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.     

Preparation of La0.75Sr0.25Cr0.5Mn0.5O3−δ fine powders by carbonate coprecipitation for solid oxide fuel cells

A range of La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) powders is prepared by the carbonate coprecipitation method for use as anodes in solid oxide fuel cells. The supersaturation ratio (R = [(NH₄)₂CO₃]/([La³⁺] + [Sr²⁺] + [Cr³⁺] + [Mn²⁺])) during the coprecipitation determines the relative compositions of La, Sr, Cr, and Mn. The composition of the precursor approaches the stoichiometric one at the supersaturation range of 4 ≤ R ≤ 12.5, whereas Sr and Mn components are deficient at R < 4 and excessive at R = 25. The fine and phase-pure LSCM powders are prepared by heat treatment at very low temperature (1000 °C) at R = 7.5 and 12.5. By contrast, the solid-state reaction requires a higher heat-treatment temperature (1400 °C). The catalytic activity of the LSCM electrodes is enhanced by using carbonate-derived powders to manipulate the electrode microstructures.     

Electrical properties of Mg-doped Gd0.1Ce0.9O1.95 under different sintering conditions

Ce_0.9Gd_0.1O_1.95 with various Mg doping contents was synthesized by citric acid-nitrate low temperature combustion process and sintered under different conditions. The crystal structures, microstructures and electrical properties were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and ac impedance spectroscopy. Low solubility of Mg²⁺ in Ce_0.9Gd_0.1O_1.95 lattice was evidenced by XRD and FESEM micrographs. The samples sintered at 1300 °C exhibited the higher total conductivity than those sintered at 1100 and 1500 °C, with the maximum value of 1.48 × 10⁻² S cm⁻¹ (measured at 600 °C) at the Mg doping content of 6 mol%, corresponding to the minimum total activation energy (E_tol) of 0.84 eV (150–400 °C). The effect of Mg doping on the electrical conductivity was significant particularly at higher sintering temperatures. At the sintering temperature of 1500 °C, the addition of Mg (10 mol%) enhanced the grain boundary conductivity by over 10² times comparing with that of undoped Ce_0.9Gd_0.1O_1.95, which may be explained by the optimization of space charge layer due to the segregation of Mg²⁺ to the grain boundaries.     

Performance of strontium- and magnesium-doped lanthanum gallate electrolyte with lanthanum-doped ceria as a buffer layer for IT-SOFCs

La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM8080) powder, showing the highest electrical conductivity among LSGMs of various compositions, is synthesized using the glycine nitrate process (GNP) and used as the electrolyte for an intermediate-temperature solid oxide fuel cell (IT-SOFC). The LDC (Ce_0.55La_0.45O_1.775) powder is synthesized by a solid-state reaction and employed as the material for a buffer layer to prevent the reaction between the anode and electrolyte materials. The LDC also serves as the skeleton material for the anode. An anode-supported single cell with an active area of 1 cm² is constructed for performance evaluation. A single-cell test is performed at 750 and 800 °C. The maximum power density of the cell 459 and 664 mW cm⁻² at 750 and 800 °C, respectively.     

Enhanced CO2 stability of oxyanion doped Ba2In2O5 systems co-doped with La, Zr

In the solid oxide fuel cell (SOFC) field, proton conducting perovskite electrolytes offer many potential benefits. However, an issue with these electrolytes is their stability at elevated temperatures in the presence of CO₂. Recently we have reported enhanced oxide ion/proton conductivity in oxyanion (silicate, phosphate) doped Ba₂In₂O₅, and in this paper we extend this work to examine the stability at elevated temperatures towards CO₂. The results show improved CO₂ stability compared to the undoped system, and moreover this can be further improved by co-doping on either the Ba site with La, or the In site with Zr. While this co-doping strategy does reduce the conductivity slightly, the greatly improved CO₂ stability would suggest there is technological potential for these co-doped samples.     

Improved electrical conductivity of Ce0.9Gd0.1O1.95 and Ce0.9Sm0.1O1.95 by co-doping

Solid electrolytes are the most important and indispensable part of a solid oxide fuel cell (SOFC) where hydrogen is used as one of the fuels to obtain electricity. Ce_0.9Gd_0.1O_1.95 and Ce_0.9Sm_0.1O_1.95 were chosen to be the base electrolytes. The effects of MgO and Nd₂O₃ as co-dopants on the electrical conductivity were investigated, respectively. For 4 mol% Mg-doped Ce_0.9Gd_0.1O_1.95 or Ce_0.9Sm_0.1O_1.95, MgO phases were detected by FESEM micrographs, which showed a very low solubility of Mg²⁺ in ceria lattice. The existence of MgO phases was observed to have negligible effect on the grain conductivity, but improve the grain boundary conductivity measured by ac impedance spectroscopy. However, when Nd₂O₃ was used as a co-dopant, XRD patterns and FESEM both indicated a pure cubic phase. Ce_0.9Gd_0.05Nd_0.05O_1.95 and Ce_0.9Sm_0.05Nd_0.05O_1.95 were found to exhibit higher grain conductivity, comparing with single-doped ceria.     

Structural,electrical, and electrochemical properties of cobalt-doped NiFe2O4 as a potential cathode material for solid oxide fuel cells

In this work, Co-doped NiFe₂O₄ spinels (NFCO-x) are successfully fabricated and characterized as possible cathode materials for the intermediate-temperature solid oxide fuel cells (SOFC). Results of the binding energy calculations using the density functional theory suggest that the reverse spinel structure is stable when Co³⁺ occupies the octahedral interstitial sites. Total and ionic-only conductivities indicate that NFCO-x are a kind of mixed electronic-ionic conductors. Ionic transferring numbers are approximately 0.049 and 0.006 for NFCO-0.1 and NFCO-0.5, respectively, measured at 700 °C in air. Co dopant in the NFCO-x improves the electronic conductivity at the expense of the ionic conductivity. For NFCO-0.5, electronic and ionic conductivities are approximately 0.24 and 9.6 × 10⁻⁴ S cm⁻¹, respectively, measured also at 700 °C in air. Unlike behaviour of the conductivities, the polarization resistance of symmetric cells with NFCO-x electrodes decreases when increasing the Co content (x) to a certain level, and then increases. The cell containing the NFCO-0.5 electrode exhibits the lowest polarization resistance (R_p), which is approximately 1.51 Ω cm² at 650 °C. For single cells, the maximum power density is 320 mW cm⁻² measured at 650 °C using a 38-μm-thick SDC electrolyte and an NFCO-0.5 cathode.     

V2O3 modified LiFePO4/C composite with improved electrochemical performance

In addition to lattice doping and carbon-coating, surface modification with other metal oxides can also improve the electrochemical performance of LiFePO₄ powders. In this work, highly conductive vanadium oxide (V₂O₃) is in situ produced during the synthesis of carbon-coated LiFePO₄ (LiFePO₄/C) powders by a solid state reaction process and acts as a surface modifier. The structures and compositions of LiFePO₄/C samples containing 0-10 mol% vanadium are analyzed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. Their electrochemical properties are also characterized with galvanostatic cell cycling and cyclic voltammetry. It is found that vanadium is present in the form of V₂O₃ that is incorporated in the carbon phase. The vanadium-modified LiFePO₄/C samples show improved rate capability and low-temperature performance. Their apparent lithium diffusion coefficient is in the range of 10⁻¹² to 10⁻¹⁰ cm² s⁻¹ depending on the vanadium content. Among the investigated samples, the one with 5 mol% vanadium exhibits the best electrochemical performance.     

Stable glass-ceramic sealants for solid oxide fuel cells: Influence of Bi2O3 doping

Diopside (CaMgSi₂O₆) based glass-ceramics in the system SrO–CaO–MgO–Al₂O₃–B₂O₃–La₂O₃–Bi₂O₃–SiO₂ have been synthesized for sealing applications in solid oxide fuel cells (SOFC). The parent glass composition in the primary crystallization field of diopside has been doped with different amounts of Bi₂O₃ (1, 3, 5 wt.%). The sintering behavior by hot-stage microscopy (HSM) reveals that all the investigated glass compositions exhibit a two-stage shrinkage behavior. The crystallization kinetics of the glasses has been studied by differential thermal analysis (DTA) while X-ray diffraction adjoined with Rietveld-R.I.R. analysis have been employed to quantify the amount of crystalline and amorphous phases in the glass-ceramics. Diopside and augite crystallized as the primary crystalline phases in all the glass-ceramics. The coefficient of thermal expansion (CTE) of the investigated glass-ceramics varied between (9.06–10.14) × 10⁻⁶ K⁻¹ after heat treatment at SOFC operating temperature for a duration varying between 1 h and 200 h. Further, low electrical conductivity, good joining behavior and negligible reactivity with metallic interconnects (Crofer22 APU and Sanergy HT) in air indicate that the investigated glass-ceramics are suitable candidates for further experimentation as sealants in SOFC.     

Correlation between electrical properties and microstructure of nanocrystallized V2O5-P2O5 glasses

It was shown that by thermal nanocrystallization of a 90V₂O₅·10P₂O₅ glass one can obtain a novel nanomaterial exhibiting enhanced electronic conductivity. Using a combination of methods: DTA, SEM, XRD and impedance spectroscopy (IS), it was possible to find correlation between microstructure and electrical properties of the obtained material and to optimize conditions of its synthesis. The room temperature electronic conductivity of the nanocrystallized samples is σ₂₅ = 2 × 10⁻³ S cm⁻¹ and is by a factor of 25 higher than the conductivity of the as-received glass. The nanocrystallized material is thermally stable up to ca 400 °C, which is about 150 °C above the glass transition temperature of the original glass. Maximum electronic conductivity of the thermally treated samples reaches 2 × 10⁻¹ S cm⁻¹ at ca 400 °C. The activation energy for these samples (0.28 eV) are substantially lower than that found for the starting glass (0.34 eV). The experimental results were discussed in terms of a model proposed in this paper and based on a “core-shell” concept. The results obtained here can be important for the progress in the search of novel nanocrystalline cathode materials for applications in Li-ion batteries.     

Effect of additives on the thermal properties and sealing characteristic of BaO-Al2O3-B2O3-SiO2 glass-ceramic for solid oxide fuel cell application

The apparent densities, coefficients of thermal expansion (CTE), and softening points of the BaO-Al₂O₃-SiO₂-B₂O₃ glasses prepared in this study range from 2.61 to 3.92 g/cm³, 4.92 to 10.98 ppm/°C, and 656 to 854 °C, respectively, depending on the glass composition. The softening point decreases with increasing BaO or B₂O₃ content in the glass. The feasibility of using MgO, KAlSi₂O₆, and KAlSiO₄ to tune the CTE of BaO-Al₂O₃-SiO₂-B₂O₃ glass is investigated. Composites containing MgO additive show little change in CTE at high temperature and report a high structural stability with the change in time. Wetting angle of the glass on the YSZ substrate depends to a great extent on the soaking temperature and the BaO content in the glass. Composites of selected BaO-Al₂O₃-SiO₂-B₂O₃ glasses and MgO additive on the YSZ substrate are evaluated for use as sealing material of solid oxide fuel cells (SOFCs). Results indicate that leakage rates for the composites of L06-20 vol% MgO, L08-30 vol% MgO, and L09-40 vol% MgO are lower than the detectable limit in this study.     

Anodic behavior of 8Y2O3-ZrO2/NiO cermet using an anode-supported electrode

8Y₂O₃-ZrO₂ (8YSZ)/NiO cermet anode-supported symmetric cell is introduced and fabricated using a tape casting process to analyze the anodic behavior of an anode-supported cell. An anode-supported symmetric cell helps us understand the complex anode structure of cermets. The anodic behavior of 8YSZ/NiO is compared to a MIEC electrode of Sm_0.2Ce_0.8O_1.9 (SDC)/NiO. The anodic behavior of a 8YSZ/NiO cermet electrode is investigated and discussed with respect to the hydrogen partial pressure (p(H₂)), water partial pressure (p(H₂O)), area specific resistance (ASR), activation energy (E_a), thermal cycle, and redox process. Based on these studies, an empirical reaction model of 8YSZ/NiO is established, and the related reaction processes are discussed. On impedance spectra diagram, high and medium frequency arcs are associated with the charge transfer process and the H₂O formation reaction, while the low frequency arc corresponds to the dissociative adsorption and the surface diffusion/gas phase diffusion process. Changes in microstructure by redox and thermal cycling have a significant effect on the electrochemical properties and structural stability of a thick anode-supported cermet structure.     

Color change of V2O5 thin films upon exposure to organic vapors

The reaction of amorphous V₂O₅ thin films with various organic vapors is investigated using in-situ optical transmission and in-situ Raman spectroscopic measurements. When V₂O₅ thin films are exposed to vapors of methanol, ethanol, acetone, and isopropanol, changes in the Raman spectrum are observed. These changes are similar to those due to alkali ion intercalation and most pronounced for methanol and ethanol. The optical transmission also increases when the thin films are exposed to methanol and ethanol vapors. Depositing a thin catalyst layer of palladium does not promote the reaction. This result has implications for using this material in hydrogen sensor applications, as extended exposure to organic vapors may not be differentiated from the presence of hydrogen.     

Sintering and ionic conductivity of 8YSZ and CGO10 electrolytes with small addition of Fe2O3: A comparative study

Two typical electrolytes, i.e., 8YSZ (8 mol% yttria-stabilized zirconia) and CGO10 (10 mol% Gd-doped ceria), with Si contents of ∼30 ppm and ≥500 ppm were prepared, whose grain-boundary (GB) conductivities should be controlled by intrinsic (space-charge layer) and extrinsic (resistive siliceous films) effects, respectively. 1 at% FeO_1.5 was loaded into these materials via a conventional mixed-oxide method. A comparative study was carried out to demonstrate how 1 at% Fe addition affected these materials with different levels of SiO₂ impurities with respect to sintering, GB and GI (grain interior) conductivities. FeO_1.5 was found to be a sintering promoter for both 8YSZ and CGO10 ceramics, but it is more effective to enhance the densification of ceria-based electrolytes. A reduction in sintering temperature of ∼200 °C for 1 at% Fe-doped CGO10 was achieved compared with ∼110 °C reduction for the 8YSZ with the same amount of Fe loading. The effect of FeO_1.5 loading on the electrical conduction was found to be different, depending significantly on the impurity level and the types of electrolytes. In general, the loading of FeO_1.5 is positive for ceria-based ceramics since FeO_1.5 has a scavenging effect on SiO₂ impurity with little effect on the GI conduction. Although the scavenging behavior of FeO_1.5 was also found in the impure 8YSZ, it led to a significant reduction in the GI conductivity.     

Constrained sintering of Y2O3-stabilized ZrO2 electrolyte on anode substrate

Understanding the sintering processes extensively is critical in fabricating a flat cell for solid oxide fuel cell stacks, but few have reported the sintering process and stress development during the constrained sintering of the electrolyte layer on anode substrate. In this study, we show that the green tape of half cell fabricated by co-tape casting cracks into several pieces when it is heated directly to 1400 °C of profile I, while it remains flat and complete when the green tape is sintered with additional pre-sintered profile at 1300 °C of profile II. The strain rate characteristics indicate that the difference of 2.43 × 10⁻⁶ s⁻¹ between the electrolyte and the anode layer leads to the stress development in the directly sintered cell, while it reduces to 6.7 × 10⁻⁸ s⁻¹ for the pre-sintered cell, which is only 3% of that without pre-sintering. The stress based on continuum model calculated results in the sintered cell demonstrates that the stress increases from 0 at about 1000 °C to 2.60 MPa at 1300 °C, and increased from 2.60 MPa to 6.54 MPa in temperature range of 1300–1400 °C. But it was lower than half of the stress for the pre-sintered cell according to profile II. The SEM images, together with a circuit voltage of 2.22 V for two cell stack, indicate that the electrolyte of the unit cell is dense. The power is 41.7 W, with a power density of 0.26 W cm⁻² at 1.4 V and 750 °C for a two tells stacks sintered according to profile II. The ASR of the two cells stack is 2.50 Ω cm².     

Structural, thermal and electrochemical properties of layered perovskite SmBaCo2O5+d, a potential cathode material for intermediate-temperature solid oxide fuel cells

The synthesis, conductivity properties, area specific resistance (ASR) and thermal expansion behaviour of the layered perovskite SmBaCo₂O_5+d (SBCO) are investigated for use as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The SBCO is prepared and shows the expected orthorhombic pattern. The electrical conductivity of SBCO exhibits a metal–insulator transition at about 200 °C. The maximum conductivity is 570 S cm⁻¹ at 200 °C and its value is higher than 170 S cm⁻¹ over the whole temperature range investigated. Under variable oxygen partial pressure SBCO is found to be a p-type conductor. The ASR of a composite cathode (50 wt% SBCO and 50 wt% Ce_0.9Gd_0.1O_2−d, SBCO:50) on a Ce_0.9Gd_0.1O_2−d (CGO91) electrolyte is 0.05 Ω cm² at 700 °C. An abrupt increase in thermal expansion is observed in the vicinity of 320 °C and is ascribed to the generation of oxygen vacancies. The coefficients of thermal expansion (CTE) of SBCO is 19.7 and 20.0 × 10⁻⁶ K⁻¹ at 600 and 700 °C, respectively. By contrast, CTE values for SBCO:50 are 12.3, 12.5 and 12.7 × 10⁻⁶ K⁻¹ at 500, 600 and 700 °C, that is, very similar to the value of the CGO91 electrolyte.     

Structure, thermal stability and electrical properties of Ca(V0.5Mo0.5)O3 as solid oxide fuel cell anode

The Ca(V_0.5Mo_0.5)O₃ perovskite has been prepared in order to study its potential use as anode in SOFC. The crystal structure has been refined, by neutron powder diffraction, in the orthorhombic Pbnm space group (no. 62). The electrical conductivity values were over 525 S cm⁻¹ in the studied temperature range (25-800 °C). The sample is stable under reducing working conditions (H₂/N₂ 10:90, 25-900 °C). This orthorhombic phase transforms at 500 °C in air to the tetragonal I4₁/a scheelite phase. This transition is reversible and, due to the fact that the thermal expansion coefficients of both, the reduced and oxidized phases, are very similar and match well with those of the other cell components ((10-13) × 10⁻⁶ K⁻¹) this materials are presented as excellent candidates as anodes in SOFCs.     

Preparation and properties of V2O5 thin films for energy-efficient selective-surface applications

Thin V₂O₅ films have been prepared by thermal evaporation onto glass substrates at a pressure of about 1.99×10⁻³ Pa. The temperature dependence of electrical measurements exhibits an anomaly in resistivity at a temperature around 329 K. Temperature co-efficient of resistance (TCR) studies show positive values, so indicating semi-metallic behaviour up to a temperature of 363 K and the negative thereafter so indicating semi-conducting behaviour. Thickness-dependent resistivity measurement follows the Fuchs-Sordheimer size-effect theory. X-ray diffraction studies show that the material is amorphous. Optical studies show the material is highly transparent both in the visible and infrared regions. The integrated value of T_lum and T_sol is high, so indicating that the material is a potential candidate for selective surface applications.     

Protonic and electronic conductivity of the layered perovskite oxides HCa2Nb3O10 and Ca4Nb6O19

The structural and electrical properties of the Dion–Jacobson series layer perovskite HCa₂Nb₃O₁₀ were investigated. Within the intermediate temperature range (200–475 °C), the compound undergoes topochemical dehydration to Ca₄Nb₆O₁₉ and, under reducing atmospheres, partial reduction of Nb(V) to Nb(IV). These changes occur upon heating and are not reversed on cooling. Analysis of impedance data shows that the conductivity of Ca₄Nb₆O₁₉ is predominantly electronic under reducing atmospheres, consistent with the behavior of other structurally related mixed-valence layered niobates.     

Performance of double-proveskite YBa0.5Sr0.5Co2O5+δ as cathode material for intermediate-temperature solid oxide fuel cells

Double-proveskite YBa_0.5Sr_0.5Co₂O_5+δ (YBSC) was investigated as potential cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). YBSC material exhibited a good chemical compatibility with the La_0.9Sr_0.1Ga_0.8Mg_0.115Co_0.085O_2.85 (LSGMC) electrolyte up to 950 °C for 2 h. The substitution of Sr for Ba significantly enhanced the electrical conductivity of the YBSC sample compared to undoped YBaCo₂O_5+δ, and also slightly increased the thermal expansion coefficient. At 325 °C a semiconductor-metal transition was observed and the maximum electrical conductivity of YBSC was 668 S cm⁻¹. The maximum power densities of the electrolyte-supported single cell with YBSC cathode achieved 650 and 468 mW cm⁻² at 850 and 800 °C, respectively. Preliminary results suggested that YBSC could be considered as a candidate cathode material for application in IT-SOFCs.