Properties of BaCe1−xTixO3 materials for hydrogen electrochemical separators

In this work the structural, microstructural and electrical properties of BaCe_1−xTi_xO₃ materials were investigated. The series of materials with different titanium concentrations x (0–0.3) were prepared by solid-state reaction method. The structural studies by X-ray diffraction have shown that undoped material crystallizes in orthorhombic phase, while the increasing concentration of Ti dopant up to x = 0.2 leads to the ordering of the structure to phases with higher symmetries (tetragonal and even cubic). The estimated solubility limit was found to be not higher than 20 at.% of Ti. Microstructure observations by scanning electron microscopy and linear contraction determination have shown the strong influence of Ti dopant on microstructure and an improvement of sinterability. The DC four-probe electrical conductivity measurements accompanied by the potentiometric EMF measurements of solid-state electrochemical cells in controlled gas atmospheres (containing H₂, O₂ and H₂O) and temperatures (500–800 °C) allowed determination of the total and partial electrical conductivities of selected materials. It was found that the introduction of Ti dopant leads to a decrease in total electrical conductivity by ca. one order of magnitude compared to the undoped material, almost independently of Ti concentration. Also, the modification of transport properties after doping with titanium was determined.     

Sintering and conductivity of BaCe0.9Y0.1O2.95 synthesized by the sol-gel method

Ceramic powders of BaCe_0.9Y_0.1O_2.95 (BCY10) have been prepared by the sol-gel method. Barium and yttrium acetate and cerium nitrate were used as ceramic precursors in a water solution. The reaction process studied by DTA-TG and XRD showed that calcination of the precursor powder at T ≥ 1000 °C produces a single perovskite phase. The densification behaviour of green compacts studied by constant heating rate dilatometry revealed that the shrinkage rate was maximal at 1430 °C. Sintered densities higher than 95% of the theoretical one were thus obtained below 1500 °C. The bulk and additional blocking effects were characterized by impedance spectroscopy in wet atmosphere between 150 and 600 °C. A proton conduction behaviour was clearly identified. The blocking effect can be related to a space-charge depletion layer of protons in the vicinity of grain boundaries.     

Superprotonic KH(PO3H)–SiO2 composite electrolyte for intermediate temperature fuel cells

Novel thin film composite electrolyte membranes, prepared by dispersion of nano-sized SiO₂ particles in the solid acid compound KH(PO₃H), can be operated under both oxidizing and reducing conditions. Long-term stable proton conductivity is observed at 140 °C, i.e., slightly above the superprotonic phase transition temperature of KH(PO₃H), under conditions of relatively low humidification (pH₂O ≈ 0.02 atm).     

Novel cobalt-free cathode materials BaCexFe1−xO3−δ for proton-conducting solid oxide fuel cells

A series of cobalt-free and low cost BaCe_xFe_1−xO_3−δ (x = 0.15, 0.50, 0.85) materials are successful synthesized and used as the cathode materials for proton-conducting solid oxide fuel cells (SOFCs). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BaCe_xFe_1−xO_3−δ cathode layer, is assembled and tested from 600 to 700 °C with humidified hydrogen (3% H₂O) as the fuel and the static air as the oxidant. Within all the cathode materials above, the cathode BaCe_0.5Fe_0.5O_3−δ shows the highest cell performance which could obtain an open-circuit potential of 0.99 V and a maximum power density of 395 mW cm⁻² at 700 °C. The results indicate that the Fe-doped barium cerates can be promising cathodes for proton-conducting SOFCs.     

Effect of Sm0.2Ce0.8O1.9 on the carbon coking in Ni-based anodes for solid oxide fuel cells running on methane fuel

To directly use hydrocarbon fuel without a reforming process, a new microstructure for Ni/Sm_0.2Ce_0.8O_2−δ (Ni/SDC) anodes, in which the Ni surface of the anode is covered with a porous Sm_0.2Ce_0.8O_2−δ thin film, was investigated as an alternative to conventional Ni/YSZ anodes. The porous SDC thin layer was coated on the pores of the anode using the sol–gel coating method. The cell performance was improved by 20%–25% with the Ni/SDC anode relative to the cell performance with the Ni/YSZ anode due to the high ionic conductivity of the Ni/SDC anode and the increase of electrochemical reaction sites. For the SDC-coated Ni/SDC anode operating with methane fuel, no significant degradation of the cell performance was observed after 180 h due to the surface modification with the SDC film on the Ni surface, which opposes the severe degradation of the cell performance that was observed for the Ni/YSZ anode, which results from carbon deposition by methane cracking. Carbon was hardly detected in the SDC-coated Ni/SDC anode due to the catalytic oxidation of the deposited carbon on the SDC film as well as the electrochemical oxidation of methane in the triple-phase-boundary.     

Electrophoretic deposition of (Mn,Co)3O4 spinel coating for solid oxide fuel cell interconnects

We discuss here our attempt to develop (Mn,Co)₃O₄ spinel coatings on the surface of Cr-containing steel through electrophoretic deposition (EPD) followed by reduced-atmosphere sintering for solid oxide fuel cell (SOFC) interconnect application. The effects of EPD voltages and sintering atmospheres on the microstructure, electrical conductivity and long-term stability of the coated interconnects are examined by means of scanning electron microscopy (SEM), energy dispersion spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and four-probe resistance techniques. For the spinel coatings generated using smaller voltage than 400 V, the interconnect surfaces exhibit good packing behavior and high conductivity. The reduced atmosphere during sintering has a beneficial impact on the minimizing chromia subscale formation and thus reducing the area specific resistance (ASR) of the coated interconnects. Moreover, it is interesting to note that a more stable long-term performance is achieved for the spinel coating sintered in H₂/H₂O atmosphere with thin chromia sub-scale and no Cr penetration. Based on the current results, EPD followed by reduced-atmosphere sintering is a fast and economic way to deposit (Mn,Co)₃O₄ coating for SOFC interconnect applications.     

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.     

Characterization of the 75% Gd0.8Sr0.2CoO3−δ/25% Ce0.9Gd0.1O2−δ composite cathode system for use in intermediate temperature solid oxide fuel cells

The composite cathode system is examined for suitability on a Ce_0.9Gd_0.1O_2−δ electrolyte based solid oxide fuel cell at intermediate temperatures (500–700 °C). The cathode is characterized for electronic conductivity and area specific charge transfer resistance. This cathode system is chosen for its excellent thermal expansion match to the electrolyte, its relatively high conductivity (115 S cm⁻¹ at 700 °C), and its low activation energy for oxygen reduction (99 kJ mol⁻¹). It is found that the decrease of sintering temperature of the composite cathode system produces a significant decrease in charge transfer resistances to as low as 0.25 Ω cm². The conductivity of the cathode systems is between 40 and 88 S cm⁻¹ for open porosities of 30–40%.     

Vacuum-assisted electroless copper plating on Ni/(Sm,Ce)O2 anodes for intermediate temperature solid oxide fuel cells

Cu is incorporated by vacuum-assisted electroless plating into porous Ni/Sm_0.2Ce_0.8O_1.9 (Ni/SDC) anodes as the active anodes for the oxidation reaction of hydrogen and methane of intermediate temperature solid oxide fuel cells (IT-SOFCs). The scanning electron microscopy (SEM) observation indicates the formation of a uniformly distributed nano-structured Cu network within the porous Ni/SDC microstructure. The maximum power density of the cell with the Cu electroless-plated Ni/SDC anodes is 0.84 and 0.54 W cm⁻² in dry H₂ and dry CH₄ at 600 °C, respectively, enhanced by ∼30% as compared to the cell with conventional Ni/SDC anodes. The increase in the performance of the cell with the Cu electroless-plated Ni/SDC anodes is most likely attributed to the enlarged effective three-phase boundaries (TPBs) by interconnecting the isolated Ni and/or SDC particles with the electroless-plated Cu network and the formation of TPBs at the Cu/SDC interface due to the activation of SDC surface by the Cu deposition. The stability test shows that cell degradation in dry methane due to carbon deposition is significantly reduced by the electroless copper plating.     

Microstructural and electrochemical impedance study of nickel-Ce0.9Gd0.1O1.95 anodes for solid oxide fuel cells fabricated by ultrasonic spray pyrolysis

Optimization of the electrode microstructure in a solid oxide fuel cell (SOFC) is an important approach to performance enhancement. In this study, the relationship between the microstructure and electrochemical performance of an anode electrode fabricated by ultrasonic spray pyrolysis was investigated. Nickel-Ce_0.9Gd_0.1O_1.95 (Ni-CGO) anodes were deposited on a dense yttria stabilized zirconia (YSZ) substrate by ultrasonic spray pyrolysis, and the resulting microstructure was analyzed. Scanning electron microscope (SEM) examinations revealed the impact of deposition temperature and precursor solution concentration on anode morphology, particle size and porosity. The electrochemical performance of the anode was measured by electrochemical impedance spectroscopy (EIS) using a Ni-CGO/YSZ/Ni-CGO symmetrical cell. The deposited anode had a particle size and porosity in ranging between 1.5-17 μm and 21%-52%, respectively. The estimated volume-specific triple phase boundary (TPB) length increased from 1.37 × 10⁻³ μm μm⁻³ to 1.77 × 10⁻¹ μm μm⁻³as a result of decrease of the particle size and increase of the porosity. The corresponding area specific charge transfer resistance decreased from 5.45 ohm cm² to 0.61 ohm cm² and the activation energy decreased from 1.06 eV to 0.86 eV as the TPB length increased.     

Characterization of Pr1−xSrxCo0.8Fe0.2O3−δ (0.2 ≤ x ≤ 0.6) cathode materials for intermediate-temperature solid oxide fuel cells

Cathode materials consisting of Pr_1−xSr_xCo_0.8Fe_0.2O_3−δ (x = 0.2–0.6) were prepared by the sol–gel process for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The samples had an orthorhombic perovskite structure. The electrical conductivities were all higher than 279 S cm⁻¹. The highest conductivity, 1040 S cm⁻¹, was found at 300 °C for the composition x = 0.4. Symmetrical cathodes made of Pr_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (PSCF)–Ce_0.85Gd_0.15O_1.925 (50:50 by weight) composite powders were screen-printed on GDC electrolyte pellets. The area specific resistance value for the PSCF–GDC cathode was as low as 0.046 Ω cm² at 800 °C. The maximum power densities of a cell using the PSCF–GDC cathode were 520 mW cm⁻², 435 mW cm⁻² and 303 mW cm⁻² at 800 °C, 750 °C and 700 °C, respectively.     

Ni-Sm2O3 cermet anodes for intermediate-temperature solid oxide fuel cells with stabilized zirconia electrolytes

Ni-LnO_x cermets (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd), in which LnO_x is not an oxygen ion conductor, have shown high performance as the anodes for low-temperature solid oxide fuel cells (SOFCs) with doped ceria electrolytes. In this work, Ni-Sm₂O₃ cermets are primarily investigated as the anodes for intermediate-temperature SOFCs with scandia stabilized zirconia (ScSZ) electrolytes. The electrochemical performances of the Ni-Sm₂O₃ anodes are characterized using single cells with ScSZ electrolytes and LSM-YSB composite cathodes. The Ni-Sm₂O₃ anodes exhibit relatively lower performance, compared with that reported Ni-SDC (samaria doped ceria) and Ni-YSZ (yttria stabilized zirconia) anodes, the state-of-the-art electrodes for SOFCs based on zirconia electrolytes. The relatively low performance is possibly due to the solid-state reaction between Sm₂O₃ and ScSZ in fuel cell fabrication processes. By depositing a thin interlayer between the Ni-Sm₂O₃ anode and the ScSZ electrolyte, the performance is substantially improved. Single cells with a Ni-SDC interlayer show stable open circuit voltage, generate peak power density of 410 mW cm⁻² at 700 °C, and the interfacial polarization is about 0.7 Ω cm².     

Development of Ag-(BaO)0.11(Bi2O3)0.89 composite cathodes for intermediate temperature solid oxide fuel cells

The electrochemical performances of Ag-(BaO)_0.11(Bi₂O₃)_0.89 (BSB) composite cathodes on Ce_0.8Sm_0.2O_1.9 electrolytes have been investigated for intermediate temperature solid oxide fuel cells (ITSOFCs) using ac impedance spectroscopy from 500 to 700 °C. Results indicate that the electrochemical properties of these composites are quite sensitive to the composition and the microstructure of the cathode. The optimum BSB addition (50% by volume) to Ag resulted in about 20 times lower area specific resistance (ASR) at 650 °C. The ASR values for the Ag50-BSB and Ag cathodes were 0.32 and 6.5 Ω cm² at 650 °C, respectively. The high performances of Ag-BSB cathodes are determined by the high catalytic activity for oxygen dissociation and ionic conductivity of BSB, and by the excellent catalytic activity for oxygen reduction of silver. The maximum power density of the Ag50-BSB cathode was 224 mWcm⁻² at 650 °C, which classify this composite as a promising material for ITSOFC.     

Coking-resistant NbOx-Ni-Ce0.8Sm0.2O1.9 anode material for methanol-fueled solid oxide fuel cells

NbO_x is added in Ni-Ce_0.8Sm_0.2O_1.9 by impregnation as an anode material for solid oxide fuel cells fed with methanol. Nb (IV) and Nb (V) exist in the reduced anode. The addition of Nb reduces the binding energy of Ni. The catalytic activity of the anode and the performance of the single cell both increase with the increase of Nb. At 700 °C, the cell with 5NbO_x-Ni-Ce_0.8Sm_0.2O_1.9 anode and Ce_0.8Sm_0.2O_1.9-carbonate electrolyte shows a output power density of 687 mW cm^?2. Meanwhile, water produced in the anode is absorbed by NbO_x and forms surface hydroxyl groups, which facilitates the removal of carbon. The addition of NbO_x decreases the amount of deposited carbon in the humidified methanol atmosphere significantly, and an improved stability of the single cell is achieved.     

Sr2Fe4/3Mo2/3O6 as anodes for solid oxide fuel cells

Sr₂Fe_4/3Mo_2/3O₆ has been synthesized by a combustion method in air. It shows a single cubic perovskite structure after being reduced in wet H₂ at 800 °C and demonstrates a metallic conducting behavior in reducing atmospheres at mediate temperatures. Its conductivity value at 800 °C in wet H₂ (3% H₂O) is about 16 S cm⁻¹. This material exhibits remarkable electrochemical activity and stability in H₂. Without a ceria interlayer, maximum power density (P_max) of 547 mW cm⁻² is achieved at 800 °C with wet H₂ (3% H₂O) as fuel and ambient air as oxidant in the single cell with the configuration of Sr₂Fe_4/3Mo_2/3O₆|La_0.8Sr_0.2Ga_0.83Mg_0.17O₃ (LSGM)| La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF). The P_max even increases to 595 mW cm⁻² when the cell is operated at a constant current load at 800 °C for additional 15 h. This anode material also shows carbon resistance and sulfur tolerance. The P_max is about 130 mW cm⁻² in wet CH₄ (3% H₂O) and 472 mW cm⁻² in H₂ with 100 ppm H₂S. The cell performance can be effectively recovered after changing the fuel gas back to H₂.     

Study on Sm1.8Ce0.2CuO4-Ce0.9Gd0.1O1.95 composite cathode materials for intermediate temperature solid oxide fuel cell

Sm_1.8Ce_0.2CuO₄-xCe_0.9Gd_0.1O_1.95 (SCC-xCGO, x = 0-12 vol.%) composite cathodes supported on Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte are studied for applications in IT-SOFCs. Results show that Sm_1.8Ce_0.2CuO₄ material is chemically compatible with Ce_0.9Gd_0.1O_1.95 at 1000 °C. The composite electrode exhibits optimum microstructure and forms good contact with the electrolyte after sintering at 1000 °C for 4 h. The polarization resistance (R_p) reduces to the minimum value of 0.17 Ω cm² at 750 °C in air for SCC-CGO06 composite cathode. The relationship between R_p and oxygen partial pressure indicates that the reaction rate-limiting step is the surface diffusion of the dissociative adsorbed oxygen on the composite cathode.     

A novel design of anode-supported solid oxide fuel cells with Y2O3-doped Bi2O3, LaGaO3 and La-doped CeO2 trilayer electrolyte

Anode-supported solid oxide fuel cells (SOFCs) with a trilayered yttria-doped bismuth oxide (YDB), strontium- and magnesium-doped lanthanum gallate (LSGM) and lanthanum-doped ceria (LDC) composite electrolyte film are developed. The cell with a YDB (18 μm)/LSGM (19 μm)/LDC (13 μm) composite electrolyte film (designated as cell-A) shows the open-circuit voltages (OCVs) slightly higher than that of a cell with an LSGM (31 μm)/LDC (17 μm) electrolyte film (designated as cell-B) in the operating temperature range of 500-700 °C. The cell-A using Ag-YDB composition as cathode exhibits lower polarization resistance and ohmic resistance than those of a cell-B at 700 °C. The results show that the introduction of YDB to an anode-supported SOFC with a LSGM/LDC composite electrolyte film can effectively block electronic transport through the cell and thus increased the OCVs, and can help the cell to achieve higher power output.     

Enhanced performance of solid oxide fuel cells with Ni/CeO2 modified La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes

The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) anodes are modified using Ni(NO₃)₂ and/or Ce(NO₃)₃/(Sm,Ce)(NO₃)_x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO₂ to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (P_max) at 850 °C is 198 mW cm⁻² when dry H₂ and air are used as the fuel and oxidant, respectively. When H₂ is changed to CH₄, the value of P_max is 32 mW cm⁻². After 8.9 wt.% Ni and 5.8 wt.% CeO₂ are introduced into the LSCrM anode, the cell exhibits increased values of P_max 432, 681, 948 and 1135 mW cm⁻² at 700, 750, 800 and 850 °C, respectively, with dry H₂ as fuel and air as oxidant. When O₂ at 50 mL min⁻¹ is used as the oxidant, the value of P_max increases to 1450 mW cm⁻² at 850 °C. When dry CH₄ is used as fuel and air as oxidant, the values of P_max reach 95, 197, 421 and 645 mW cm⁻² at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.     

La0.84Sr0.16MnO3−δ cathodes impregnated with Bi1.4Er0.6O3 for intermediate-temperature solid oxide fuel cells

La_0.84Sr_0.16MnO_3−δ–Bi_1.4Er_0.6O₃ (LSM–ESB) composite cathodes are fabricated by impregnating LSM electronic conducting matrix with the ion-conducting ESB for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The performance of LSM–ESB cathodes is investigated at temperatures below 750 °C by AC impedance spectroscopy. The ion-impregnation of ESB significantly enhances the electrocatalytic activity of the LSM electrodes for the oxygen reduction reactions, and the ion-impregnated LSM–ESB composite cathodes show excellent performance. At 750 °C, the value of the cathode polarization resistance (R_p) is only 0.11 Ω cm² for an ion-impregnated LSM–ESB cathode, which also shows high stability during a period of 200 h. For the performance testing of single cells, the maximum power density is 0.74 W cm⁻² at 700 °C for a cell with the LSM–ESB cathode. The results demonstrate the ion-impregnated LSM–ESB is one of the promising cathode materials for intermediate-temperature solid oxide fuel cells.     

Cobalt-free layered perovskite GdBaFe2O5+x as a novel cathode for intermediate temperature solid oxide fuel cells

A cobalt-free layered perovskite oxide, GdBaFe₂O_5+x (GBF), was investigated as a novel cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Area-specific resistance (ASR) of GBF was measured by impedance spectroscopy in a symmetrical cell. The observed ASR was as low as 0.15 Ω cm² at 700 °C and 0.39 Ω cm² at 650 °C, respectively. A laboratory sized Sm_0.2Ce_0.8O_1.9 (SDC)-based tri-layer cell of NiO-SDC/SDC/GBF was tested under intermediate temperature conditions of 550-700 °C with humidified H₂ (∼3% H₂O) as a fuel and the static ambient air as an oxidant. A maximal power density of 861 mW cm⁻² was achieved at 700 °C. The electrode polarization resistance was as low as 0.57, 0.22, 0.13 and 0.08 Ω cm² at 550, 600, 650 and 700 °C, respectively. The experimental results indicate that the layered perovskite GBF is a promising cathode candidate for IT-SOFCs.