Novel layered perovskite GdBaCoFeO5+δ as a potential cathode for proton-conducting solid oxide fuel cells

While cobalt-containing perovskite-type cathode materials facilitate the activation of oxygen reduction, they also suffer from problems like poor chemical stability in CO₂, high thermal expansion coefficients, etc. Partial B site substitution with Fe element is expected to be able to mitigate these problems while keeping high catalyst performance. In this paper, a layered perovskite GdBaCoFeO_5+δ (GBCF) was developed as a cathode material for protonic ceramic membrane fuel cells (PCMFCs) based on proton-conducting electrolyte of stable BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7). The button cells of Ni-BZCY7|BZCY7|GBCF were fabricated and tested from 600 to 700 °C with humidified H₂ (∼3% H₂O) as a fuel and ambient oxygen as oxidant. An open-circuit potential of 1.002 V, maximum power density of 482 mW cm⁻², and a low electrode polarization resistance of 0.11 Ωcm² were achieved at 700 °C. The experimental results indicated that the layered perovskite GBCF is a good candidate for cathode material, while the developed Ni-BZCY7|BZCY7|GBCF cell is a promising functional material system for intermediate temperature solid oxide fuel cells.     

Novel layered perovskite SmBaCu2O5+δ as a potential cathode for intermediate temperature solid oxide fuel cells

A novel layered perovskite SmBaCu₂O_5+δ (SBCO) as a potential cathode for intermediate temperature solid oxide fuel cells (IT-SOFC) has been investigated in this paper. The SmBaCu₂O_5+δ oxide was synthesized by EDTA- Citrate complexing sol-gel process. The crystal structure, the thermal expansion, the electrical conductivity and electrochemical properties have been characterized by X-ray diffraction (XRD), dilatometer, four-probe dc method, electrochemical impedance spectroscopy (EIS) and cathodic polarization examinations. The average thermal expansion coefficient (TEC) of SBCO was 14.6 × 10⁻⁶/ °C in the temperature range of 50-800 °C, which matched Sm-doped ceria (SDC) electrolytes. The electrode polarization resistance was 0.469 Ωcm². Considering low thermal expansions and good electrochemical properties, layered perovskite SBCO shows promising performance as cathode material for IT-SOFCs.     

Electrochemical performance of PrBaCo2O5+δ layered perovskite as an intermediate-temperature solid oxide fuel cell cathode

PrBaCo₂O_5+δ (PBCO) powder was prepared by a combined EDTA and citrate complexing method. The electrochemical performance of PBCO as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs) was evaluated. A porous layer of PBCO was deposited on a 42 μm thick electrolyte consisting of Ce_0.8Sm_0.2O_1.9 (SDC), prepared by a dry-pressing process. A fuel cell with a structure PBCO/SDC/Ni-SDC provides a maximum power density of 866, 583, 313 and 115 mW cm⁻² at 650, 600, 550 and 500 °C, respectively, using hydrogen as the fuel and stationary air as the oxidant. The total resistance of the cell was about 0.41, 0.51, 0.57 and 0.77 Ω cm², respectively. This encouraging data identifies PBCO as a potential cathode material for IT-SOFCs.     

Characterization of cation-ordered perovskite oxide LaBaCo2O5+δ as cathode of intermediate-temperature solid oxide fuel cells

A-site cation-ordered perovskite oxide LaBaCo₂O_5+δ (LBCO) was synthesized and evaluated as a cathode material of intermediate-temperature solid oxide fuel cells (IT-SOFCs). LBCO was structurally stable when calcined at 850 °C in air but transformed into cation-disordered structure at 1050 °C. LBCO showed chemical compatibility with Gd_0.1Ce_0.9O_1.95 (GDC) electrolyte at 850 °C and 1000 °C in air. Conductivity of LBCO firstly increased slightly with higher temperature to a maximum of 470 S cm⁻¹ at ∼250 °C and then decreased gradually with further increase in temperature. Electrochemical impedance spectra of the LBCO/GDC/LBCO symmetric cell were measured, and electrode reaction mechanism for the LBCO cathode was analyzed. The electrode polarization resistance of LBCO was mainly contributed by oxygen ionic transfer across the cathode/electrolyte interface and oxygen atom diffusion-electronic charge transfer process. Low area-specific resistances with values ranging from 0.15 Ω cm² at 650 °C to 0.0086 Ω cm² at 800 °C were obtained. These results have demonstrated that the A-site cation-ordered perovskite oxide LBCO is a promising cathode material for IT-SOFCs.     

A novel cobalt-free layered GdBaFe2O5+δ cathode for proton conducting solid oxide fuel cells

While cobalt-containing perovskite-type cathode materials facilitate the activation of oxygen reduction, they also suffer from problems like poor chemical stability in CO₂ and high thermal expansion coefficients. In this research, a cobalt-free layered GdBaFe₂O_5+δ (GBF) perovskite was developed as a cathode material for protonic ceramic membrane fuel cells (PCMFCs) based on proton conducting electrolyte of stable BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7). The button cells of Ni-BZCY7|BZCY7|GBF were fabricated and characterized using complex impedance technique from 600 to 700 °C. An open-circuit potential of 1.007 V, maximum power density of 417 mW cm⁻², and a low electrode polarization resistance of 0.18 Ω cm² were achieved at 700 °C. The results indicate that layered GBF perovskite is a good candidate for cobalt-free cathode material, while the developed Ni-BZCY7|BZCY7|GBF cell is a promising functional material system for solid oxide fuel cells.     

Cobalt-free Sr0.7Y0.3CuO2+δ as a cathode for intermediate-temperature solid oxide fuel cell

Cobalt-free oxide Sr_0.7Y_0.3CuO_2+δ (SYCu) with one-dimensional structure has been investigated as potential cathode material for intermediate temperature solid oxide fuel cell (IT-SOFC) applications. The crystal structure, chemical compatibility, thermal expansion and electrochemical performance were examined by X-ray diffraction technique, electrochemical workstation and thermal dilatometer. One-dimensional structure Sr_1−xY_xCuO_2+δ and Sr_2−xY_xCuO_3+δ phases appeared as the main parts after calcination above 900 °C. The copper based oxide SYCu showed a thermal expansion coefficient (TEC) about 11.1 × 10⁻⁶/°C at 25–800 °C, exhibiting good physical compatibility with samarium doped cerium (SDC) electrolyte. High electro-catalytic performance was obtained for SYCu cathode in a symmetrical cell with a polarization resistance (R_p) of 0.029 Ω cm² and an overpotential of 4.9 mV at 100 mA/cm² at 800 °C, showing great promising use as cathode materials for IT-SOFCs. In addition, the polarization resistance of SYCu cathode remain constant after operation at 800 °C for 100 h, showing excellent long-term stability at operation temperature.     

SrCo1−yTiyO3−δ as potential cathode materials for intermediate-temperature solid oxide fuel cells

The perovskites SrCo_1−yTi_yO_3−δ (SCTy, y = 0.00-0.20) are synthesized and assessed as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) based on the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte. SCTy composites with y ≥ 0.05 adopt a cubic perovskite structure with thermal stability between 30 °C and 1000 °C in air. Substitution of Ti significantly enhances the electrical conductivity of the SCTy composites relative to the undoped SrCoO_3−δ. The highest electrical conductivity of the sample with y = 0.05 varied from 430 S cm⁻¹ to 160 S cm⁻¹ between 300 °C to 800 °C in air. The area-specific resistances of the SCTy cathodes on the LSGM electrolyte gradually increase from 0.084 Ω cm² at y = 0.05 to 0.091 Ω cm² at y = 0.20 with increasing Ti content at 750 °C. Single-cells that used SCTy cathodes with y = 0.05, 0.10, 0.15, and 0.20 on a 300 μm-thick LSGM electrolyte achieve peak power densities of 793, 608, 525, and 425 mW cm⁻² at 800 °C, respectively. These novel SCTy cubic perovskites demonstrate considerable potential for application in IT-SOFC cathodes.     

SrCo0.7Fe0.2Ta0.1O3−δ perovskite as a cathode material for intermediate-temperature solid oxide fuel cells

Perovskite oxide SrCo_0.7Fe_0.2Ta_0.1O_3−δ (SCFT) was synthesized by a solid–state reaction and investigated as a potential cathode material for intermediate-temperature solid oxide fuel cell (IT-SOFC). The single phase SCFT having a cubic perovskite structure was obtained by sintering the sample at 1200 °C for 10 h in air. Introduction of Ta improved the phase stability of SCFT. The SCFT exhibited a good chemical compatibility with the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte at 950 °C for 10 h. The average thermal expansion coefficient was 23.8 × 10⁻⁶ K⁻¹ between 30 and 1000 °C in air. The electrical conductivities of the SCFT sample were 71–119 S cm⁻¹ in the 600−800 °C temperature range in air, and the maximum conductivity reached 247 S cm⁻¹ at 325 °C. The polarization resistance of the SCFT cathode on the LSGM electrolyte was 0.159 Ω cm² at 700 °C. The maximum power density of a single-cell with the SCFT cathode on a 300 μm-thick LSGM electrolyte reached 652.9 mW cm⁻² at 800 °C. The SCFT cathode had shown a good electrochemical stability over a period of 20 h short-term testing. These findings indicated that the SCFT could be a suitable alternative cathode material for IT-SOFCs.     

Electrochemical performance of Pr1−xYxBaCo2O5+δ layered perovskites as cathode materials for intermediate-temperature solid oxide fuel cells

Pr_1−xY_xBaCo₂O_5+δ (x = 0.3, 0.5 and 0.7) oxides were prepared and evaluated as cathode materials for intermediate-temperature solid oxide fuel cells. The effect of Y-doping on the crystal structure, oxygen vacancy concentration, thermal expansion coefficient (TEC), electrical conductivity and cathode performance of Pr_1−xY_xBaCo₂O_5+δ was investigated. These properties were compared with that of GdBaCo₂O_5+δ having a middle element of lanthanides. Pr_1−xY_xBaCo₂O_5+δ shows TEC (∼17.6 × 10⁻⁶ K⁻¹) lower than that of undoped PrBaCo₂O_5+δ, but similar to the one for GdBaCo₂O_5+δ. Y-doping causes a decrease in electrical conductivity, but at the same time induces an increase in oxygen vacancy concentration. With increasing Y-doping level, the area specific resistance (ASR) of Pr_1−xY_xBaCo₂O_5+δ-based electrode in a symmetrical cell increases, and correspondingly, the peak power density of single-cell decreases slightly. Nevertheless, comparing to GdBaCo₂O_5+δ-based electrode, Pr_1−xY_xBaCo₂O_5+δ (x = 0.3–0.7) exhibits significantly lower ASR, and allows to obtain cells with higher maximum power density.     

Proton conducting solid oxide fuel cells with layered PrBa0.5Sr0.5Co2O5+δ perovskite cathode

BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBa_0.5Sr_0.5Co₂O_5+δ (PBSC) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni–BZCY7|BZCY7|PBSC. Experimental results show that the cell may achieve the open-circuit potential of 1.005 V, the maximal power density of 520 mW cm⁻², and a low electrode polarization resistance of 0.12 Ωcm² at 700 °C. Increasing operating temperature leads to the decrease of total cell resistance, among which electrolyte resistance becomes increasingly dominant over polarization resistance. The results also indicate that PBSC perovskite cathode is a good candidate for intermediate temperature PCMFC development, while the developed Ni–BZCY7|BZCY7|PBSC cell is a promising functional material system for SOFCs.     

Characterization and evaluation of NdBaCo2O5+δ cathode for proton-conducting solid oxide fuel cells

The layered perovskite structure oxide NdBaCo₂O_5+δ (NBCO) with rapid oxygen ion diffusion and surface exchange kinetics was synthesized by auto ignition process and initially examined as a cathode for proton-conducting fuel cells (H-SOFCs). The single cell, consisting of NdBaCo₂O_5+δ (NBCO)/BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY)/NiO–BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) structure, was assembled and tested from 650 to 700 °C with humidified hydrogen (∼3% H₂O) as the fuel and air as the oxidant. A maximum power density of 438 mW cm⁻² at 700 °C was obtained for the single cell and electrochemical performance of the cell was studied.     

Evaluation of layered perovskites YBa1−xSrxCo2O5+δ as cathodes for intermediate-temperature solid oxide fuel cells

This study is focused on the structural characteristics, oxygen nonstoichiometry, electrical conductivity, electrochemical performance and oxygen reduction mechanism of YBa_1−xSr_xCo₂O_5+δ (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5). The high oxygen nonstoichiometry, δ = 0.18–0.43 at 700 °C, indicates the large oxygen vacancy concentrations in oxides. The electrical conductivity is improved due to the greater amount of electronic holes originated from the increased interstitial oxygen, and the conductivities of all samples are above 100 S cm⁻¹ at 400–700 °C in air. The results demonstrate the promising performance of YBa_1−xSr_xCo₂O_5+δ cathodes at intermediate temperatures, as evidenced by low area-specific resistances (ASRs) e.g. 0.21–0.59 Ω cm² at 700 °C. The lowest ASR, 0.44 Ω cm², and the cathodic overpotential, −40 mV at a current density of −136 mA cm⁻², are obtained in YBaCo₂O_5+δ cathode at 650 °C. The dependence of polarization resistance on oxygen partial pressure suggests that the charge transfer process is the rate-limiting step for oxygen reduction reaction in YBaCo₂O_5+δ cathode.     

Neodymium-deficient nickelate oxide Nd1.95NiO4+δ as cathode material for anode-supported intermediate temperature solid oxide fuel cells

The neodymium-deficient nickelate Nd_1.95NiO_4+δ, mixed conducting K₂NiF₄-type oxide, was evaluated as cathode for solid oxide fuel cells. The electrochemical properties were investigated on planar Ni–YSZ anode-supported SOFC based on co-tape casted and co-fired HTceramix^® cells. Using a layer of strontium doped lanthanum cobaltite as current collector, a current density of 1.31 A cm⁻² (at 0.70 V) was obtained at 800 °C using hydrogen fuel with small single cells, after optimizing the cathode sintering temperature. Impedance spectroscopy measurements were performed; the different resistive contributions and the values of the corresponding equivalent capacities are discussed.     

Double-perovskites YBaCo2−xFexO5+δ cathodes for intermediate-temperature solid oxide fuel cells

Double-perovskites YBaCo_2−xFe_xO_5+δ (YBCF, x = 0.0, 0.2, 0.4 and 0.6) are synthesized with a solid-state reaction and are assessed as potential cathode materials for utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs) on the La_0.9Sr_0.1Ga_0.8Mg_0.115Co_0.085O_2.85 (LSGMC) electrolyte. The YBCF materials exhibit chemical compatibility with the LSGMC electrolyte up to a temperature of 950 °C. The conductivity of the YBCF samples decreases with increasing Fe content, and the maximum conductivity of YBCF is 315 S cm⁻¹ at 325 °C for the x = 0.0 sample. A semiconductor-metal transition is observed at about 300-400 °C. The thermal expansion coefficient of the YBCF samples increases from 16.3 to 18.0 × 10⁻⁶ K⁻¹ in air at temperatures between 30 and 900 °C with increase in Fe content. The area-specific resistances of YBCF cathodes at x = 0.0, 0.2 and 0.4 on the LSGMC electrolyte are 0.11, 0.13 and 0.15 Ω cm² at a temperature of 700 °C, respectively. The maximum power densities of the single cells fabricated with the LSGMC electrolyte, Ce_0.8Sm_0.2O_1.9 (SDC) interlayer, NiO/SDC anode and YBCF cathodes at x = 0.0, 0.2 and 0.4 reach 873, 768 and 706 mW cm⁻², respectively. This study suggests that the double-perovskites YBCF (0 ≤ x ≤ 0.4) can be potential candidates for utilization as IT-SOFC cathodes.     

Electrochemical evaluation of La2NiO4+δ as a cathode material for intermediate temperature solid oxide fuel cells

La₂NiO_4+δ powders were synthesized using a polyaminocarboxylate complex precursor method. La₂NiO_4+δ electrodes were prepared on Ce_0.8Sm_0.2O_1.9 (SDC) substrates using a screen-printing technique. The microstructure feature and electrocatalytic activity of the electrodes were investigated with respect to the calcination temperature of the starting powders and sintering temperature of the electrodes. The effects of microstructure features on the electrochemical properties of La₂NiO_4+δ electrodes have been inspected. Moreover, the electrochemical performance of the La₂NiO_4+δ cathode has been evaluated based on a Ni-SDC anode supported single cell. The single cell showed a modified electrochemical performance compared with the literature results, attaining a maximum power density of 295 mW cm⁻² at 800 °C. For the single cell, applying an Au layer onto the La₂NiO_4+δ cathode led to an evident reduction of ohmic resistance and a substantial enhancement of the maximum power density to 464 mW cm⁻².     

Layered perovskite PrBa0.5Sr0.5Co2O5+δ as high performance cathode for solid oxide fuel cells using oxide proton-conducting electrolyte

The layered perovskite PrBa_0.5Sr_0.5Co₂O_5+δ (PBSC) was investigated as a cathode material for a solid oxide fuel cell using an oxide proton conductor based on BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY). The sintering conditions for the PBSC-BZCY composite cathode were optimized, resulting in the lowest area-specific resistance and apparent activation energy obtained with the cathode sintered at 1200 °C for 2 h. The maximum power densities of the PBSC-BZCY/BZCY/NiO-BZCY cell were 0.179, 0.274, 0.395, and 0.522 W cm⁻² at 550, 600, 650, and 700 °C, respectively with a 15 μm thick electrolyte. A relatively low cell interfacial polarization resistance of 0.132 Ω cm² at 700 °C indicated that the PBSC-BZCY could be a good cathode candidate for intermediate temperature SOFCs with BZCY electrolyte.     

Investigation of cobalt-free perovskite Ba0.95La0.05FeO3−δ as a cathode for proton-conducting solid oxide fuel cells

Cobalt-free perovskite Ba_0.95La_0.05FeO_3−δ (BLF) was synthesized. The conductivity of BLF was measured with a DC four-point technique. The thermal expansion coefficient of the BLF was measured using a dilatometer. The BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) electrolyte based proton conducting solid oxide fuel cells (SOFCs) were fabricated. A composite cathode with BLF + BZCY7 was used to mitigate the thermal expansion mismatch with the BZCY7 electrolyte. The polarization processes of the button cell NiO-BZCY7/BZCY7/BLF + BZCY7 were characterized using the complicated electrochemical impedance spectroscopy technique. The open circuit voltage of 0.982 V, 1.004 V, and 1.027 V was obtained at 700 °C, 650 °C, and 600 °C, respectively, while the peak power density of 325 mW cm⁻², 240 mW cm⁻², and 152 mW cm⁻², was achieved accordingly.     

Characterization and electrochemical performances of Ba2−xSrxFeO4+δ as a novel cathode material for intermediate-temperature solid oxide fuel cells

Novel cathode materials, Ba_2−xSr_xFeO_4+δ (x = 0.5, 0.6, 0.7, 0.8, 1.0), for intermediate-temperature solid oxide fuel cells on a samaria-doped ceria (SDC) electrolyte were prepared by the glycine–nitrate route and characterized by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), thermogravimetric (TG) analysis, electrochemical impedance spectroscopy and steady-state polarization measurement. SEM results showed that the electrode formed a good contact with the SDC electrolyte after sintering at 1000 °C for 2 h. The value of δ in Ba_1.0Sr_1.0FeO_4+δ materials was calculated from the TG results. The electrochemical impedance spectra revealed that Ba_2−xSr_xFeO_4+δ had a better electrochemical performance than that of Ln₂NiO₄ (Ln = La, Pr, Nd, Sm). In the Ba_2−xSr_xFeO_4+δ (x = 0.5, 0.6, 0.7, 0.8, 1.0) family, the composition Ba_1.0Sr_1.0FeO_4+δ exhibited the best electrochemical activity for oxygen reduction. The polarization resistance of Ba_1.0Sr_1.0FeO_4+δ on SDC electrolyte was 1.11 Ω cm² at 700 °C, which was less than half that reported for Ln₂NiO₄ at the same temperature.     

Scandium-doped PrBaCo2−xScxO6−δ oxides as cathode material for intermediate-temperature solid oxide fuel cells

Scandium-doped PrBaCo_2−xSc_xO_6−δ(PBCS-x, x = 0.00–1.00) oxides have been evaluated as cathode materials of intermediate-temperature solid oxide fuel cells (IT-SOFCs) with respect to phase structure, oxygen content, thermal expansion behavior and electrical and electrochemical properties. The XRD results have demonstrated a phase transition in PBCS-x due to Sc³⁺ doping from tetragonal double-layered perovskite structure at x = 0.00–0.20, bi-phase mixtures at x = 0.30–0.40, to cubic perovskite structure at x = 0.50–0.90. The oxygen contents (6-δ) and average valences of cobalt ions in PBCS-x decrease with the higher Sc³⁺ content and increasing temperatures in air. Sc³⁺ doping has also led to decreased thermal expansion coefficients, lowered electrical conductivities and enhanced electrochemical reaction activities for PBCS-x characterized by decreased area-specific resistances (ASRs) and smaller reaction activation energies. Among the studied samples, the PBCS-0.50 oxide with Sc³⁺-doping content of x = 0.50 exhibits the best electrochemical performance on Ce_0.9Gd_0.1O_1.95 electrolyte. Its ASR values range from 0.123 Ω cm² at 600 °C to 0.022 Ω cm² at 750 °C, which are much lower than the related cathode materials. These results have demonstrated that the PBCS-0.50 oxide is a promising cathode material for IT-SOFCs.     

Novel SrCo1−yNbyO3−δ cathodes for intermediate-temperature solid oxide fuel cells

Perovskite oxides SrCo_1−yNb_yO_3−δ (SCNy, y = 0.00-0.20) are investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte. Compared to the undoped SrCoO_3−δ, the Nb doping significantly improves the thermal stability and enhances the electrical conductivity of the SCNy oxides. The cubic phase of the SCNy oxides with high thermal stability can be totally obtained when the Nb doping content y ≥ 0.10. Among the investigated compositions, the SrCo_0.9Nb_0.1O_3−δ oxide exhibits the highest electrical conductivity of 461-145 S cm⁻¹ over the temperature range of 300-800 °C in air. The SCNy cathode has a good chemical compatibility with the LSGM electrolyte for temperatures up to 1050 °C for 5 h. The area specific resistances of SCNy with y = 0.10, 0.15 and 0.20 cathodes on LSGM electrolyte are 0.083, 0.099 and 0.110 Ω cm² at 700 °C, respectively. At y = 0.10, 0.15 and 0.20, the maximum power densities of a single-cell with SCNy cathodes on 300-μm thick LSGM electrolyte achieve 675, 642 and 625 mW cm⁻² at 800 °C, respectively. These results indicate that SCNy perovskite oxides with cubic phase are potential cathode materials for application in IT-SOFCs.