Performances of LnBaCo2O5+x-Ce0.8Sm0.2O1.9 composite cathodes for intermediate-temperature solid oxide fuel cells

Double-perovskite oxides, LnBaCo₂O_5+x (LnBCO) (Ln = Pr, Nd, Sm, and Gd), are prepared using a solid-state reaction as cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The performances of LnBCO-Ce_0.8Sm_0.2O_1.9 (SDC) composite cathodes were investigated for IT-SOFCs on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte. The thermal expansion coefficient can be effectively reduced in the case of the composite cathodes. No chemical reactions between LnBCO cathodes and SDC electrolyte, and LnBCO and LSGM are found. The electrochemical performances of LnBCO cathodes and LnBCO-SDC composite cathodes decrease with decreasing Ln³⁺ ionic radii, which is closely related to the decrease of the electrical conductivity and fast oxygen diffusion property. The area specific resistances of the LnBCO cathodes and LnBCO-SDC composite cathodes on LSGM electrolyte are all lower than 0.13 Ω cm² and 0.15 Ω cm² at 700 °C, respectively. The maximum power densities of single-cell consisted of LnBCO-SDC composite cathodes, LSGM electrolyte, and Ni-SDC anode achieve 758-608 mW cm⁻² at 800 °C with the change from Ln = Pr to Gd, respectively. These results indicate that LnBCO-SDC composite oxides are candidates as a promising cathode material for IT-SOFCs.     

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.     

Electrochemical performance of (Ba0.5Sr0.5)0.9Sm0.1Co0.8Fe0.2O3−δ as an intermediate temperature solid oxide fuel cell cathode

This study presents the electrochemical performance of (Ba_0.5Sr_0.5)_0.9Sm_0.1Co_0.8Fe_0.2O_3−δ (BSSCF) as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFC). AC-impedance analyses were carried on an electrolyte supported BSSCF/Sm_0.2Ce_0.8O_1.9 (SDC)/Ag half-cell and a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF)/SDC/Ag half-cell. In contrast to the BSCF cathode half-cell, the total resistance of the BSSCF cathode half-cell was lower, e.g., at 550 °C; the values for the BSSCF and BSCF were 1.54 and 2.33 Ω cm², respectively. The cell performance measurements were conducted on a Ni-SDC anode supported single cell using a SDC thin film as electrolyte, and BSSCF layer as cathode. The maximum power densities were 681 mW cm⁻² at 600 °C and 820 mW cm⁻² at 650 °C.     

Optimisation of the Solid Oxide Fuel Cell (SOFC) cathode material Ca3Co4O9−δ

This paper focuses on the electrochemical potentialities of the 2D misfit compound Ca₃Co₄O_9−δ, so far mainly investigated for its thermoelectric properties. Its expansion coefficient (TEC = (9-10) × 10⁻⁶ °C⁻¹) and its chemical stability are compatible with standard CGO IT-electrolyte and the first optimisation steps of the deposited cathode have been performed with the aim to minimise the ASR and increase the cell durability. Particular attention has been paid on the effect of thickness and microstructure for pure and composite cathodes. The electrode reaction was performed on symmetrical cells. The preliminary results presented here show that the composite (70 wt.% Ca₃Co₄O_9−δ-30 wt.% CGO) gives the lowest ASR values compare to single-phased electrodes. Strikingly, the ASR values increase for thinner deposited layers. The effect of various current collectors (gold grid vs. platinum paste) has been also checked.     

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.     

Performance and durability of nanostructured (La0.85Sr0.15)0.98MnO3/yttria-stabilized zirconia cathodes for intermediate-temperature solid oxide fuel cells

In this communication we report the fabrication of nanostructured (La_0.85Sr_0.15)_0.98MnO₃ (LSM)/yttria-stabilized zirconia (YSZ) composite cathodes consisting of homogeneously distributed and connected LSM and YSZ grains approximately 100 nm large. We also investigate for the first time the role of the cathode nanostructure on the performance and the durability of intermediate-temperature solid oxide fuel cells. The cathodes were fabricated using homogenous LSM/YSZ nanocomposite particles synthesized by co-precipitation, using YSZ nanoparticles of 3 nm as seed crystals. Detailed microstructural characterization by transmission electron microscopy with energy-dispersive X-ray spectroscopy revealed that many of the LSM/YSZ junctions in the cathode faced the homogeneously connected pore channels, indicating the formation of a considerable number of triple phase boundaries. The nanostructure served to reduce cathodic polarization. As a result, these anode-supported solid oxide fuel cells showed high power densities of 0.18, 0.40, 0.70 and 0.86 W cm⁻² at 650, 700, 750 and 800 °C, respectively, under the cell voltage of 0.7 V. Furthermore, no significant performance degradation of the cathode was observed during operation at 700 °C for 1000 h under a constant current density of 0.2 A cm⁻².     

Electrochemical performance of La1.6Sr0.4NiO4-Ag composite cathodes for intermediate-temperature solid oxide fuel cells

La_1.6Sr_0.4NiO₄-Ag (LSN-Ag) composite cathodes are prepared and characterized by XRD and SEM, respectively. The electrochemical properties of the composite cathodes are investigated using AC impedance and DC polarization methods from 500 to 700 °C under different oxygen partial pressures. The polarization resistance (R_p) decreases with the increase of Ag content in the composite electrode. The addition of 5 vol.% Ag in LSN results in the lowest R_p of 0.21 Ω cm² at 700 °C in air. Oxygen partial pressure dependence study indicates that the charge transfer process is the reaction rate limiting step, while the diffusion process has no sensitive to the Ag loading. LSN-5Ag cathode exhibits the lowest overpotential of about 32 mV at a current density of 144 mA cm⁻² at 700 °C in air.     

Fabrication and evaluation of Ag-impregnated BaCe0.8Sm0.2O2.9 composite cathodes for proton conducting solid oxide fuel cells

Ag-BaCe_0.8Sm_0.2O_2.9 (BCS) composite cathodes are fabricated by an ion impregnation technique in this work, and the effect of fabrication details on their electro-performance is studied. The firing temperature of impregnated Ag has little effect on Ag loading but has a great impact on the polarization resistances. When fired at 400 °C, the minimum polarization resistance for symmetric cells reaches 0.11 Ω cm² measured at 600 °C with an Ag loading of 0.40 mg cm⁻². When fired at 600 °C, the minimum polarization resistance is 29.73 Ω cm² at 600 °C with 0.24 mg cm⁻² Ag-impregnated cathodes due to severe aggregation. The performance of Ag-impregnated cathodes is also compared with that of a Sm_0.5Sr_0.5CoO_3−δ (SSC) impregnated cathode. With the same volume ratio of 57%, the polarization resistance of an Ag-impregnated cathode is only about half of that for a SSC-impregnated cathode. Resistance simulation suggests that the reduction of low frequency resistances is the main reason for the decrease in polarization resistances in Ag-impregnated cathodes, which is consistent with its high oxygen diffusion coefficient. With a 57 vol.% Ag-impregnated cathode fired at 400 °C, the maximum power density of single cells is 283 mW cm⁻² at 600 °C, about 16% larger than that for a 57 vol.% SSC-impregnated cathode.     

A high-performance Gd0.8Sr0.2CoO3–Ce0.9Gd0.1O1.95 composite cathode for intermediate temperature solid oxide fuel cell

Powders of Gd_0.8Sr_0.2CoO₃ (GSC) were prepared by a glycine–nitrate process. Symmetrical cathodes of GSC–50Ce_0.9Gd_0.1O_1.95 (GDC) (50:50 by volume) powders were deposited on GDC electrolyte pellets, and the electrochemical properties of the interfaces between the porous cathode and the electrolyte were investigated at intermediate temperature (500–750 °C) using electrochemical impedance spectroscopy. The addition of 50 vol.% GDC to GSC resulted in an additional factor ≈3 decrease in the area-specific resistance (ASR). The ASR values for the GSC–50GDC cathodes were as low as 0.064 Ω cm² at 700 °C and 0.16 Ω cm² at 600 °C, respectively. The maximum power density of a cell using the GSC–50GDC cathode was 356 mW cm⁻² at 700 °C.     

Study of oxygen reduction mechanism on Ag modified Sm1.8Ce0.2CuO4 cathode for solid oxide fuel cell

Different amount of metal silver particles are infiltrated into porous Sm_1.8Ce_0.2CuO₄ (SCC) scaffold to form SCC–Ag composite cathodes. The chemical stability, microstructure evolution and electrochemical performance of the composite cathode are investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and AC impedance spectroscopy respectively. The composite cathode exhibits enhanced chemical stability. The metal Ag remains un-reacted with SCC and Ce_0.9Gd_0.1O_1.95 (CGO) at 800 °C for 72 h. The polarization resistance of the composite cathode decreases with the addition of metal Ag. The optimum cathode SCC-Ag05 exhibits the lowest area specific resistance (ASR, 0.43 Ω cm²) at 700 °C in air. Investigation shows that metal Ag accelerates the charge transfer process in the composite cathode, and the rate limiting step for electrochemical oxygen reduction reaction (ORR) changes to oxygen dissociation and diffusion process.     

Improved electrochemical performance and thermal compatibility of Fe- and Cu-doped SmBaCo2O5+δ-Ce0.9Gd0.1O1.95 composite cathode for intermediate-temperature solid oxide fuel cells

Fe- and Cu-doped SmBaCo₂O_5+δ (FC-SBCO)-Ce_0.9Gd_0.1O_1.95 (CGO) composites with various CGO contents (0-40 wt.%) are investigated as new cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) based on a Ce_0.9Gd_0.1O_1.95 electrolyte. The effect of CGO incorporation on the thermal expansion coefficient (TEC), electrochemical properties and thermal stability of the FC-SBCO-CGO composites is investigated. A composite cathode of 30 wt.% CGO-70 wt.% FC-SBCO (CS30-70) coated on a Ce_0.9Gd_0.1O_1.95 electrolyte shows the lowest area specific resistance (ASR), i.e., 0.049 Ω cm² at 700 °C. The TEC of the CS30-70 cathode is 14.1 × 10⁻⁶ °C⁻¹ up to 900 °C, which is a lower value than that of the FC-SBCO (16.6 × 10⁻⁶ °C⁻¹) counterpart. Long-term thermal stability and thermal cycle tests of the CS30-70 cathode are performed. Stable ARS values are observed during both type of test. An electrolyte-supported (300-μm thick) single-cell configuration of CS30-70/CGO/Ni-CGO delivers a maximum power density of 535 mW cm⁻² at 700 °C. The unique composite composition of CS30-70 demonstrates improved electrochemical performance and good thermal stability for IT-SOFCs.     

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.     

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.     

Enhanced electrochemical performance of solution impregnated La0.8Sr0.2Co0.8Ni0.2O3−δ cathode for intermediate temperature solid oxide fuel cells

Solution impregnated La_0.8Sr_0.2Co_0.8Ni_0.2O₃ + Gd-doped CeO₂ (LSCN + GDC) cathodes for intermediate temperature solid oxide fuel cells (IT-SOFC) are prepared and their electrochemical properties are evaluated and compared with the conventional LSCN cathodes. The results indicate that the cathode performance can be enhanced by the presence of the nanosized microstructure produced with the solution impregnation method. It is determined that the amount of LSCN loading in the LSCN + GDC composite cathode needs to be higher than 35 wt% in order to achieve a performance superior to that of the conventional LSCN cathode. The optimum amount of LSCN loading is in the range of 45-55 wt% with an activation energy near 1.32 eV for oxygen reduction. At temperatures between 600 and 750 °C, the polarization resistance of the 55 wt% LSCN loaded LSCN + GDC cathode is in the range of 1.07 and 0.08 Ω cm², which is only about one half of that for the conventional cathode.     

Effects of roasting temperature and modification on properties of Li2FeSiO4/C cathode

Li₂FeSiO₄/C cathodes were synthesized by combination of wet-process method and solid-state reaction at high temperature, and effects of roasting temperature and modification on properties of the Li₂FeSiO₄/C cathode were investigated. The XRD patterns of the Li₂FeSiO₄/C samples indicate that all the samples are of good crystallinity, and a little Fe₃O₄ impurity was observed in them. The primary particle size rises as the roasting temperature increases from 600 to 750 °C. The Li₂FeSiO₄/C sample synthesized at 650 °C has good electrochemical performances with an initial discharge capacity of 144.9 mAh g⁻¹ and the discharge capacity remains 136.5 mAh g⁻¹ after 10 cycles. The performance of Li₂FeSiO₄/C cathode is further improved by modification of Ni substitution. The Li₂Fe_0.9Ni_0.1SiO₄/C composite cathode has an initial discharge capacity of 160.1 mAh g⁻¹, and the discharge capacity remains 153.9 mAh g⁻¹ after 10 cycles. The diffusion coefficient of lithium in Li₂FeSiO₄/C is 1.38 × 10⁻¹² cm² s⁻¹ while that in Li₂Fe_0.9Ni_0.1SiO₄/C reaches 3.34 × 10⁻¹² cm² s⁻¹.     

Improved high temperature performance of La0.8Sr0.2MnO3 cathode by addition of CeO2

Ceria is proposed as an additive for La_0.8Sr_0.2MnO₃ (LSM) cathodes in order to increase both their thermal stability and electrochemical properties after co-sintering with an yttria-stabilized zirconia (YSZ) electrolyte at 1350 °C. Results show that LSM without CeO₂ addition is unstable at 1350 °C, whereas the thermal stability of LSM is drastically improved after addition of CeO₂. In addition, results show a correlation between CeO₂ addition and the maximum power density obtained in 300 μm thick electrolyte-supported single cells in which the anode and modified cathode have been co-sintered at 1350 °C. Single cells with cathodes not containing CeO₂ produce only 7 mW cm⁻² at 800 °C, whereas the power density increases to 117 mW cm⁻² for a CeO₂ addition of 12 mol%. Preliminary results suggest that CeO₂ could increase the power density by at least two mechanisms: (1) incorporation of cerium into the LSM crystal structure, and (2) by modification or reduction of La₂Zr₂O₇ formation at high temperature. This approach permits the highest LSM-YSZ co-sintering temperature so far reported, providing power densities of hundreds of mW cm⁻² without the need for a buffer layer between the LSM cathode and YSZ electrolyte. Therefore, this method simplifies the co-sintering of SOFC cells at high temperature and improves their electrochemical performance.     

A comparative study of La0.8Sr0.2MnO3 and La0.8Sr0.2Sc0.1Mn0.9O3 as cathode materials of single-chamber SOFCs operating on a methane-air mixture

As candidates of cathode materials for single-chamber solid oxide fuel cells, La_0.8Sr_0.2MnO₃ (LSM) and La_0.8Sr_0.2Sc_0.1Mn_0.9O₃ (LSSM) were synthesized by a combined EDTA-citrate complexing sol-gel process. The solid precursors of LSM and LSSM were calcined at 1000 and 1150 °C, respectively, to obtain products with similar specific surface area. LSSM was found to have higher activity for methane oxidization than LSM due to LSSM's higher catalytic activity for oxygen reduction. Single cells with these two cathodes initialized by ex situ reduction had similar peak power densities of around 220 mW cm⁻² at 825 °C. The cell using the LSM cathode showed higher open-circuit-voltage (OCV) at corresponding temperatures due to its reduced activity for methane oxidation relative to LSSM. A negligible effect of methane and CO₂ on the cathode performance was observed for both LSM and LSSM via electrochemical impedance spectroscopy analysis. The high phase stability of LSSM under reducing atmosphere allows a more convenient in situ reduction for fuel cell initiation. The resultant cell with LSSM cathode delivered a peak power density of ∼200 mW cm⁻² at 825 °C, comparable to that from ex situ reduction.     

LiFePO4 water-soluble binder electrode for Li-ion batteries

A new water-soluble elastomer from ZEON Corp. was evaluated as binder with LiFePO₄ cathode material in Li-ion batteries. The mechanical characteristic of this cathode was compared to that with PVdF-based cathode binder. The elastomer-based cathode shows high flexibility with good adhesion. The electrochemical performance was also evaluated and compared to PVdF-based cathodes at 25 and at 60 °C. A lower irreversible capacity loss was obtained with the elastomer-based cathode, however, aging at 60 °C shows a comparable cycle life to that observed with PVdF-based cathodes. The LiFePO₄–WSB at high rate shows a good performance with 120 mAh g⁻¹ at 10C rate at 60 °C.     

Significant impact of the current collection material and method on the performance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ electrodes in solid oxide fuel cells

The effects of the current collection material and method on the performance of SOFCs with Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) cathodes are investigated. Ag paste and LaCoO₃ (LC) oxide are studied as current collection materials, and five different current collecting techniques are attempted. Cell performances are evaluated using a current-voltage test and electrochemical impedance spectra (EIS) based on two types of anode-supported fuel cells, i.e., NiO + SDC|SDC|BSCF and NiO + YSZ|YSZ|SDC|BSCF. The cell with diluted Ag paste as the current collector exhibits the highest peak power density, nearly 16 times that of a similar cell without current collector. The electrochemical characteristics of the BSCF cathode with different current collectors are further determined by EIS at 600 °C using symmetrical cells. The cell with diluted Ag paste as the current collector displays the lowest ohmic resistance (1.4 Ω cm²) and polarization resistance (0.1 Ω cm²). Meanwhile, the surface conductivities of various current collectors are measured by a four-probe DC conductivity technique. The surface conductivity of diluted Ag paste is 2-3 orders of magnitude higher than that of LC or BSCF. The outstanding surface conductivity of silver may reduce the contact resistance at the current collector/electrode interface and, thus, contributes to better electrode performance.     

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.