Electrochemical properties of nanostructured lanthanum strontium manganite cathode fabricated by electrostatic spray deposition

Electrostatic spray deposition was applied to prepare nanoporous lanthanum strontium manganite (LSM) films with high specific surface area (37.34 m²/g) for the cathode application in solid oxide fuel cell (SOFC). The electrochemical characteristics were investigated at a temperature range from 546 to 777 °C and oxygen partial pressure from 0.01 to 1.0 atm. The diffusion of atomic oxygen and oxygen ion transfer from three-phase boundary to the YSZ electrolyte were found to be the rate-determining steps for oxygen reduction reaction on LSM cathode. The polarization resistance of the LSM prepared using electrostatic spray deposition decreased from 15 to 1.2 Ωcm² with increasing temperature from 546 to 777 °C and the activation energy was 0.81 eV. It was demonstrated that the ESD method offers a promising approach for the preparation of electrochemically active nanoporous layers, particularly applicable for solid oxide fuel cells.     

H2S Solid oxide fuel cell based on a modified Barium cerate perovskite proton conductor

Urea combustion method was adopted to prepare precursor powder, MCeO₃ doped with Zr (M is alkaline earth element, such as barium, strontium, and calcium). The precursor powder has typically perovskite structure after being calcined at 873 K. In 773 K∼1,273 K, BaCe_0.425Zr_0.475Y_0.1O₃ has the highest conductivity above 10⁻² S cm⁻¹ and good chemical stability, while the phase transition may exist in H₂S atmosphere for the proton conductors. In the single fuel cell composed of MoS₂-BaCe_0.425Zr_0.475Y_0.1O_3-σ-Ag with BaCe_0.425Zr_0.475Y_0.1O_3-σ as electrolyte, the best performance is obtained. The open circuit voltage of fuel cell is all about 0.72 V, the max power density, 1.55 mW cm⁻². The performance drop is attributed to ohmic loss resulting from the separation of electrolyte and electrode, and improvement is required to bring out new anode materials compatible to the proton conductor, BaCe_0.425Zr_0.475Y_0.1O_3-σ, as electrolyte.     

Characterization of solid oxide fuel cells based on solid electrolytes or mixed ionic electronic conductors

The relation between cell voltage (V_cell), applied chemical potential difference (Δμ(O₂)) and cell current (I_t) for solid oxide fuel cells (SOFC) based on mixed ionic electronic conductors is derived by considering also the effect of electrode impedance. Four-probe measurements, combined with current interruption analysis, are considered to yield the relation between ionic current (I_i) and overpotential (η). The theoretical relations are used to analyze experiments on fuel cells with Ce_0.8Sm_0.2O_1.9 and Ce_0.8Gd_0.2O_1.9 electrolytes with La_0.8Sr_0.16CoO₃ or Pt as the cathode and Ni/Ce_0.9Ca_0.1O_1.9−xor Pt as the anode. The electrode overpotentials of these cells, determined by current interruption measurements, are discussed assuming different models including impeded mass transport in the gas phase for molecular and monoatomic oxygen and Butler-Volmer type charge transfer overpotential.     

Stable and high conductivity ceria/bismuth oxide bilayer electrolytes for lower temperature solid oxide fuel cells

A highly conductive bismuth oxide/ceria bilayer electrolyte was developed to reduce solid oxide fuel cell (SOFC) operating temperatures. Bilayer electrolytes were fabricated by depositing a layer of Er_0.2Bi_0.8O_1.5 (ESB) of varying thickness via pulsed laser deposition and dip-coating on a Sm_0.2Ce_0.8O_1.9 (SDC) substrate. The open-circuit potential (OCP) and ionic transference number (t _i) of ESB/SDC electrolytes were tested in a fuel cell arrangement as a function of relative thickness, temperature, and with H₂/H₂O and CO/CO₂ on the anode side and air on the cathode side. These EMF measurements showed a significant increase in OCP and t _i with the bilayer structure, as compared to the cells with a single SDC electrolyte layer. Furthermore, improvement in the OCP and t _i of bilayer SOFCs was observed with increasing relative thickness of the ESB layers. Hence, the bilayer structure overcomes the limited thermodynamic stability of bismuth oxides and prevents electronic conductivity of ceria-based oxides in reducing atmosphere.     

On the reversibility of anode supported proton conducting solid oxide cells

Reversible proton conducting solid oxide cells (SOCs) off a highly efficient route to matching supply from intermittent, renewable resources, with power demand by consumers. The cells would store excess electrical energy as chemical fuel during times of peak production, and operate in reverse during times of peak demand. In this study we examine the operation of anode supported proton conducting SOCs in electrolysis mode. The required overpotential for a given current density decreases with increasing humidity at the anode and increasing temperature. All of the V-I curves show distinct curvature. The electrode polarization resistance increases and electrolyte ohmic resistance decreases with increasing current density. This is accompanied by a deviation below the theoretical rate of hydrogen production. We interpret these changes as resulting from deviation away from pure proton conduction in the cell with increasing polarization.     

High temperature oxidation behavior of interconnect coated with LSCF and LSM for solid oxide fuel cell by screen printing

The current study examined the effect of La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) and La_0.7Sr_0.3MnO₃ (LSM) coatings on the electrical properties and oxidation resistance of Crofer22 APU at 800 °C hot air. LSCF and LSM were coated on Crofer22 APU by screen printing and sintered over temperatures ranging from 1000 to 1100 °C in N₂. The coated alloy was first checked for compositions, morphology and interface conditions and then treated in a simulated oxidizing environment at 800 °C for 200 h. After measuring the long-term electrical resistance, the area specific resistance (ASR) at 800 °C for the alloy coated with LSCF was less than its counterpart coated with LSM. This work used LSCF coating as a metallic interconnect to reduce working temperature for the solid oxide fuel cell.     

Electrodeposited cobalt coating on Crofer22APU steels for interconnect applications in solid oxide fuel cells

A gas-tight cobalt-based protective coating was successfully applied by electroplating and subsequent oxidation. The coating covered all the surfaces of the machined gas channels of the metallic interconnect and adhered well to this substrate. Such a gas-tight coating offers effective blocking of Cr diffusion or evaporation from the interconnect and hence a reliable protection against Cr poisoning of the SOFC cathode. Chemical interactions were observed between the cobalt coating and the LSM contact layer, resulting in layer spallation during oxidation under pressureless conditions. Applying a pressure to the layers, spallation was effectively prevented. Although the area specific resistance (ASR) of the coated interconnect was higher than the uncoated one, it decreased steadily with time within the measurement period. The ASR was 28 mΩ cm² after an exposure of 1170 h. It seems thus that electroplating followed by oxidation is a promising method for the fabrication of spinel protective coatings for SOFC interconnects or other balance-of-plant components with complicated gas flow paths.     

Electrical properties of triple-doped bismuth oxide electrolyte for solid oxide fuel cells

In this study, the quaternary solid solutions of (Bi₂O₃)_(0.8?x)(Tb₄O₇)_0.1(Ho₂O₃)_0.1(Dy₂O₃)_x (x = 0.05, 0.10, 0.15, 0.20) as an electrolyte were synthesized for solid oxide fuel cells by the technique of solid-state synthesis.

The products were characterized by X-ray powder diffraction, differential thermal analysis/thermal gravimetry and the four-point probe technique (4PPT). The total electrical conductivity is measured on the temperature and the doped concentration by 4PPT.

All samples have been obtained as the δ-phase. According to the measurements of the 4PPT, the electrical conductivities of the samples increase with the temperature but decrease with the amount of doping rate. The value of the highest conductivity (σ) is found as 1.02?×?10^?1 S cm^?1 for the system of (Bi₂O₃)_0.75(Tb₄O₇)_0.1(Ho₂O₃)_0.1(Dy₂O₃)_0.05 at 850 °C. The thermal gravimetry (TG) curve shows that there is no mass loss of sample during the measurement. The analyses of differential thermal reveal that there are neither endothermic peaks nor exothermic peaks during the heating and cooling cycles (ranging from 30 to 1000 °C).     

Niobium based tetragonal tungsten bronzes as potential anodes for solid oxide fuel cells: synthesis and electrical characterisation

In this paper we report studies on a range of niobate based tungsten bronzes, with a view to analysing their potential as anode materials in SOFCs. Six systems were studied, (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃, Sr_0.6−xLa_xTi_0.2+xNb_0.8−xO₃, (Sr_0.4−xBa_x)Na_0.2NbO₃, (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃, Ba_0.5−xA_xNbO₃ (A=Ca, Sr), and Ba_0.3NbO_2.8, and the electrical conductivities were examined over a range of oxygen partial pressures (10⁻²⁰–1 bar). All the systems showed good conductivity in low oxygen partial pressures, with values as high as 8 S cm⁻¹ at 930°C (P(O₂)=10⁻²⁰ bar). As the oxygen partial pressure was raised the conductivity dropped showing in most cases an approximate [P(O₂)]^−1/4 dependence and good re-oxidation kinetics. Of all the samples studied the (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃ and (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃ systems appear most promising for potential use as anode materials in SOFCs.     

Highly dispersed anodes for solid oxide fuel cells using NiO/YSZ/BZY triple-phase composite powders prepared by spray pyrolysis

NiO/Y₂O₃-stabilized ZrO₂ (YSZ)/Y-doped BaZrO₃ (BZY) triple-phase composite powders were prepared by spray pyrolysis and evaluated for Ni/YSZ/BZY cermet anodes, which are considered effective for dry CH₄ operation in solid oxide fuel cells. The structure of the particles in these powders was fine crystal fragments, and the individual material phases were clearly separated and highly dispersed within the particles. The Ni/YSZ/BZY cermet anodes fabricated with these composite powders maintained a fine electrode microstructure equivalent to that in a simple Ni/YSZ cermet anode manufactured using a composite powder prepared by spray pyrolysis. Furthermore, the addition of BZY improved the anode performance in humidified H₂ and dry CH₄ operation.     

Metal-supported solid oxide fuel cells with barium-containing in-situ cathodes

Materials containing barium (Ba), such as SmBa_0.5Sr_0.5Co₂O_5-d/Ce_0.9Gd_0.1O_1.9 (SBSC50) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-d (BSCF), are considered for use as an in-situ cathode in metal-supported solid oxide fuel cells (SOFCs). The electrochemical properties and sintering behavior of these materials are investigated in terms of area specific resistances (ASRs), I-V-P characteristics and microstructure. The properties of in-situ cathodes comprised of SBSC50 and BSCF are compared with those of conventional cathodes, such as La_0.8Sr_0.2MnO_3-d (LSM), La_0.8Sr_0.2FeO_3-d (LSF), La_0.6Sr_0.4Co_0.2Fe_0.8O_3-d (LSCF) and Sm_0.5Sr_0.5CoO_3-d/Ce_0.8Sm_0.2O_1.9 (SSC40). Impedance spectroscopy analysis using Nyquist and Bode plots and microstructure analysis is conducted to understand the reason behind electrochemical performance differences between in-situ cathodes and sintered cathodes. From this analysis, we are also able to verify the electrochemical behavior of well-defined in-situ cathodes. SBSC50 and BSCF are the incorporated in our metal-supported cells without the use of any additional sintering process. The metal-supported cells are successfully fabricated using a high temperature sinter-joining process and we fail to detect any defects or deformation after fabrication. At an operating temperature of 800 °C, metal-supported cells with SBSC50 and BSCF cathodes exhibit maximum power densities of 0.50 Wcm^-2 and 0.65 Wcm^-2, respectively.     

A tubular segmented-in-series solid oxide fuel cell with metallic interconnect films: A performance study through mathematical simulations

In a segmented-in-series solid oxide fuel cell (SIS-SOFC), an interconnect (IC) provides electrical contact and sealing between the anode of one cell and the cathode of the next. A metallic silver-glass composite (SGC) is considered a promising alternative to ceramic IC materials in SIS-SOFCs. In this work, a simulation study is performed on a tubular SIS-SOFC to assess the effectiveness of the SGC-IC design and to predict the SOFC performance characteristics for various IC geometries and conductivities. The developed model provides detailed information on cell behavior, such as the internal resistance, the potential/current distribution, and the local gas species concentration. The results demonstrate that the SGC material greatly reduces a potential drop across the IC film. Thus, it provides the following substantial advantages over conventional ceramic IC materials: (i) increased power density and (ii) a larger degree of flexibility in the cell design. Moreover, the validation test, i.e., comparison of the simulated results with the experimental data, indicates that the model could serve as a valuable tool for design optimization to achieve the required SOFC performance.     

Gadolinia-doped ceria films deposited by RF reactive magnetron sputtering

Gadolinia-doped ceria (GDC) films were prepared by RF reactive magnetron sputtering from a Gd-10 at.% Ce alloy target in reactive O₂/Ar gas mixtures and annealed at 700 °C for 2 h. Material characteristics and chemical compositions of GDC films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). Electrical behaviors were measured by AC impedance in the range of 500–700 °C at OCV for air condition. The microstructure of GDC films was found to be an assembly of columnar crystallites with a cubic fluorite structure. The total conductivity of 700 °C-annealed GDC (GDC-1) with the obtained composition of (Ce_0.911Gd_0.089)O_1.938 was higher than that of bulk yttria-stabilized zirconia (YSZ), but smaller than bulk GDC. The governing mechanism of conduction of sputtered-GDC electrolyte films was mainly governed by a grain boundary process, which resulted in a blocking effect and the lower conductivity of thin films than that of bulk GDC samples. Our results suggested that sputtered-GDC films with a comparable conductivity can be used as solid electrolyte layers for a solid oxide fuel cell (SOFC) system as compared to the well-known YSZ.     

Fabrication of solid oxide fuel cell based on doped ceria electrolyte by one-step sintering at 800 °C

Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) electrolyte was prepared by a carbonate co-precipitation method. Lithium nitrate at 1, 1.5, 2 and 3 mol% was added to GYDC as sintering additive. 96% relative density was achieved for GYDC at sintering temperature of 800 °C with addition of 1.5 mol% LiNO₃. The conductivities of GYDC with sintering aids LiNO₃ were measured by a.c. impedance spectroscopy and showed comparable values to that of pure GYDC sample sintered at 1400 °C. A single cell with 1.5 mol% LiNO₃ infiltrated GYDC electrolyte was fabricated by sintering at 800 °C for only 2 h. Lithiated NiO was synthesized by the glycine-nitrate combustion method and employed as cathode material. The cell was tested at temperatures from 500 to 575 °C and a maximum power density of 73 mW cm^− 2 was obtained at 575 °C. These preliminary results indicate that LiNO₃ is a very effective sintering additive for intermediate temperature solid oxide fuel cell fabrication.     

Electrochemical performance of mixed ionic–electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic–electronic conducting (MIEC) oxides, SrFeCo_0.5O_x, SrCo_0.8Fe_0.2O_3−δ and La_0.6Sr_0.4Fe_0.8Co_0.2O_3−δ have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H₂ and CH₄ fuels, giving maximum power densities of around 0.1 W/cm² at 950°C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. In particular, for the SrFeCo_0.5O_x oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm² on CH₄, exceeding those of both SrFeCo_0.5O_x and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo_0.5O_x and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment.     

Double-layer indium doped zinc oxide for silicon thin-film solar cell prepared by ultrasonic spray pyrolysis

Indium doped zinc oxide(ZnO:In) thin films were prepared by ultrasonic spray pyrolysis on corning eagle 2000 glass substrate.1 and 2 at.% indium doped single-layer ZnO:In thin films with different amounts of acetic acid added in the initial solution were fabricated.The 1 at.% indium doped single-layers have triangle grains.The 2 at.% indium doped single-layer with 0.18 acetic acid adding has the resistivity of 6.82×10-3Ω·cm and particle grains.The doublelayers structure is designed to fabricate the ZnO:In thin film with low resistivity(2.58×10-3Ω·cm) and good surface morphology.It is found that the surface morphology of the double-layer ZnO:In film strongly depends on the substratelayer,and the second-layer plays a large part in the resistivity of the double-layer ZnO:In thin film.Both total and direct transmittances of the double-layer ZnO:In film are above 80% in the visible light region.Single junction a-Si:H solar cell based on the double-layer ZnO:In as front electrode is also investigated.     

Ln1−xSrxCoO3(Ln = Sm, Dy) for the electrode of solid oxide fuel cells

The perovskite-type oxides were synthesized in the series of Ln_1−xSr_xCoO₃(Ln = Sm, Dy). The formation of solid solutions in Dy_{1 − x}Sr_xCoO₃ was limited, compared with that in Sm_{1 − x}Sr_xCoO₃. The electrical conductivities of the sintered samples were measured as a function of x in the temperature range 30 to 1000 °C. The highest conductivity of around 500 S/cm at 1000 °C was found in Sm_0.7Sr_0.3CoO₃. The reactivity of all the samples with YSZ was examined at 800–1000 °C for 96 h. The Sr-doped perovskite oxides were more reactive with YSZ and produced SrZrO₃ at 900 °C after 96 h. However, no reaction product between SmCoO₃ and YSZ was observed at 1000 °C for 96 h. The cathodic polarization of the oxide electrodes, sputtered on yttria stabilized zirconia (YSZ), was studied at 800–1000 °C in air. SmCoO₃ shows no degradation of the electrode performance at higher temperatures. The thermal expansion measurements on the sintered samples were carried out from room temperature to 1000 °C. Large thermal expansion coefficients were found in these samples.     

Influence of colloidal templates on the impedance spectroscopic behaviour of Pr0.7Sr0.3Fe0.8Ni0.2O3 for solid oxide fuel cell applications

The creation of porous materials with three-dimensional periodicity has been identified as being of potential interest for increasing the overall performance of solid oxide fuel cells (SOFC). In this work, we have investigated the formation of pore systems in the nanometer scale by replicating colloidal templates. Templating methods have been used to prepare iron-nickel-based perovskite Pr_0.7Sr_0.3Fe_0.8Ni_0.2O₃ material with nanoporous microstructure. Polymethyl methacrylate (PMMA), polystyrene (PS) and polycarboxylate (PC) microspheres with different diameters were used as pore formers. These samples were synthesized and characterized by thermogravimetric analysis, inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction, transmission electron microscopy and field emission scanning electron microscopy. The polarization resistance of the materials was studied by Electrochemical Impedance Spectroscopy. The study demonstrated that templated porosity is maintained and highly influences on the impedance spectroscopic behaviour, being the material synthesized with policarboxylate microspheres the most interesting of the three used templates for SOFC applications.     

Columnar-grown porous films of lithium manganese oxide spinel (LiMn2O4) prepared by ultrasonic spray deposition

Using LiNO₃ and Mn(Ac)₂ as raw materials, ultrasonic spray deposition (USD) technique was used to fabricate LiMn₂O₄ films on platinum substrate at different substrate temperatures from 310 to 390 °C. The prepared thick films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrochemical performance of the USD-derived films was also evaluated with LiMn₂O₄/Li cells. It is found that all of the LiMn₂O₄ films are porous and composed of orderly oriented columnar particles. The substrate temperature affects the fine microstructure of the columnar particles. The film prepared at 360 °C substrate temperature give rise to best electrochemical behavior.     

Structural,morphological, composition and optical properties of undoped zinc oxide thin films prepared by spray pyrolysis method: effect of solution concentrations

Abstract

The aim of this paper is the study of transparent undoped zinc oxide thin films obtained by spray pyrolysis technique on glass substrates heated at 350?°C from 0.1 to 0.4?mol solution concentrations using zinc acetate dehydrate as precursor. The X-ray diffraction patterns and Raman spectrometry with respect to Urbach energy and wurtzite structure, show that the maximum value of the high frequency intensity E₂ and the optimal value of the optical gap are obtained at 0.2?mol concentration. Furthermore, an appropriate transparency is obtained and that makes these films suitable for photovoltaic windows layer cells.