilayered sealants with different ceramic fiber contents are fabricated to investigate the effect of ceramic fiber quantity also. The mechanical performances of the samples are measured via tensile tests by placing them between two metallic interconnector plates after the glass formation process as well as after 1, 5 and 10 thermal cycles. The results show that the mechanical strength in general tends to decrease with increasing the ceramic filler content, which can be attributed to poor adhesion due to reduced glass ceramic composition. On the other hand, thermal cycle behavior of the samples with ceramic fibers is found to be improved at some extend. This may be due to the behavior of ceramic filler network and relatively slow crystallization with increasing the amount of the filler as proven by microstructural observations. Especially for the sample including 4 ceramic fiber interlayers each having 0.030 g ceramic fibers, the mechanical strength shows an increasing trend with the number of thermal cycles.     

Fabrication of electrolyte materials for solid oxide fuel cells by tape-casting

In this research, solid oxide fuel cell electrolytes were fabricated by aqueous tape-casting technique. The basic compositions for SOFC electrolyte systems were focused on yttria-stabilized zirconia (YSZ) system. The powders used in this study were from different sources. ZrO₂-based system doped with 3, 8, and 10 mol% of Y₂O₃, and 8YSZ electrolyte tape illustrated the desirable properties. The grain size of the sintered electrolyte tapes was in the range of 0.5–1 μm with 98–99% of theoretical density. Phase and crystal structure showed the pure cubic fluorite structure for 8–10 mol% YSZ and tetragonal phase for 3 mol% doped. The electrolyte tapes sintered at 1450 °C for 4 h had the highest ionic conductivity of 30.11 × 10⁻³ S/cm which was measured at 600 °C. The flexural strengths were in the range of 100–180 MPa for 8–10 mol% YSZ, and 400–680 MPa for 3 mol% YSZ.     

Development of ceramic fiber reinforced glass ceramic sealants for microtubular solid oxide fuel cells

Ceramic fibers in various forms with different fiber sizes are tested to improve the sealing performance of glass ceramic seals for microtubular solid oxide fuel cell applications. In this regard, several sealing pastes are prepared by mixing each ceramic fibers type with glass ceramics at 1.25 wt %. Five layered microtubular anode supported cells are also fabricated by extrusion and dip coating methods to evaluate the sealing performance of the composite sealants. The pastes are applied between the cells and gas manifolds made of Crofer22 APU. The electrochemical and sealing performances at an operating temperature of 800 °C under hydrogen are investigated after the glass forming process. Microstructures of the sealants are also examined by a scanning electron microscope. Experimental investigations reveal that the cells sealed by the pastes with ceramic bulk fiber and ceramic fiber rope gasket show acceptable open circuit potentials close to the theoretical one. These cells can be also pressurized up to around 150 kPa back pressure in the sealing performance tests. On the other hand, the pastes without any filler, with ceramic rope and with ceramic blanket exhibit poor sealing performance due to gas leakage originated from flowing of the main glass ceramic matrix from the joints. Therefore, ceramic bulk fiber and ceramic fiber rope gasket are found to behave as a stopper and can be used to prevent glass ceramics from flowing for microtubular solid oxide fuel cells or similar applications.     

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.     

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.     

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.     

Modeling the temperature field in the reforming anode of a button-shaped solid oxide fuel cell

A model predicting the temperature field in the porous reforming anode of a solid oxide fuel cell is presented herein. The model is based on mass, momentum, and heat balances of a chemically reacting mixture of gases within the porous matrix of the anode. The important novel characteristic of the model is the consideration of the both internal reforming and electrochemical reactions in the bulk of the porous anode. The electronic and ionic currents in the anodes are calculated utilizing the solution of the Poisson equations for the electric potentials in the porous medium. The transfer current density is described by the Butler–Volmer equation.The model is applied to investigate the temperature field and the reactive flow in button-shaped fuel cells with uniform and graded (multi-layer) anodes composed of Ni and YSZ particles with methane/water vapor mixture used as the fuel. The maximum temperature difference between the hot and cold spots of the anodes is found to reach up to 200 K. The results indicate that the generation of Joule heating caused by the current passing through the anode and the activation losses are the dominating heat sources compared to the gas-water shift and electrochemical reactions.     

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.     

Fabrication of dense and defect-free diffusion barrier layer via constrained sintering for solid oxide fuel cells

To enable the development of next-generation solid oxide fuel cells (SOFCs), the fabrication of dense and defect-free diffusion barrier layers via constrained sintering has been a significant challenge. Here, we present a double layer technique that enables complete densification of a defect-free gadolinia-doped ceria diffusion barrier layer. In this approach, top and bottom layers were individually designed to perform unique functions based on systematic analysis of constrained sintering. The top layer, which contains 1 wt% CuO as a sintering aid, provides sufficient sintering driving force via liquid-phase sintering to allow complete densification of the film, while the bottom layer without a sintering aid prevents detrimental chemical reactions and regulates the global sintering rate to eliminate macro-defects. Such fabrication of dense diffusion barrier layers via a standard ceramic processing route would allow the use of novel cathode materials in practical SOFC manufacturing. Furthermore, the strategy presented in this study could be exploited in various multi-layer ceramic applications involving constrained sintering.     

Influence of doctor blade gap on the properties of tape cast NiO/YSZ anode supports for solid oxide fuel cells

In this study, various tape cast NiO/YSZ anode support layers with similar geometric properties are fabricated by varying the doctor blade from 100?µm to 200?µm with an increment of 25?µm. The mechanical properties of the anode support layers are investigated by three point bending tests of 30 samples for each doctor blade gap. The reliability curves of the flexural strength data are also obtained via two-parameter Weibull distribution method. The effects of the doctor blade gap on the microstructure and the electrochemical performance of the anode support layers are determined via SEM investigations and single cell performance-impedance tests, respectively. The apparent porosities of the samples are also measured by Archimedes’ principle. The results indicate that the doctor blade gap or the resultant tape thickness influences the microstructure of tape cast NiO/YSZ anode supports significantly, yielding different mechanical and electrochemical characteristics. At a reliability level of 70%, the highest flexural strength of 110.20?MPa is obtained from the anode support layer with a doctor blade gap of 175?µm and the 16?cm² active area cell with this anode support layer also exhibits the highest peak performance of 0.483?W/cm² at an operating temperature of 800?°C. Thus, a doctor blade gap of 175?µm is found to have such a microstructure that provides not only better mechanical strength but also higher electrochemical performance.     

硫化氢固体氧化物燃料电池研究进展

综述了H2 S固体氧化物燃料电池 (SOFC)的发展历史和研制现状 ,包括固体电解质薄膜如质子传导膜和氧离子传导膜的开发、电极催化材料尤其是阳极催化材料的研制、以及整个电池系统的性能研究。指出H2 SSOFC在工业化过程中所面临和必须解决的关键技术问题是 :电解质薄膜材料的研制及其制备 ,尤其是薄膜化的制备技术 ;电极材料的开发及制备 ,特别是阳极催化材料的选择与制备技术 ;膜 -电极三合一制备技术。并对H2 SSOFC的开发及工业应用前景作了展望