Fuel utilization and fuel sensitivity of solid oxide fuel cells

Fuel utilization and fuel sensitivity are two important process variables widely used in operation of SOFC cells, stacks, and generators. To illustrate the technical values, the definitions of these two variables as well as practical examples are particularly given in this paper. It is explicitly shown that the oxygen-leakage has a substantial effect on the actual fuel utilization, fuel sensitivity and V-I characteristics. An underestimation of the leakage flux could potentially results in overly consuming fuel and oxidizing Ni-based anode. A fuel sensitivity model is also proposed to help extract the leakage flux information from a fuel sensitivity curve. Finally, the “bending-over” phenomenon observed in the low-current range of a V-I curve measured at constant fuel-utilization is quantitatively coupled with leakage flux.     

Fabrication and optimization of LSM infiltrated cathode electrode for anode supported microtubular solid oxide fuel cells

In this study, anode supported microtubular solid oxide fuel cells (SOFCs) with LSM (lanthanum strontium manganite) catalyst infiltrated LSM-YSZ (yttria stabilized zirconia) cathodes are developed to increase the density of triple/three phase boundaries (TPBs) in the cathode, thereby to improve the cell performance. For this purpose, two different porous YSZ layers are formed on the dense YSZ electrolyte, i.e., one is with co-sintering while the other one is not. Incorporation of LSM into these porous YSZ layers is achieved via dip coating of a sol-gel based infiltration solution. The effects of the fabrication method for porous YSZ, LSM solution dwelling time and the thickness of the porous YSZ layer on the cell performance are experimentally investigated and optimized in the given order. A reference cell having a conventional dip coated cathode prepared by mixing the commercial LSM and YSZ powders is also fabricated for comparison. The results show that among the cases considered, the highest peak power density of 0.828 W/cm² can be obtained from the cell, whose single dip coated porous electrolyte layer co-sintered with the dense electrolyte is impregnated with LSM for a dwelling time of 45 min. On the other hand, the peak power density of the reference cell is measured as only 0.558 W/cm². These results reveal that ～50% increase in the maximum cell performance compared to that of the reference cell can be achieved by LSM infiltration after the optimizations.     

Electrochemical characterizations of microtubular solid oxide fuel cells under a long-term testing at intermediate temperature operation

We report the long-term stability of a microtubular solid oxide fuel cell (SOFC) operable at ∼500 °C. The SOFC consists of NiO-Gd doped ceria (GDC) as the anode as well as the tubular support, GDC as an electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)-GDC as the cathode. A single tubular cell with a diameter of approximately 1.8 mm and an effective electrode length of approximately 20 mm generated 150 mW cm⁻² and 340 mW cm⁻² at 500 °C and 550 °C, respectively, under the operation conditions of 0.7 V and humidified H₂ fuel flow. The cell exhibited good stability with a degradation rate of 0.25%/100 h under operation conditions of 200 mA and 0.75 V.     

Theoretical models for effective electrical and electrochemical properties of nano-particle infiltrated electrode of solid oxide fuel cell

Single- and binary-phase nano-particle infiltrated electrodes (SIE and BIE) have been actively studied experimentally. To properly understand the experimental results and the benefits of SIE and BIE designs, new models for electrical conductivities of BIE and TPB lengths of SIE and BIE are proposed here. The models agree with experiments on the variation of conductivity with LSM loading. SIE and BIE may provide adequate electronic conductivity at low loading of conducting material. The theoretical effective properties are further used in multi-physics modeling and the obtained I–V curves also agree with the experiments. Quantitative comparisons of the ionic conductivities of SIE, BIE and conventional composite electrode (CE) are made. BIE possesses the longest TPB length and SIE may also yield a TPB length that is one order of magnitude larger than that of CE. The new theory allows for in-depth analysis and design optimization of BIE and SIE for improved performance.     

A new anode material for intermediate solid oxide fuel cells

A new anode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) with a composite of La_0.7Sr_0.3Cr_1−xNi_xO₃ (LSCN), CeO₂ and Ni has been synthesized. EDX analysis showed that 1.19 at% Ni was doped into the perovskite-type La_0.7Sr_0.3CrO₃ and Ce could not be detected in the perovskite phases. Results showed that the fine CeO₂ and Ni were highly dispersed on the La_0.7Sr_0.3Cr_1−xNi_xO₃ substrates after calcining at 1450 °C and reducing at 900 °C. The thermal expansion coefficient (TEC) of the as-prepared anode material is 11.8 × 10⁻⁶ K⁻¹ in the range of 30–800 °C. At 800 °C, the electrical conductivity of the as-prepared anode material calcined at 1450 °C for 5 h is 1.84 S cm⁻¹ in air and 5.03 S cm⁻¹ in an H₂ + 3% H₂O atmosphere. A single cell with yttria-stabilized zirconia (YSZ, 8 mol% Y₂O₃) electrolyte and the new materials as anodes and La_0.8Sr_0.2MnO₃ (LSM)/YSZ as cathodes was assembled and tested. At 800 °C, the peak power densities of the single cell was 135 mW cm⁻² in an H₂ + 3% H₂O atmosphere.     

Microstructure and electrochemical characterization of solid oxide fuel cells fabricated by co-tape casting

A co-tape casting technique was applied to fabricate electrolyte/anode for solid oxide fuel cells. YSZ and NiO-YSZ powders are raw materials for electrolyte and anode, respectively. Through adjusting the Polyvinyl Butyral (PVB) amount in slurry, the co-sintering temperature for electrolyte/anode could be dropped. After being co-sintered at 1400 °C for 5 h, the half-cells with dense electrolytes and large three phase boundaries were obtained. The improved unit cell exhibited a maximum power density of 589 mW cm⁻² at 800 °C. At the voltage of 0.7 V, the current densities of the cell reached 667 mA cm⁻². When the electrolyte and the anode were cast within one step and sintered together at 1250 °C for 5 h and the thickness of electrolyte was controlled exactly at 20 μm, the open-circuit voltage (OCV) of the cell could reach 1.11 V at 800 °C and the maximum power densities were 739, 950 and 1222 mW cm⁻² at 750, 800 and 850 °C, respectively, with H₂ as the fuel under a flow rate of 50 sccm and the cathode exposed to the stationary air. Under the voltage of 0.7 V, the current densities of cell were 875, 1126 and 1501 mA cm⁻², respectively. These are attributed to the large anode three phase boundaries and uniform electrolyte obtained under the lower sintering temperature. The electrochemical characteristics of the cells were investigated and discussed.     

Thermal stress modeling of anode supported micro-tubular solid oxide fuel cell

An anode-supported micro-tubular solid oxide fuel cell (SOFC) is analyzed by a two-dimensional axisymmetric numerical model, which is validated with the experimental I-V data. The temperature distribution generated by the thermo-electrochemical model is used to calculate the thermal stress field in the tubular SOFC. The results indicate that the current transport in the anode is the same at every investigated position. The stress of the micro-tubular cell occurs mainly because of the residual stress due to the mismatch between the coefficients of thermal expansion of the materials of the membrane electrode assembly. The micro-tubular cell can operate safely, but if there is an interfacial defect or a high enough tensile stress applied at the electrolyte, a failure can arise.     

Thermal imaging of solid oxide fuel cell anode processes

A Si-charge-coupled device (CCD), camera-based, near-infrared imaging system is demonstrated on Ni/yttria-stabilized zirconia (YSZ) fragments and the anodes of working solid oxide fuel cells (SOFCs). NiO reduction to Ni by H₂ and carbon deposition lead to the fragment cooling by 5 ± 2 °C and 16 ± 1 °C, respectively. When air is flowed over the fragments, the temperature rises 24 ± 1 °C as carbon and Ni are oxidized. In an operational SOFC, the decrease in temperature with carbon deposition is only 4.0 ± 0.1 °C as the process is moderated by the presence of oxides and water. Electrochemical oxidation of carbon deposits results in a ΔT of +2.2 ± 0.2 °C, demonstrating that electrochemical oxidation is less vigorous than atmospheric oxidation. While the high temperatures of SOFCs are challenging in many respects, they facilitate thermal imaging because their emission overlaps the spectral response of inexpensive Si-CCD cameras. Using Si-CCD cameras has advantages in terms of cost, resolution, and convenience compared to mid-infrared thermal cameras. High spatial (0.1 mm) and temperature (0.1 °C) resolutions are achieved in this system. This approach provides a convenient and effective analytical technique for investigating the effects of anode chemistry in operating SOFCs.     

Effect of Ba doping on performance of LST as anode in solid oxide fuel cells

The level of barium doping in lanthanum strontium titanate (La_0.4Sr_0.6−xBa_xTiO₃, 0 ≤ x ≤ 0.2; LST, x = 0; LSBT, x > 0), prepared by solid state synthesis, affects its performance as anode in solid oxide fuel cells (SOFCs). Cell structures of LST and all LSBT were similar. The oxidation state of Ti in all compounds was reduced by a comparable amount when LST or LSBT was heated under reducing conditions to form La_0.4Sr_0.6−xBa_xTi_0.59⁴⁺Ti_0.41³⁺O_2.97. All fuel cells using LST or LSBT had high activity for conversion of hydrogen or methane, and the activity increased with the level of substitution by Ba. In addition, performance was enhanced when H₂S was present in either CH₄ or H₂ fuel. There was good contact between YSZ electrolyte and each LSBT or LSB anode.     

Effects of applied current density and thermal cycling on the degradation of a solid oxide fuel cell cathode

Effects of applied current density and thermal cycles on the durability of a solid oxide fuel cell (SOFC) cathode have been studied. SOFC half-cells with and without a gadolinium-doped ceria (GDC) interlayer were fabricated and tested for 1000 h at 900 °C under various current densities and thermal cycles. Performance degradation of the half-cells was assessed by increment of the area specific resistance (ASR). Initially, the ASR of the half-cells without the GDC interlayer decreased for around 150 h due to cathode activation and thereafter increased. A rapid increase in the ASR was observed at higher applied current density, which is attributed to delamination of the electrolyte/cathode interface due to the formation of Sr zirconates, and microstructural change in the cathode. However, these adverse effects were prevented by the GDC interlayer. The half-cells with the GDC interlayer exhibited a smaller degradation rate as compared to that without the GDC interlayer. During the thermal cycling test, ASR values of all GDC interlayer thickness cells increased with an increasing number of thermal cycles. The thermally cycled cell with a GDC interlayer thickness of 3.4 μm showed a lower degradation rate due to the dense GDC interlayer, which resulted in less interfacial resistance and prevented elemental diffusion towards the electrolyte. However, the half-cells with GDC interlayer thickness of 2.4 and 4.5 μm showed a higher increase in the ASR due to relatively higher Sr diffusion and delamination of the cathode/GDC interlayer interface, respectively.     

Fabrication and characterization of metal-supported solid oxide fuel cells

Metal-supported solid oxide fuel cells (SOFCs) are an acceptable approach to solving the serious problems of SOFC technology, such as sealing and mechanical strength. In this work, commercial stainless-steel plates, STS430, are used as supporting bodies for a metal-supported SOFC in order to decrease the number of fabrication steps. The metal support for a single-cell has a diameter of 28 mm, a thickness of 1 mm, and a channel width of 0.4 mm. A thin ceramic layer, composed of yttria-stabilized zirconia (YSZ) and NiO/YSZ, is attached to the metal support by using a cermet adhesive. La_0.8Sr_0.2Co_0.4Mn_0.6O₃ perovskite oxide serves as the cathode material because of its low impedance on the YSZ electrolyte, according to half-cell tests. The maximum power density of the cell is 0.09 W cm⁻² at 800 °C. The effects of temperature, oxygen partial pressure, and current collection by pastes are investigated. The oxygen reduction reaction at the cathode dominates the overall cell performance, according to experimental and numerical analyses.     

Modeling of thermal stresses and lifetime prediction of planar solid oxide fuel cell under thermal cycling conditions

A typical operating temperature of a solid oxide fuel cell (SOFC) is above 600 °C, which leads to severe thermal stresses caused by the difference in material mechanical properties during thermal cycling. Interfacial shear stress and peeling stress are the two types of thermal stresses that can cause the mechanical failure of the SOFC. Two commonly used SOFC configurations (electrolyte-supported and anode-supported) were considered for this study. The paper developed a mathematical model to estimate the thermal stresses and to predict the lifetime of the cell (Ni/8YSZ-YSZ-LSM). Due to the mismatch of the material mechanical properties of the cell layers, a crack nucleation induced by thermal stresses can be predicted by the crack damage growth rate and the initial damage distribution in the interfacial layer for each thermal cycle. It was found that the interfacial shear stress and peeling stress were more concentrated near the electrode free edge areas. The number of cycles needed for failure decreased with the increase in the porosity of electrode. The number of cycle for failure decreased with increase in electrolyte thickness for both anode- and electrolyte-supported SOFC. The model provides insight into the distribution of interfacial shear stress and peeling stress and can also predict damage evolution in a localized damage area in different SOFC configurations.     

The effect of temperature gradients on thermal cycling and isothermal ageing of micro-tubular solid oxide fuel cells

Isothermal ageing and thermal cycling are performed on micro-tubular solid oxide fuel cells (SOFCs) in-order to understand degradation and failure mechanisms in micro-tubular SOFCs. For isothermal ageing, the effect of temperature gradients is investigated at 800 °C on two micro-tubular SOFC samples (1) 25 mm long and (2) 55 mm long. A temperature gradient is induced across the cells by passing 25% excess fuel for combustion at the cell outlet, thereby raising the temperature at this end to 950 °C. 25 mm long samples presented higher power density than the later ones and their rates of degradation were similar. Also, the effect of temperature gradients is investigated during the thermal cycling of micro-tubular SOFC to understand their contribution to electrochemical performance degradation. Two micro-tubes were characterized; one with optimum hydrogen flow rate and the other with 25% excess. No micro-cracking or de-lamination was observed in the micro-tube without a temperature gradient, whereas severe de-laminations and micro-cracking were observed when 25% excess hydrogen flow was used during thermal cycling.In conclusion, the effect of temperature gradients during isothermal ageing was marginal, and Ni sintering was found to dominate the degradation mechanism. On the other hand during thermal cycling, the temperature gradients were found to be contributive to degradation by opening micro-cracks and de-laminations.     

Novel nano-network cathodes for solid oxide fuel cells

A novel nano-network of Sm_0.5Sr_0.5CoO_3−δ (SSC) is successfully fabricated as the cathodes for intermediate-temperature solid oxide fuel cells (SOFCs) operated at 500–600 °C. The cathode is composed of SSC nanowires formed from nanobeads of less than 50 nm thus exhibiting high surface area and porosity, forming straight path for oxygen ion and electron transportation, resulting in high three-phase boundaries, and consequently showing remarkably high electrode performance. An anode-supported cell with the nano-network cathode demonstrates a peak power density of 0.44 W cm⁻² at 500 °C and displays exceptional performance with cell operating time. The result suggests a new direction to significantly improve the SOFC performance.     

Theoretical analysis of reversible solid oxide fuel cell based on proton-conducting electrolyte

A single reversible solid oxide fuel cell (RSOFC) can accomplish two functions: (1) as a solid oxide steam electrolyzer (SOSE) for hydrogen production and (2) as a solid oxide fuel cell (SOFC) for power generation. An electrochemical model was developed to study the performance of an RSOFC based on a proton-conducting electrolyte (RSOFC-H). In both SOSE and SOFC modes, the hydrogen electrode-supported configuration was identified as the most favorable design to achieve high energy conversion efficiency of RSOFC-H. For comparison, in a previous study on conventional RSOFC based on an oxygen ion-conducting electrolyte (RSOFC-O), the hydrogen electrode-supported configuration was found to be favorable in the SOFC mode but such configuration would cause high concentration overpotential in the SOSE mode. Thus, the oxygen electrode-supported configuration was desirable for RSOFC-O operating in the SOSE mode. The results obtained in this study show that RSOFC-H has a natural advantage over RSOFC-O in terms of structural design. The modeling study signifies the difference between RSOFC-H and RSOFC-O and can serve as a useful tool for further design optimization.     

Integrated thermal management strategy and materials for solid oxide fuel cells

The application of positive temperature coefficient (PTC) thermistors to thermal management of solid oxide fuel cells (SOFCs) is considered. A strategy is proposed for eliminating hotspots and reducing temperature gradients in SOFCs via inclusion of a material that exhibits a dramatic change in resistance near the desired maximum cell temperature. Three PTC thermistor materials with transition temperatures near the maximum desirable SOFC operating temperature are identified and screened for compatibility with common SOFC materials. All are found to be unsuitable because of reaction with the SOFC materials or unacceptably small PTC effect.     

Y-doped SrTiO3 based sulfur tolerant anode for solid oxide fuel cells

A solid oxide fuel cell (SOFC) anode with high sulfur tolerance was developed starting from a Y-doped SrTiO₃ (SYTO)-yttria stabilized zirconia (YSZ) porous electrode backbone, and infiltrated with nano-sized catalytic ceria and Ru. The size of the infiltrated particles on the SYTO-YSZ pore walls was 30–200 nm, and both infiltrated materials improved the performance of the SYTO-YSZ anode significantly. The infiltrated ceria covered most of the surface of the SYTO-YSZ pore walls, while Ru was dispersed as individual nano-particles. The performance and sulfur tolerance of a cathode supported cell with ceria- and Ru-infiltrated SYTO-YSZ anode was examined in humidified H₂ mixed with H₂S. The anode showed high sulfur tolerance in 10–40 ppm H₂S, and the cell exhibited a constant maximum power density 470 mW cm⁻² at 10 ppm H₂S, at 1073 K. At an applied current density 0.5 A cm⁻², the addition of 10 ppm H₂S to the H₂ fuel dropped the cell voltage slightly, from 0.79 to 0.78 V, but completely recovered quickly after the H₂S was stopped. The ceria- and Ru-infiltrated SYTO-YSZ anode showed much higher sulfur tolerance than conventional Ni-YSZ anodes.     

Preparation and characterization of Pr1−xSrxFeO3 cathode material for intermediate temperature solid oxide fuel cells

A kind of cathode material of Pr_1−xSr_x FeO₃ (x = 0–0.5) for intermediate temperature solid oxide fuel cells (IT-SOFCs) was prepared by the coprecipitation method. Crystal structure, thermal expansion, electrical conductivity and electrochemical performance of the Pr_1−xSr_xFeO₃ perovskite oxide cathodes were studied by different methods. The results revealed that Pr_l−xSr_xFeO₃ exhibited similar orthorhombic structure from x = 0.1 to 0.3 and took cubic structure when x = 0.4–0.5. The unit cell volume decreased and the thermal expansion coefficient (TEC) of the materials increased as the strontium content increased. When 0 < x ≤ 0.3, the samples exhibited good thermal expansion compatibility with YSZ electrolyte. The electrical conductivity increased with the increasing of doped strontium content. When x = 0.3–0.5, the electrical conductivities were higher than 100 S cm⁻¹. The conductivity of Pr_0.8Sr_0.2FeO₃ was 78 S cm⁻¹ at 800 °C. Compared with the La_0.8Sr_0.2MnO₃ cathode, Pr_0.8Sr_0.2FeO₃ showed higher polarization current density and lower polarization resistance (0.2038 Ω cm²). The value of I₀ for Pr_0.8Sr_0.2FeO₃ at 800 °C is 123.6 mA cm⁻². It is higher than that of La_0.8Sr_0.2MnO₃. Therefore, Pr_1−xSr_xFeO₃ can be considered as a candidate cathode material for IT-SOFCs.     

Investigation of compatible anode systems for LaNbO4-based electrolyte in novel proton conducting solid oxide fuel cells

In the current manufacturing process of novel LaNbO₄-based proton conducting fuel cells a thin layer of the electrolyte is deposited by wet ceramic coating on NiO-LaNbO₄ based anode and co-sintered at 1200-1300 °C. The chemical compatibility of NiO with acceptor doped LaNbO₄ material is crucial to ensure viability of the cell, so potential effects of other phases resulting from off-stoichiometry in acceptor doped LaNbO₄ should also be explored. Compatibility of NiO with Ca-doped LaNbO₄ and its typical off-set compositions (La₃NbO₇ and LaNb₃O₉) are investigated in this work. It is shown that while NiO does not react with Ca-doped LaNbO₄, fast reaction occurs with La₃NbO₇ or LaNb₃O₉. La₃NbO₇ and NiO form a mixed conducting perovskite phase LaNi_2/3Nb_1/3O₃, while LaNb₃O₉ and NiO form either NiNb₂O₆ or Ni₄Nb₂O₉ depending on the annealing temperature. This implies that manufacturing LaNbO₄-based proton conducting fuel cells requires a strict control of the stoichiometry of the electrolyte.     

Electrical conductivity and structural stability of La-doped SrTiO3 with A-site deficiency as anode materials for solid oxide fuel cells

A-site-deficient (La_0.3Sr_0.7)_1−xTiO_3−δ materials were synthesized by conventional solid-state reaction. The A-site deficiency limit in (La_0.3Sr_0.7)_1−xTiO_3−δ was below 10 mol% in 5%H₂/Ar at 1500 °C. A-site deficiency level promoted the sintering process of (La_0.3Sr_0.7)_1−xTiO_3−δ. The ionic conductivity increased but the electronic conductivity decreased with increasing A-site deficiency level. The ionic conductivity of (La_0.3Sr_0.7)_0.93TiO_3−δ sample was as high as 0.2–1.6 × 10⁻² S/cm in 500–950 °C and 1.0 × 10⁻² S/cm at 800 °C, over twice of La_0.3Sr_0.7TiO_3−δ. Its electrical conductivity was in the range of 83–299 S/cm in 50–950 °C and 145 S/cm at 800 °C. A-site deficiency improved the thermal stability of (La_0.3Sr_0.7)_1−xTiO_3−δ and ensured the material with a stable electrical performance in different atmospheres.