Electrical properties of SDC–BCY composite electrolytes for intermediate temperature solid oxide fuel cell

The electrolyte material Ce_0.85Sm_0.15O_1.92 (SDC) powders are synthesized by glycine–nitrate processes and BaCe_0.83Y_0.17O_3−δ (BCY) powders are synthesized by sol–gel processes, respectively. Then SDC–BCY composite electrolytes are prepared by mixing SDC and BCY. The SDC and BCY powders are mixed in the weight ratio of 95:5, 90:10 and 85:15 and named as SB95, SB90 and SB85, respectively. The electrical properties of SDC and SDC–BCY composites are investigated. The experimental results show that SDC–BCY composites exhibit the excellent conductivity and could significantly enhance the fuel cell performances. The behavior that SDC–BCY composites display hybrid proton and oxygen ion conduction is substantiated. Among these electrolytes, the maximum power density reaches as high as 159 mW cm⁻² for the fuel cell based on SB90 composite electrolyte at 600 °C.     

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.     

Sintering and electrical properties of Ce0.75Sm0.2Li0.05O1.95

Ceria-based electrolytes have been widely investigated in intermediate-temperature solid oxide fuel cell (SOFC), which might be operated at 500–600 °C. Samarium doped (20 mol%) ceria (20SDC) one of the most promising material in this class of compounds. In this work we report effect of lattice substitution of 5 mol % Li on Sm in (20SDC). It was prepared by citrate–nitrate auto combustion synthesis having a powder of average particle size ∼50 nm. The sintered density of more than 98% of the theoretical density at 950 °C has been achieved. Increased ionic conductivity (lattice) at 500 °C has also been achieved in Ce_0.75Sm_0.2Li_0.05O_1.95 compare to that of Ce_0.8Sm_0.2O_1.95. Corresponding activation energy of conduction ∼0.7 eV has been calculated in the temperature range of 200–600 °C. In reducing atmosphere the electrical conductivity has not been altered much. Thus Ce_0.75Sm_0.2Li_0.05O_1.95 has been found to be quite promising in terms of reducing the processing temperature as well as operating temperature of SOFC.     

Identification of oxygen reduction processes at (La,Sr)MnO3 electrode/La9.5Si6O26.25 apatite electrolyte interface of solid oxide fuel cells

Oxygen reduction reaction of (La,Sr)MnO₃ (LSM) cathode on La_9.5Si₆O_26.25 apatite (LSO) electrolyte is studied over the temperature range 750–900 °C and the oxygen partial pressure range 0.01–1 atm by electrochemical impedance spectroscopy. The impedance responses show two separable arcs and are analyzed in terms of two different equivalent circuits with comparable information on the electrode processes at high and low frequencies. The electrode process associated with the high frequency arc (σ₁) is basically independent of oxygen partial pressure. The activation energy of σ₁ is 188 ± 15 kJ mol⁻¹ for the O₂ reduction reaction on the LSM electrode sintered at 1150 °C, and decreases to 120 kJ mol⁻¹ for the O₂ reduction reaction on the LSM electrode sintered at 850 °C, which is close to 80–110 kJ mol⁻¹ observed for the same electrode process at LSM/YSZ interface. The reaction order with respect to PO₂$P_{{\text{O}}_2}$ and the activation energy of the electrode process associated with low frequency arc (σ₂) are generally close to that of σ₂ at the LSM/YSZ interface. The activation process of the cathodic polarization treatment is noticeably slower for the reaction at LSM/LSO interface as compared to that at LSM/YSZ interface. The impedance responses of O₂ reduction reaction at the LSM/LSO interface are significantly higher than that at the LSM/YSZ interface due to the silicon spreading. The impedance responses decrease with the decrease of the sintering temperature of LSM electrode on LSO electrolyte. At the sintering temperature of 1000 °C, the impedance responses of O₂ reduction reaction is 1.74 Ω cm² at 900 °C, which is significantly smaller than that of LSM electrode sintered at 1150 °C.     

Optimization of La0.6Ca0.4Fe0.8Ni0.2O3-Ce0.8Sm0.2O2 composite cathodes for intermediate-temperature solid oxide fuel cells

Sample of nominal composition La_0.6Ca_0.4Fe_0.8Ni_0.2O₃ (LCFN) was prepared by liquid mix method. The structure of the polycrystalline powder was analyzed with X-ray powder diffraction data. This compound shows orthorhombic perovskite structure with a space group Pnma. In order to improve the electrochemical performance, Sm-doped ceria (SDC) powder was added to prepare the LCFN-SDC composite cathodes. Electrochemical characteristics of the composites have been investigated for possible application as cathode material for an intermediate-temperature-operating solid oxide fuel cell (IT-SOFC). The polarization resistance was studied using Sm-doped ceria (SDC). Electrochemical impedance spectroscopy measurements of LCFN-SDC/SDC/LCFN-SDC test cell were carried out. These electrochemical experiments were performed at equilibrium from 850 °C to room temperature, under both zero dc current intensity and air. The best value of area-specific resistance (ASR) was for LCFN cathode doped with 10% of SDC (LCFN-SDC9010), 0.13 Ω cm² at 850 °C. The dc four-probe measurement exhibits a total electrical conductivity over 100 S cm⁻¹ at T ≥ 600 °C for LCFN-SDC9010 composite cathode.     

SmBaCo2O5+x double-perovskite structure cathode material for intermediate-temperature solid-oxide fuel cells

SmBaCo₂O_5+x (SBCO), an oxide with double-perovskite structure, has been developed as a novel cathode material for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The electrical conductivity of an SBCO sample reaches 815–434 S cm⁻¹ in the temperature range 500–800 °C. XRD results show that an SBCO cathode is chemically compatible with the intermediate-temperature electrolyte materials Sm_0.2Ce_0.8O_1.9 (SDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM). The polarization resistances of an SBCO cathode on SDC and LSGM electrolytes are 0.098 and 0.054 Ω cm² at 750 °C, respectively. The maximum power densities of a single cell with an SBCO cathode on SDC and LSGM electrolytes reach 641 and 777 mW cm⁻² at 800 °C, respectively. The results of this study demonstrate that the double-perovskite structure oxide SBCO is a very promising cathode material for use in IT-SOFCs.     

A comparative study of electrochemical performance of La0.5Ba0.5CoO3−δ and La0.5Ba0.5CoO3−δ–Gd0.1Ce0.9O1.95 cathodes

Cubic perovskite oxide La_0.5Ba_0.5CoO_3−δ (LBCO) and its composite with Gd_0.1Ce_0.9O_1.95 (GDC) electrolyte, LBCO–GDC in 1:1 weight ratio were prepared. Chemical compatibility between LBCO and GDC was studied and no serious phase reaction occurred at temperatures up to 1050 °C in air. Electrochemical performance of the cathodes was measured by Electrochemical Impedance Spectroscopy (EIS) as a function of temperature and oxygen partial pressure. Electrode reaction mechanism was analyzed based on fitting results of the EIS with proper equivalent circuit models. Comparison of the results demonstrated that introduction of the ionic conductive GDC component to the LBCO–GDC composite cathode hardly influenced gas diffusion through bulk of the cathode (low-frequency process) while greatly enhanced oxygen ionic transfer across the cathode/electrolyte interface (high-frequency process) and the electrode reaction occurring in the medium-frequency range. As a result, the LBCO–GDC composite cathode exhibited lower area-specific resistance (ASR) than the LBCO cathode, with ASR value ranging from ∼0.12 Ω cm² at 600 °C to ∼0.01 Ω cm² at 800 °C. These results have demonstrated that the LBCO–GDC composite (1:1 weight ratio) is highly promising as a cathode for intermediate temperature solid oxide fuel cell.     

LaNi0.6Fe0.4O3-Ce0.8Sm0.2O1.9-Ag composite cathode for intermediate temperature solid oxide fuel cells

LaNi_0.6Fe_0.4O₃ (LNF), LNF-Sm_0.2Ce_0.8O_1.9 (SDC), and LNF-SDC-Ag cathodes on SDC electrolytes were investigated at intermediate temperatures using AC impedance spectroscopy. Results show that adding 50 wt.% SDC into LNF yields a significant low area specific resistance (ASR) which was found to be 0.92 Ω cm² at 700 °C. Infiltrating 0.3 mg/cm² Ag into LNF-50 wt.% SDC can improve the electronic conductivity and oxygen exchange reaction activity, and thereby remarkably decrease the ASRs. The ASR value of the LNF-SDC-Ag cathode is as low as 0.18 Ω cm² at 700 °C, and 0.46 Ω cm² at 650 °C. The long-term test shows that the LNF-SDC-Ag cathode may be a promising candidate for solid oxide fuel cells operating at temperatures lower than 650 °C.     

Electrochemical behavior of Ba0.5Sr0.5Co0.2−xZnxFe0.8O3−δ (x = 0-0.2) perovskite oxides for the cathode of solid oxide fuel cells

Zinc-doped barium strontium cobalt ferrite (Ba_0.5Sr_0.5Co_0.2−xZn_xFe_0.8O_3−δ (BSCZF), x = 0, 0.05, 0.1, 0.15, 0.2) powders with various proportions of zinc were prepared using the ethylenediamine tetraacetic acid (EDTA)-citrate method with repeated ball-milling and calcining. They were then evaluated as cathode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFCs) using XRD, H₂-TPR, SEM, and electrochemical tests. By varying the zinc doping (x) from zero to 0.2 (as a substitution for cobalt which ranged from zero to 100%), it was found that the lowest doping of 0.05 (BSCZF05) resulted in the highest electrical conductivity of 30.7 S cm⁻¹ at 500 °C. The polarization resistances of BSCZF05 sintered at 950 °C were 0.15 Ω cm², 0.28 Ω cm² and 0.59 Ω cm² at 700 °C, 650 °C and 600 °C, respectively. The resistance decreased further by about 30% when Sm_0.2Ce_0.8O_2−δ (SDC) electrolyte particles were incorporated and the sintering temperature was increased to 1000 °C. Compared to BSCF without zinc, BSCZF experienced the lowest decrease in electrochemical properties when the sintering temperature was increased from 950 °C to 1000 °C. This decrease was due to an increase in thermal stability and a minimization in the loss of some cobalt cations without a decrease in the electrical conductivity. Using a composite cathode of BSCZF05 and 30 wt.% of SDC, button cells composed of an Ni-SDC support with a 30 μm dense SDC membrane exhibited a maximum power density of 605 mW cm⁻² at 700 °C.     

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.     

La0.4Ce0.6O1.8–La0.8Sr0.2MnO3–8 mol% yttria-stabilized zirconia composite cathode for anode-supported solid oxide fuel cells

The composite cathodes of La_0.4Ce_0.6O_1.8 (LDC)–La_0.8Sr_0.2MnO₃ (LSM)–8 mol% yttria-stabilized zirconia (YSZ) with different LDC contents were investigated for anode-supported solid oxide fuel cells with thin film YSZ electrolyte. The oxygen temperature-programmed desorption profiles of the LDC–LSM–YSZ composites indicate that the addition of LDC increases surface oxygen vacancies. The cell performance was improved largely after the addition of LDC, and the best cell performance was achieved on the cells with the composite cathodes containing 10 wt% or 15 wt% LDC. The electrode polarization resistance was reduced significantly after the addition of LDC. At 800 °C and 650 °C, the polarization resistances of the cell with a 10 wt% LDC composite cathode are 70% and 40% of those of the cell with a LSM–YSZ composite cathode, respectively. The impedance spectra show that the processes associated with the dissociative adsorption of oxygen and diffusion of oxygen intermediates and/or oxygen ions on LSM surface and transfer of oxygen species at triple phase boundaries are accelerated after the addition of LDC.     

Chemical compatibility between MgO–SiO2–B2O3–La2O3 glass sealant and low,high temperature electrolytes for solid oxide fuel cell applications

The chemical interaction study of MgO–SiO₂–B₂O₃–La₂O₃ (ML) glass with low and high-temperature electrolytes is reported as a function of different heating durations. The as prepared diffusion couples with high-temperature and low temperature electrolytes have been heat-treated at 850 °C and 800 °C, respectively, for 5, 100 and 750 h. The heat-treated diffusion couples have been characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray dot mapping and electron probe microanalysis (EPMA). Microstructural analysis of diffusion couples completely precludes the presence of any unwanted oxides and reaction products at the interface. The glass has shown good bonding characteristics and absence of delamination particularly with yttria stabilized zirconia (YSZ). Efforts have also been made to understand the interfacial reaction by considering different theoretical parameters associated with ML glass.     

Combustion synthesis and properties of highly phase-pure perovskite electrolyte Co-doped La0.9Sr0.1Ga0.8Mg0.2O2.85 for IT-SOFCs

The highly phase-pure perovskite electrolyte, La_0.9Sr_0.1Ga_0.8Mg_0.115Co_0.085O_2.85 (LSGMCO), was prepared by means of glycine–nitrate process (GNP) for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The perovskite phase evolution, sintering, electrical conductivity and electrochemical performance of LSGMCO were investigated. The results show that the highly phase-pure perovskite electrolyte LSGMCO can be obtained after calcining at 1150 °C. The sample sintered at 1450 °C for 20 h in air exhibited a better sinterability, and the relative density of LSGMCO was higher than 95%. The stoichiometric indexes of the elements in the sintered sample LSGMCO determined experimentally by EDS were in good agreement with the nominal composition. The electrical conductivities of the sample were 0.094 and 0.124 S· cm⁻¹ at 800 °C and 850 °C in air, respectively. The ionic conduction of the sample was dominant at high temperature with the higher activation energies. While at lower temperature the electron hole conduction was predominated with the lower activation energies. The maximum power densities of the single cell fabricated with LSGMCO electrolyte with Ce_0.8Sm_0.2O_1.9 (SDC) interlayer, SmBaCo₂O_5+x cathode and NiO/SDC anode achieved 643 and 802 mW cm⁻² at 800 °C and 850 °C, respectively.     

Effects of salt composition on the electrical properties of samaria-doped ceria/carbonate composite electrolytes for low-temperature SOFCs

Samaria-doped ceria (SDC)/carbonate composite electrolytes were developed for low-temperature solid oxide fuel cells (SOFCs). SDC powders were prepared by oxalate co-precipitation method and used as the matrix phase. Binary alkaline carbonates were selected as the second phase, including (Li–Na)₂CO₃, (Li–K)₂CO₃ and (Na–K)₂CO₃. AC conductivity measurements showed that the conductivities in air atmosphere depended on the salt composition. A sharp conductivity jump appeared at 475 °C and 450 °C for SDC/(Li–Na)₂CO₃ and SDC/(Li–K)₂CO₃, respectively. However, the conductivities of SDC/(Na–K)₂CO₃ increase linearly with temperature. Single cells based on above composite electrolytes were fabricated by dry-pressing and tested in hydrogen/air at 500–600 °C. A maximum power density of 600, 550 and 550 mW cm⁻² at 600 °C was achieved with SDC/(Li–Na)₂CO₃, SDC/(Li–K)₂CO₃ and SDC/(Na–K)₂CO₃ composite electrolyte, respectively, which we attribute to high ionic conductivities of these composite electrolytes in fuel cell atmosphere. We discuss the conduction mechanisms of SDC/carbonate composite electrolytes in different atmospheres according to defect chemistry theory.     

Carbon doped MO–SDC material as an SOFC anode

Oxide mixtures MO–SDC, M = Cu, Ni, Co, SDC = Ce_0.9Sm_0.1O_1.95 were synthesized by employing a citrate/nitrate combustion technique. Two kinds of Carbon materials, activated carbon (AC) and vapor grown carbon fiber (VGCF) were homogeneously dispersed into the MO–SDC. The materials can be used as anodes to fabricate single cells using a uniaxial die-press method. The sintering temperature was studied to optimize cell performance. Experimental results showed that cells sintered at 700 °C had better performance. When the temperature was above 750 °C, the cells were severely distorted, and cannot be tested. Compared with the basic MO–SDC anode, AC and VGCF improve the solid oxide fuel cell (SOFC) anode properties, due to a change of the microstructures of the anode materials which enhance their electron conductivity. Single cell performances were evaluated by I–V measurements, and when 1.25 wt.%VGCF was introduced into the MO–SDC by ball-milling, termed: 1.25 wt.%VGCF–MO–SDC, the 1.25 wt.%VGCF–MO–SDC anode material could achieve the highest power density of up to 0.326 W cm⁻² with H₂ as fuel. The calcination temperature of the MO–SDC dry gel also strongly influenced the electrochemical performance of the 1.25 wt.%VGCF–MO–SDC material. XRD spectra for each calcined temperature and the I–V measurement both suggest that calcinations at 550 °C for 1 h are suitable. 1.0 wt.%AC–MO–SDC and 1.25 wt.%VGCF–MO–SDC have similar performance when the cell was fed in methanol/3%H₂O, and the corresponding power density was up to 0.253 W cm⁻². Traces of carbon were found in the off-gases.     

Electrochemical performance of a solid oxide fuel cell based on Ce0.8Sm0.2O2−δ electrolyte synthesized by a polymer assisted combustion method

A polyvinyl alcohol assisted combustion synthesis method was used to prepare Ce_0.8Sm_0.2O_2−δ (SDC) powders for an intermediate temperature solid oxide fuel cell (IT-SOFC). The XRD results showed that this combustion synthesis route could yield phase-pure SDC powders at a relatively low calcination temperature. A thin SDC electrolyte film with thickness control was produced by a dry pressing method at a lower sintering temperature of 1250 °C. With Sm_0.5Sr_0.5Co₃-SDC as the composite cathode, a single cell based on this thin SDC electrolyte was tested from 550 to 650 °C. The maximum power density of 936 mW cm⁻² was achieved at 650 °C using humidified hydrogen as the fuel and stationary air as the oxidant.     

Optimization of electrochemical performance of Ca3Co2O6 cathode on yttria-stabilized zirconia electrolyte for intermediate temperature solid oxide fuel cells

Ca₃Co₂O₆ (CCO) is synthesized by solid state reaction for intermediate temperature solid oxide fuel cells (IT-SOFCs) on yttria-stabilized zirconia (YSZ) electrolyte. Thermal expansion coefficient (TEC), electrical conductivity (σ) and chemical compatibility of CCO with YSZ are characterized. The experiment results show that CCO and YSZ are chemical compatible only up to 800 °C. By introducing a Sm_0.2Ce_0.8O_1.9 (SDC) interlayer to avoid the direct contact of CCO with YSZ, the area specific resistance (ASR) of CCO cathode is significantly decreased from 13.06 Ω cm² to 0.60 Ω cm² at 750 °C. Furthermore, the addition of frit can lower the sintering temperature of the cathode to ∼800 °C, also resulting in a remarkable decreasing of the ASR to 3.87 Ω cm² at 750 °C.     

A double-layer composite electrode based on SrSc0.2Co0.8O3−δ perovskite with improved performance in intermediate temperature solid oxide fuel cells

Dual-layer composite electrodes consisting of a layer adjoining to an Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte composed of 70 wt.% SrSc_0.2Co_0.8O_3−δ + 30 wt.% Sm_0.2Ce_0.8O_1.9 (SScC + SDC composite) and a second layer composed of 70 wt.% SrSc_0.2Co_0.8O_3−δ + 30 wt.% Sm_0.5Sr_0.5CoO_3−δ (SScC + SmSC composite) were fabricated and investigated as potential cathodes in intermediate temperature solid-oxide fuel cells. Thermo-mechanical compatibility between the two electrode layers and between the electrode and the electrolyte were examined by SEM, XRD and EIS. After sintering, no clear boundary between SScC + SDC and SScC + SmSC layers was observable by SEM. The repeated thermal cycling didn’t induce the delamination of the electrode from the electrolyte nor the formation of cracks within the electrode. As a result, stable electrode performance was achieved during thermal cycling and long-term operation. Symmetric cell tests demonstrated that the dual-layer electrode with a ∼10-μm SScC + SDC layer and a ∼50-μm SScC + SmSC layer (SScC + SDC/SScC + SmSC (1:5)) had the lowest electrode-polarization resistance among those tested. Anode-supported fuel cells with an SDC electrolyte and SScC + SDC/SScC + SmSC (1:5) cathode were fabricated. Peak power density as high as 1326 mW cm⁻² was achieved at 650 °C, which was higher than for similar fuel cells with a single-layer SScC + SDC or an SScC + SmSC composite electrode.     

Preparation and characterization of silver-modified La0.8Sr0.2MnO3 cathode powders for solid oxide fuel cells by chemical reduction method

Herein a chemical reduction method is proposed in order to modify the solid oxide fuel cells (SOFC) traditional cathode material La_0.8Sr_0.2MnO_3−x (LSM). Silver nanoparticles were prepared by the reduction of ammoniacal silver nitrate with ascorbic acid in dilute aqueous solutions containing PVP. The obtained LSM–Ag composite powders were characterized by XRD, SEM, EDX, and STEM. The results showed that the LSM–Ag composite powder possess an elaborated fine structure with a homogeneous distribution of Ag and LSM, which effectively shortens the diffusion pathway for electrons and adsorbed oxygen. The electrochemical performance of the LSM–Ag cathode with different Ag loadings was investigated. A cathode loading with 1 wt.% Ag exhibited an area specific resistance as low as 0.45 Ω cm² at 750 °C, compared to around 1.1 Ω cm² for a pure LSM electrode. Similarly an anode-supported SOFC with 1 wt.% Ag in the cathode shows a peak power density of 1199 mW cm⁻¹, higher than the value of 717 mW cm⁻¹ achieved for a similar cell with a LSM cathode. Increasing the Ag loading is shown to have an insignificant effect on improving electrocatalytic performance at 750 °C, however it can increase output power at 650 °C.     

ZnO-doped BaZr0.85Y0.15O3−δ proton-conducting electrolytes: Characterization and fabrication of thin films

ZnO-doped BaZr_0.85Y_0.15O_3−δ perovskite oxide sintered at 1500 °C has bulk conductivity of the order of 10⁻² S cm⁻¹ above 650 °C, which makes it an attractive proton-conducting electrolyte for intermediate-temperature solid oxide fuel cells. The structure, morphology and electrical conductivity of the electrolyte vary with sintering temperature. Optimal electrochemical performance is achieved when the sintering temperature is about 1500 °C. Cathode-supported electrolyte assemblies were prepared using spin coating technique. Thin film electrolytes were shown to be dense using SEM and EDX analyses.