Preparation and characterization of La0.8Sr0.2Ga0.83Mg0.17O3 electrolyte by polyol method for solid oxide fuel cells

Perovskite type La_0.8Sr_0.2Ga_0.83Mg_0.17O₃ powders were prepared via simple polyol method for the first time in literature. Obtained material was characterized by using XRD, SEM, Impedance Spectroscopy and density measurements. Pure LSGM powders were achieved after heat treatment at 1100 °C for 12 h. 87% relative density was obtained after pressing of these powders under 1 MPa and sintering at 1250 °C for 12 h. Average particle size was calculated as 1.77–2.4 μm from SEM micrographs. Overall conductivity of the LSGM pellet was found to be 0.0014 S/cm at 850 °C with impedance analysis and showed that the preparation process needs improvements.     

High-conductivity electrolyte with a low sintering temperature for solid oxide fuel cells

Bismuth oxide and scandia co-doped zirconia (Sc₂O₃)_0.06(Bi₂O₃)_x(ZrO₂)_0.94–x (ScSZB, x = 0, 0.01, 0.03, 0.05, 0.07, 0.1) powders are prepared via a citrate sol-gel method. Bi₂O₃ promotes the sintering process of scandia stabilized zirconia (ScSZ) and increases electrical conductivity of system. A high conductivity of ～0.094 S/cm at 800 °C is achieved on 5 mol% Bi₂O₃ doped ScSZ (ScSZB05). X-ray Rietveld refinement and transmission electron microscope (TEM) analysis of the ScSZB05 reveal the formation of cubic phase and rhombohedral phase at room temperature. The electrolyte-supported cell constructed by the ScSZ electrolyte gives the maximum power density of 258.3 mW/cm² at 800 °C, while the cell with ScSZB05 electrolyte shows a higher value of 387.6 mW/cm². The performance obtained by theoretical simulation of the two electrolyte-supported cells is in good agreement with the experimental results.     

Intermediate temperature solid oxide fuel cell based on lanthanum gallate electrolyte

The Kansai Electric Power Co. Inc. (KEPCO) and Mitsubishi Materials Corporation (MMC) have been developing intermediate temperature solid oxide fuel cells (IT-SOFCs) which are operable at a temperature range between 600 and 800 °C. There are some significant features in IT-SOFC of KEPCO–MMC: (1) highly conductive lanthanum gallate-based oxide is adopted as an electrolyte to realize high-performance disk-type electrolyte-supported cells; (2) the cell-stacks with seal-less structure using metallic separators allow residual fuel to burn around the stack and the combustion heat is utilized for thermally self-sustainable operation; (3) the separators have flexible arms by which separate compressive forces can be applied for manifold parts and interconnection parts. We are currently participating in the project by New Energy and Industrial Technology Development Organization (NEDO) to develop 10 kW-class combined heat and power (CHP) systems. In FY2006, a 10 kW-class module was developed, with which the electrical efficiency of 50%HHV was obtained based on DC 12.6 kW. In the first quarter of FY2007, the 10 kW-class CHP system using the module gave the electrical efficiency of 41%HHV on AC 10 kW and the overall efficiency of 82%HHV when exhaust heat was recovered as 60 °C hot water. Currently, the operation has been accumulated for about 2500 h to evaluate the long-term stability of the system.     

Bismuth oxide doped scandia-stabilized zirconia electrolyte for the intermediate temperature solid oxide fuel cells

Electrical and structural properties of bismuth oxide doped scandia-stabilized zirconia (ScSZ) electrolyte for solid oxide fuel cells (SOFCs) have been evaluated by means of XRD, TGA, DTA, and impedance spectroscopy. The amount of Bi₂O₃ in the ScSZ was varied in the range of 0.25–2.0 mol%. The original ScSZ samples indicated a rhombohedral crystalline structure that in general has lower conductivity than the cubic phase. However, the addition of Bi₂O₃ to ScSZ electrolyte was found to stabilize the cubic crystalline phase as detected by XRD. Impedance spectroscopy measurements in the temperature range between 350 and 900 °C indicated a sharp increase in conductivity for the system containing 2 mol% of Bi₂O₃ that is attributed to the presence of the cubic phase. In addition, impedance spectroscopy measurements revealed significant decrease of both the grain bulk and grain boundary resistances with respect to the temperature change from 600 to 900 °C and concentration of Bi₂O₃ from 0.5 to 2 mol%. The electrical conductivity at 600 °C obtained for 2 mol% Bi₂O₃ doped ScSZ was 0.18 S cm⁻¹.     

Intermediate temperature solid oxide fuel cells using LaGaO3 based oxide film deposited by PLD method

Dense La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ (LSGM, 5 μm in thickness)/Ce_0.8Sm_0.2O_2-δ (SDC, 400 nm in thickness) bilayer films were deposited on a dense NiO (Fe₃O₄)-SDC anode substrate by a pulsed laser deposition (PLD) method. After in-situ reduction, the substrate turned to be porous and it can be used as a porous anode substrate. The power density was strongly affected by the oxide ion conductor combined with LSGM and it was found that SDC is the most useful for achieving the high power density. Preparation of Sm_0.5Sr_0.5CoO₃ cathode film by PLD method is also studied for decreasing the contact resistance of cathode. Preparation of SSC film by PLD is effective for decreasing cathodic overpotential and 400 nm thick film is the most effective for achieving the high power density. At 773 K, the maximum power density of the cell becomes higher than 500 mW/cm².     

GdBaCo2O5+x layered perovskite as an intermediate temperature solid oxide fuel cell cathode

GdBaCo₂O_5+x (GBCO) was evaluated as a cathode for intermediate-temperature solid oxide fuel cells. A porous layer of GBCO was deposited on an anode-supported fuel cell consisting of a 15 μm thick electrolyte of yttria-stabilized zirconia (YSZ) prepared by dense screen-printing and a Ni–YSZ cermet as an anode (Ni–YSZ/YSZ/GBCO). Values of power density of 150 mW cm⁻² at 700 °C and ca. 250 mW cm⁻² at 800 °C are reported for this standard configuration using 5% of H₂ in nitrogen as fuel. An intermediate porous layer of YSZ was introduced between the electrolyte and the cathode improving the performance of the cell. Values for power density of 300 mW cm⁻² at 700 °C and ca. 500 mW cm⁻² at 800 °C in this configuration were achieved.     

Effect of thickness of Gd0.1Ce0.9O1.95 electrolyte films on electrical performance of anode-supported solid oxide fuel cells

In the present paper, we investigated the electrical performance of anode-supported solid oxide fuel cells (SOFCs) composed of Gd_0.1Ce_0.9O_1.95 (GDC) electrolyte films of 1-75 μm in thickness prepared by simple and cost-effective methods (dry co-pressing process and spray dry co-pressing process), and discussed the effect of thickness of the GDC electrolyte films on the electrical performance of the anode-supported SOFCs. It was shown that reducing the thickness of the GDC electrolyte films could increase the maximum power densities of the anode-supported SOFCs. The increase of the maximum power densities was attributed to the decrease of the electrolyte resistance with reducing the electrolyte thickness. However, when the thickness of the GDC electrolyte films was less than a certain value (approximately 5 μm in this study), the maximum power densities decreased with the decrease in the thickness of the GDC electrolyte films. The calculated electron fluxes through the GDC electrolyte films increased obviously with reducing the thickness of the GDC electrolyte films, which was the reason why the maximum power densities decreased. Therefore, for anode-supported SOFCs based on electrolytes with mixed electronic-ionic conductivity, there was an optimum electrolyte thickness for obtaining higher electrical performance.     

Evaluation of Ba2(In0.8Ti0.2)2O5.2−n(OH)2n as a potential electrolyte material for proton-conducting solid oxide fuel cell

Electrochemical measurements of fuel cells based on proton conductor electrolyte Ba₂(In_0.8Ti_0.2)₂O_5.2−n(OH)_2n and prepared through a tape casting process and a co-pressing of anode-composite powder and electrolyte tape were performed at 500 °C under wet H₂. The varying parameter between the prepared cells was the thickness of the electrolyte that can be controlled during the tape casting process. The maximum power density was obtained for the cell with the thinnest electrolyte (35 μm) and was about 22 mW cm⁻² with an ohmic resistance about 2 Ω cm² at 500 °C.     

Heterogeneous electrolyte (YSZ–Al2O3) based direct oxidation solid oxide fuel cell

Bilayers comprised of dense and porous YSZ–Al₂O₃ (20 wt%) composite were tape cast, processed, and then fabricated into working solid oxide fuel cells (SOFCs). The porous part of the bilayer was converted into anode for direct oxidation of fuels by infiltrating CeO₂ and Cu. The cathode side of the bilayer was coated with an interlayer [YSZ–Al₂O₃ (20 wt%)]: LSM (1:1) and LSM as cathode. Several button cells were evaluated under hydrogen/air and propane/air atmospheres in intermediate temperature range and their performance data were analyzed. For the first time the feasibility of using YSZ–Al₂O₃ material for fabricating working SOFCs with high open circuit voltage (OCV) and power density is demonstrated. AC impedance spectroscopy and scanning electron microscopy (SEM) techniques were used to characterize the membrane and cell.     

Flash-sintering of Co2MnO4 spinel for solid oxide fuel cell applications

We show that cobalt manganese oxide (Co₂MnO₄) spinel can be sintered (without the application of external pressure) in a few seconds at about ∼325 °C by applying a DC electrical field of 12.5 V cm⁻¹, by a process known as flash-sintering. A transition from normal to flash-sintering occurs when the field is ≥7.5 V cm⁻¹. The flash sintering phenomenon has also been observed in yttria-stabilized zirconia (3YSZ). Together, the results for 3YSZ and Co₂MnO₄ point towards the generality of the process, since 3YSZ is an ionic conductor while the spinel is a predominantly electronic conductor. The Co₂MnO₄ spinels are used to protect metals, such as stainless steels, in solid oxide fuel cells. The low temperatures employed in flash sintering can obviate interfacial interdiffusion with the metal substrate; in nominal sintering these interfacial reactions can produce deleterious interfacial phases.     

Silver infiltrated La0.6Sr0.4Co0.2Fe0.8O3 cathodes for intermediate temperature solid oxide fuel cells

Porous La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) electrodes on anode support cells were infiltrated with AgNO₃ solutions in citric acid and ethylene glycol. Two types of solid oxide fuel cells with the LSCF–Ag cathode, Ni–YSZ/YSZ/LSCF–Ag and Ni–Ce_0.9Gd_0.1O_1.95(GDC)/GDC/LSCF–Ag, were examined in a temperature range 530–730 °C under air oxidant and moist hydrogen fuel. The infiltration of about 18 wt.% Ag fine particles into LSCF resulted in the enhancement of the power density of about 50%. The maximum power density of Ni–YSZ/YSZ/LSCF was enhanced from 0.16 W cm⁻² to 0.25 W cm⁻² at 630 °C by infiltration of AgNO₃. No significant degradation of out-put power was observed for 150 h at 0.7 V and 700 °C. The Ni–GDC/GDC/LSCF–Ag cell showed the maximum power density of 0.415 W cm⁻² at 530 °C.     

Internal shorting and fuel loss of a low temperature solid oxide fuel cell with SDC electrolyte

A solid oxide fuel cell with Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte of 10 μm in thickness and Ni–SDC anode of 15 μm in thickness on a 0.8 mm thick Ni–YSZ cermet substrate was fabricated by tape casting, screen printing and co-firing. A composite cathode, 75 wt.% Sm_0.5Sr_0.5CoO₃ (SSCo) + 25 wt.% SDC, approximately 50 μm in thickness, was printed on the co-fired half-cell, and sintered at 950 °C. The cell showed a high electrochemical performance at temperatures ranging from 500 to 650 °C. Peak power density of 545 mW cm⁻² at 600 °C was obtained. However, the cell exhibited severe internal shorting due to the mixed conductivity of the SDC electrolyte. Both the amount of water collected from the anode outlet and the open circuit voltage (OCV) indicated that the internal shorting current could reach 0.85 A cm⁻² or more at 600 °C. Zr content inclusions were found at the surface and in the cross-section of the SDC electrolyte, which could be one of the reasons for reduced OCV and oxygen ionic conductivity. Fuel loss due to internal shorting of the thin SDC electrolyte cell becomes a significant concern when it is used in applications requiring high fuel utilization and electrical efficiency.     

Evaluation of nano-structured Ir0.5Mn0.5O2 as a potential cathode for intermediate temperature solid oxide fuel cell

A novel Ir_0.5Mn_0.5O₂ cathode has been synthesized by thermal decomposition of mixed H₂IrCl₆ and Mn(NO₃)₂ water solution. The Ir_0.5Mn_0.5O₂ cathode has been characterized by XRD, field emission SEM (FESEM) and AC impedance spectroscopy. XRD result shows that rutile-structured Ir_0.5Mn_0.5O₂ phase is formed by thermal decomposition of mixed H₂IrCl₆ and Mn(NO₃)₂ water solution. FESEM micrographs show that a porous structure with well-necked particles forms in the cathode after sintering at 1000 °C. The average grain size is between 20 and 30 nm. Two depressed arcs appear in the medium-frequency and low-frequency region, indicating that there are at least two different processes in the cathode reaction: charge transfer and molecular oxygen dissociation followed by surface diffusion. The minimum area specific resistance (ASR) is 0.67 Ω cm² at 800 °C. The activation energy for the total oxygen reduction reaction is 93.7 kJ mol⁻¹. The maximum power densities of the Ir_0.5Mn_0.5O₂/LSGM/Pt cell are 43.2 and 80.7 mW cm⁻² at 600 and 700 °C, respectively.     

B-site doping of lanthanum strontium titanate for solid oxide fuel cell anodes

In this study the properties of the compounds La_0.33Sr_0.67Ti_0.92X_0.08O_3+δ where X = Al³⁺, Ga³⁺, Feⁿ⁺, Mg²⁺, Mnⁿ⁺ and Sc³⁺, have been investigated in the search for alternative solid oxide fuel cell anodes. The choice of dopant controls the structure, redox properties, conductivity and electrocatalytic properties of the compound.     

Plasma spray synthesis of La10(SiO4)6O3 as a new electrolyte for intermediate temperature solid oxide fuel cells

The apatite-type lanthanum silicate films were successfully synthesized by modified atmosphere plasma spraying using lanthanum oxide and silicon oxide mixed powders and precalcined hypereutectic powders in the size range 1–3 μm and 5–8 μm, respectively, as starting feedstock materials. The films differed not only in microstructural scale, but also in the characteristic of the degree of film densification. A detail describing the evolution of microstructure has been discussed. A considerable improvement in densification of the La₁₀(SiO₄)₆O₃ electrolyte films has been observed.     

Cathode contact optimization and performance evaluation of intermediate temperature-operating solid oxide fuel cell stacks based on anode-supported planar cells with LaNi0.6Fe0.4O3 cathode

This paper reports the development of intermediate temperature-operating solid oxide fuel cell stacks using anode-supported planar cells with LaNi_0.6Fe_0.4O₃ (LNF)cathode. We developed metallic separators with radial gas flow channels and an anode seal structure. To achieve good power-generating characteristics, we propose two cathode contact methods. According to a performance evaluation at 800 °C, power density of 0.5 W cm⁻² is obtained at the current density of 1.0 A cm⁻² when operating with a sufficient fuel amount, and power conversion efficiency of over 50% LHV is obtained at the current density of more than 0.2 A cm⁻² when operating at a high fuel utilization rate.     

Preparation and characterization of nanocrystalline Ce0.8Sm0.2O1.9 for low temperature solid oxide fuel cells based on composite electrolyte

Nanocrystalline Ce_0.8Sm_0.2O_1.9 (SDC) has been synthesized by a combined EDTA–citrate complexing sol–gel process for low temperature solid oxide fuel cells (SOFCs) based on composite electrolyte. A range of techniques including X-ray diffraction (XRD), and electron microscopy (SEM and TEM) have been employed to characterize the SDC and the composite electrolyte. The influence of pH values and citric acid-to-metal ions ratios (C/M) on lattice constant, crystallite size and conductivity has been investigated. Composite electrolyte consisting of SDC derived from different synthesis conditions and binary carbonates (Li₂CO₃–Na₂CO₃) has been prepared and conduction mechanism is discussed. Water was observed on both anode and cathode side during the fuel cell operation, indicating the composite electrolyte is co-ionic conductor possessing H⁺ and O²⁻ conduction. The variation of composite electrolyte conductivity and fuel cell power output with different synthesis conditions was in accordance with that of the SDC originated from different precursors, demonstrating O²⁻ conduction is predominant in the conduction process. A maximum power density of 817 mW cm⁻² at 600 °C and 605 mW cm⁻² at 500 °C was achieved for fuel cell based on composite electrolyte.     

Reactivity between La(Sr)FeO3 cathode,doped CeO2 interlayer and yttria-stabilized zirconia electrolyte for solid oxide fuel cell applications

Detailed X-ray diffraction (XRD) analysis of two different Sr-doped LaFeO₃ cathodes, YSZ electrolyte and two Sm/Gd-doped CeO₂ interlayer and their mixtures were used to evaluate the formation of undesired secondary reaction compounds. The analysis of room temperature X-ray diffraction data of the mixtures indicates the crystallization of strontium and/or lanthanum zirconates between the cathode and the electrolyte materials and no detected reaction between the cathode and the interlayer materials.     

Thermal properties of Li4/3Ti5/3O4/LiMn2O4 cell

The thermal properties of Li_4/3Ti_5/3O₄ and Li_1+xMn₂O₄ electrodes were investigated by isothermal micro-calorimetry (IMC). The 150-mAh g⁻¹ capacity of a Li/Li_4/3Ti_5/3O₄ half cell was obtained through the voltage plateau that occurs at 1.55 V during the phase transition from spinel to rock salt. Extra capacity below 1.0 V was attributed to the generation of a new phase. The small and constant entropy change of Li_4/3Ti_5/3O₄ during the spinel/rock-salt phase transition indicated its good thermal stability. Accelerated rate calorimetry confirmed that Li_4/3Ti_5/3O₄ has better thermal characteristics than graphite. The IMC results for a Li/Li_1+xMn₂O₄ half cell indicated less heat variation due to the suppression of the order/disorder change by lithium doping. The heat profiles of the Li_4/3Ti_5/3O₄/Li_1+xMn₂O₄ full cell indicated less heat generation compared with a mesocarbon-microbead graphite/Li_1+xMn₂O₄ cell.     

Electrical properties of nanocube CeO2 in advanced solid oxide fuel cells

Search for electrolyte materials with a high ionic conductivity at low temperatures has always been a key challenge for the development of solid oxide fuel cells (SOFCs). In present work, we found un-doped CeO₂ nanocubes used as an electrolyte for advanced fuel cell showed remarkable performances. The CeO₂ nanocubes were synthesized by a simple hydrothermal approach. The synthesized CeO₂ nanocubes were used as an electrolyte sandwiched between two layers of semiconducting Ni_0.8Co_0.15Al_0.05LiO_2-δ to fabricate the fuel cell. Such device has achieved an excellent maximum power density of 406 mW cm^?2 at 600 °C. These results demonstrate CeO₂/CeO_2-δ heterogeneous interfaces could provide a high ionic conductive path conductor for the electrolyte in SOFCs, which widen the selecting range of the electrolyte candidates for advanced SOFCs.