Electron beam physical vapour deposited zirconia based ceramics for developments of solar surface coatings

Abstract

Infrared radiative properties of thermal barrier coatings have been investigated for developments of solar absorbing surface coatings. Various types of multilayer broadband optical filters were designed incorporating 7 wt-% yttria stabilised zirconia (7YSZ) and aluminium oxide (Al₂O₃). Electron beam physical vapour deposition method was employed to deposit 7YSZ thin films on quartz substrates to study their optical properties. The refractive index and thickness of 7YSZ films were estimated using spectroscopic ellipsometry technique, giving the index as 1·95 at 633 nm. Multilayer thermal barrier coating structures were fabricated by depositing alternate layers of 7YSZ and Al₂O₃ on quartz using electron beam physical vapour deposition. The spectral characteristics of multilayer 7YSZ–Al₂O₃ coatings were evaluated using a spectrometer in the visible and near infrared range. Preliminary results obtained from multilayer 7YSZ–Al₂O₃ coatings had exhibited 75% transmission over a wide band of 0·4–1·0 μm.     

Spectrally selective Al/AlN/Al/AlN tandem solar absorber by inline reactive ac magnetron sputtering

Abstract

Spectrally selective Al/AlN/Al/AlN tandem solar absorbers were deposited onto soda lime glass substrates using inline ac magnetron sputtering in a reactive atmosphere containing argon and nitrogen. To achieve a reproducible and homogenous deposition process, the deposition of multilayer Al/AlN/Al/AlN films under different process conditions was investigated. Two main variables, ac power and the speed of substrate movement in the chamber, were varied in the ranges of 1–10 kW and 10·47–31·4 mm s^?1 respectively to obtain films with high absorption and low emittance. The effects of film thickness of different layers and deposition conditions on the optical performance of selective coatings were also studied. Structural features and surface morphology of the films were investigated by X-ray diffraction and field emission scanning electron microscopy analyses respectively. In the present study, tandem solar absorber films deposited onto glass substrate with optimised sputtering parameters can consistently achieve solar absorptance α of 0·864 and thermal emittance ? of 0·03 at 80°C.     

Pulsed laser deposition of yttria stabilized zirconia for solid oxide fuel cell applications

Yttria stabilized zirconia (YSZ) films were grown by pulsed laser deposition (PLD) from a 8YSZ target using a KrF excimer laser source (248 nm). The films have been deposited under oxygen atmospheres on porous NiO/YSZ substrates heated from room temperature to 600 °C. YSZ films were obtained in the range of 1–2 μm thickness. The films have been investigated with respect to surface morphology, microstructure and film–substrate interface interaction. The film morphology varied from columnar to an irregular crystalline structure depending on the oxygen pressure and the substrate temperature. In all cases the films consisted of YSZ with the cubic fluorite structure. The formation of oxide layers under low oxygen pressures on the NiO/YSZ substrates is due to a film–substrate redox interaction. The NiO grains close to the coating interface are partially reduced and serve as an oxygen source for the oxidation of the film. The measured He leakage rates to analyze the gas tightness of the YSZ films have so far shown no improvements as compared with uncoated substrates.     

Development of intermediate temperature SOFC using LaGaO3 based oxide film

Abstract

The effect of the NiO–Fe₃O₄ (NiFeO)/Ce_0·8Sm_0·2O_2-δ (SDC) ratio on the microstructure and electrochemical activity of cermet substrates was systematically investigated. Dense NiFeO–SDC substrates, which are suitable for the deposition of thin oxide films for example, La_0·9Sr_0·1Ga_0·8Mg_0·2O_3-δ (LSGM) tend to be porous and applicable as anodes in intermediate temperature solid oxide fuel cells (IT SOFC). The porosity and electrical conductivity of the reduced substrates were evaluated with increasing NiFeO ratios. The lowest anode overpotential was measured in a substrate with a NiFeO/SDC ratio of 6:4, especially at a high current density. In a reduced substrate with this composition, continuous frames of SDC and NiFe alloy can be formed simultaneously, thus leading a longer triple phase boundary.     

Effects of sputtering pressure on properties of Al doped ZnO thin films dynamically deposited by rf magnetron sputtering

Abstract

Aluminium doped zinc oxide (AZO) films were dynamically deposited by rf magnetron sputtering under various sputtering pressures in the range of 0·3–2·0 Pa. The effect of the Ar sputtering pressure on the structural, electrical and optical properties of the AZO films was systematically investigated by X-ray diffractometry, scanning electron microscope, four-point probe measurement and UV–vis spectrophotometer. As the sputtering pressures decrease, the crystallite sizes of the films became larger, while their deposition rate turns higher. Under the condition of lower sputtering pressures, a decrease in the resistivity was observed due to an increase in carrier concentration. The AZO film deposited at 0·5 Pa in the dynamic mode has shown the lowest resistivity of 9·5×10^?4 Ω cm. This work was performed in a dynamic deposition system in order to produce a large area of AZO films, which is more important in practical fields to improve productivity.     

The role of electrical conductivity of substrate on the YSZ film formed by EPD for solid oxide fuel cell applications

Thick YSZ (8 mol% Y₂O₃–ZrO₂) films were coated by EPD, which was performed on non-conducting and graphite-coated NiO–YSZ composites. Weights of depositions had depended on the applied voltage linearly for both types of NiO–YSZ composites. In addition, weights of depositions were significantly higher when graphite-coated substrates were used. Uniform and dense depositions were successfully obtained by both methods. Adhesion strength was evaluated by micro hardness testing. However, it was observed that the interfacial adhesion was improved when graphite-coated substrates were used. The qualities of the deposited YSZ films were different after the subsequent sintering and cracks were developed on the surface of sintered YSZ films when non-conducting substrates were used. SEM observations showed that there were thicker YSZ films on the graphite-coated substrates than on the non-conducting ones. After the reduction process, NiO–YSZ composites were altered to Ni–YSZ cermet, which showed a good electrical conductivity all over it.     

Anode-supported solid oxide fuel cell with yttria-stabilized zirconia/gadolinia-doped ceria bilalyer electrolyte prepared by wet ceramic co-sintering process

To protect the ceria electrolyte from reduction at the anode side, a thin film of yttria-stabilized zirconia (YSZ) is introduced as an electronic blocking layer to anode-supported gadolinia-doped ceria (GDC) electrolyte solid oxide fuel cells (SOFCs). Thin films of YSZ/GDC bilayer electrolyte are deposited onto anode substrates using a simple and cost-effective wet ceramic co-sintering process. A single cell, consisting of a YSZ (∼3 μm)/GDC (∼7 μm) bilayer electrolyte, a La_0.8Sr_0.2Co_0.2Fe_0.8O₃–GDC composite cathode and a Ni–YSZ cermet anode is tested in humidified hydrogen and air. The cell exhibited an open-circuit voltage (OCV) of 1.05 V at 800 °C, compared with 0.59 V for a single cell with a 10-μm GDC film but without a YSZ film. This indicates that the electronic conduction through the GDC electrolyte is successfully blocked by the deposited YSZ film. In spite of the desirable OCVs, the present YSZ/GDC bilayer electrolyte cell achieved a relatively low peak power density of 678 mW cm⁻² at 800 °C. This is attributed to severe mass transport limitations in the thick and low-porosity anode substrate at high current densities.     

Electrophoretic deposition on non-conducting substrates: The case of YSZ film on NiO–YSZ composite substrates for solid oxide fuel cell application

This paper report the results of our investigation on electrophoretic deposition (EPD) of YSZ particles from its suspension in acetylacetone onto a non-conducting NiO–YSZ substrate. In principle, it is not possible to carry out electrophoretic deposition on non-conducting substrates. In this case, the EPD of YSZ particles on a NiO–YSZ substrate was made possible through the use of an adequately porous substrate. The continuous pores in the substrates, when saturated with the solvent, helped in establishing a “conductive path” between the electrode and the particles in suspension. Deposition rate was found to increase with increasing substrate porosity up to a certain value. The higher the applied voltage, the faster the deposition. For a given applied voltage, there exists a threshold porosity value below which EPD becomes practically impossible. An SOFC constructed on bi-layers of NiO–YSZ/YSZ with YSZ layer thickness of 40 μm exhibited an open circuit voltage (OCV) of 0.97 V at 650 °C and peak power density of 263.8 mW cm⁻² at 850 °C when tested with H₂ as fuel and ambient air as oxidant.     

Fabrication of bilayered YSZ/SDC electrolyte film by electrophoretic deposition for reduced-temperature operating anode-supported SOFC

Bilayered Y₂O₃-stabilized ZrO₂ (YSZ)/Sm₂O₃-doped CeO₂ (SDC) electrolyte films were successfully fabricated on porous NiO–YSZ composite substrates by electrophoretic deposition (EPD) based on electrophoretic filtration followed by co-firing with the substrates. In EPD, positively charged YSZ and SDC powders were deposited directly on the substrates, layer by layer from ethanol-based suspensions. Delamination between YSZ and SDC films was avoided by reducing the SDC films’ thickness to ca. 1 μm. A single cell was constructed on the bilayered electrolyte films composed of ca. 4 μm-thick YSZ and ca. 1 μm-thick SDC films. As a cathode in the cell, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−x (LSCF) was used. Maximum output power densities greater than 0.6 W cm⁻² were obtained at 700 °C for the bilayered YSZ/SDC electrolyte cells thus constructed.     

Nanoporous nickel thin film anode optimization for low-temperature solid oxide fuel cells

Thin film solid oxide fuel cells (TF–SOFCs) having anode–substrate nanostructure that was optimized for the low-temperature operation were fabricated. Nickel thin film anodes with four different anode thicknesses were deposited on anodic aluminum oxide templates, nanoporous substrates having two different pore sizes, by the sputtering method. Subsequently, a yttria-stabilized zirconia (YSZ) electrolyte and platinum cathode were deposited on them, which completed the entire fuel cell structure. The anode nanostructure of fuel cells in six combinations was analyzed by the cross-sectional view, surface microscopy method, and three-dimensional morphology observation. Those investigations enabled the anode nanostructure to be identified, such as the anode porosity and the roughness of the interface between anodes and electrolytes. Then, the six TF–SOFCs were electrochemically characterized in a 500 °C operating environment. The maximum power densities were obtained through the i–V–P curves, and the highest performance of 294.1 mW/cm² was measured in the cell having a combination of 200 nm–sized porous aluminum anodic oxide (AAO) and 1200 nm–thick Ni anode. This showed up to 20.1% improvement over the other cells. EIS analysis showed that the optimized ohmic and faradaic resistance originated from each part of the unique TF–SOFC structure.     

Effect of magnetron sputtered anode functional layer on the anode-supported solid oxide fuel cell performance

Nickel oxide-yttria stabilized zirconia (NiO-YSZ) thin films were reactively sputter-deposited by pulsed direct current magnetron sputtering from the Ni and ZrY targets onto heated commercial NiO-YSZ substrates. The microstructure and composition of the deposited films were investigated with regard to application as thin anode functional layers (AFLs) for solid oxide fuel cells (SOFCs). The pore size, microstructure and phase composition of both as-deposited and annealed at 1200 °C for 2 h AFLs were studied by scanning electron microscopy and X-ray diffractometry and controlled by changing the deposition process parameters. The results show that annealing in air at 1200 °C is required to improve structural homogeneity of the films. NiO-YSZ films have pores and grains of several hundred nanometers in size after reduction in hydrogen. Adhesion of deposited films was evaluated by scratch test. Anode-supported solid oxide fuel cells with the magnetron sputtered anode functional layer, YSZ electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O₃/Ce_0.9Gd_0.1O₂ (LSCF/CGO) cathode were fabricated and tested. Influence of thin anode functional layer on performance of anode-supported SOFCs was studied. It was shown that electrochemical properties of the single fuel cells depend on the NiO volume content in the NiO-YSZ anode functional layer. Microstructural changes of NiO-YSZ layers after nickel reduction-oxidation (redox) cycling were studied. After nine redox cycles at 750 °C in partial oxidation conditions, the cell with the anode NiO-YSZ layer showed stable open circuit voltage values with the power density decrease by 11% only.     

Photoelectrocatalytic activity of spray deposited ZnO thin films against E. coli Davis

Abstract

Zinc oxide (ZnO) thin films have been deposited onto fluorine doped tin oxide coated glass substrates by economical chemical spray pyrolysis technique. Films were deposited using various quantities of solution from 50 to 200 cc (substrate temperature 400°C, solution concentration 0·2M) in order to achieve different thicknesses. The films were characterised by X-ray diffraction, SEM, AFM and optical absorption techniques. The films exhibit a hexagonal wurtzite crystal structure with preferred (002) orientation. Morphological study showed a smooth and nanocrystalline surface of ZnO films. Direct optical band gap energy of ZnO thin films is found to be 3·24 eV. The average transmission is of the order of 87% in the visible region. The photoelectrocatalytic response of the film against Escherichia coli Davis is studied using a specially designed photoelectrochemical (PEC) reactor module. Thickness and UV light dependent photoelectrocatalytic bactericidal properties of ZnO thin films have been investigated. It shows that biased 1·1 μm thick ZnO thin films with 2 mW cm^?2 UV light intensity give better bactericidal response compared to others. The relative percentage of killing of bacteria is 19·81% due to UV illumination, 52·71% due to UV illumination and passing over ZnO surface and 95·03% due to UV illumination and passing through PEC reactor with ZnO thin film after 2·5 h. It can be concluded that the ZnO thin film with photochemical reactor can be used in a water purifier to get bacteria free drinking water.     

Fabrication and characterization of Cu–Ni–YSZ SOFC anodes for direct use of methane via Cu-electroplating

The Cu–Ni–YSZ cermet anodes for direct use of methane in solid oxide fuel cells have been fabricated by electroplating Cu into a porous Ni–YSZ cermet anode. The uniform distribution of Cu in the Ni–YSZ anode was obtained by electroplating in an aqueous solution mixture of CuSO₄·5H₂O and H₂SO₄ for 30 min with 0.1 A of applied current. When the Cu–Ni–YSZ anode was exposed to methane at 700 °C, the amount of carbon deposited on the anode decreased as the amount of Cu in the Cu–Ni solid solution increased. The power density (0.24 W/cm²) of a single cell with a Cu–Ni–YSZ anode was slightly lower in methane at 700 °C than the power density (0.28 W/cm²) of a single cell with a Ni–YSZ anode. However, the performance of the Ni–YSZ anode-supported single cell degraded steeply over 21 h because of carbon deposition, whereas the Cu–Ni–YSZ anode-supported single cell showed enhanced durability up to 200 h.     

Sputtered YSZ based protective thin films for SOFCs

Abstract

Protective Zr(Y)O_2–δ based films, deposited using magnetron sputtering, onto apatite type ceramics, were appraised for potential applications in solid oxide fuel cells with silicate based solid electrolytes, where performance may suffer from surface decomposition processes in reducing atmospheres. While as prepared Zr(Y)O_2–δ films without copper additive were already crystallised and single phase, fresh Cu containing Zr(Y)O_2–δ are essentially amorphous, requiring high temperature treatment in air for crystallisation. Deposition rate of 0·50–0·75 μm h^–1 at sputtering power of 300 W was achieved. Surface morphology studies using atomic force microscope revealed typical film structures with small (<50 nm) grains. The hardness of films decreases from 15·8 to 8·4 GPa with increasing copper content. Polarisation studies of electrochemical cell with cermet anodes, applied over protective films, suggested that electrochemical reaction is essentially governed by oxygen anion transfer from zirconia phase and/or hydrogen oxidation in vicinity of zirconia film surface. Copper incorporation into Zr(Y)O_2–δ film leads to higher anode resistivity.     

Dependence of polarization in anode-supported solid oxide fuel cells on various cell parameters

The performance of solid oxide fuel cells (SOFCs) is affected by various polarization losses, namely, ohmic polarization, activation polarization and concentration polarization. Under given operating conditions, these polarization losses are largely dependent on cell materials, electrode microstructures, and cell geometric parameters. Solid oxide fuel cells (SOFC) with yttria-stabilized zirconia (YSZ) electrolyte, Ni–YSZ anode support, Ni–YSZ anode interlayer, strontium doped lanthanum manganate (LSM)–YSZ cathode interlayer, and LSM current collector, were fabricated. The effect of various parameters on cell performance was evaluated. The parameters investigated were: (1) YSZ electrolyte thickness, (2) cathode interlayer thickness, (3) anode support thickness, and (4) anode support porosity. Cells were tested over a range of temperatures between 600 and 800 °C with hydrogen as fuel, and air as oxidant. Ohmic contribution was determined using the current interruption technique. The effect of these cell parameters on ohmic polarization and on cell performance was experimentally measured. Dependence of cell performance on various parameters was rationalized on the basis of a simple analytical model. Based on the results of the cell parameter study, a cell with optimized parameters was fabricated and tested. The corresponding maximum power density at 800 °C was ∼1.8 W cm⁻².     

Stress field and failure probability analysis for the single cell of planar solid oxide fuel cells

An analytical model is developed to predict the residual thermal stresses in a single cell of solid oxide fuel cells (SOFCs), which consists of a thick porous 8 mol% Y₂O₃ stabilized zirconia/nickel oxide (8YSZ/NiO) anode, a dense 8YSZ electrolyte and a porous lanthanum strontium manganite (LSM) cathode. The simulated stresses in the cell at room temperature, which are resulted from the contraction mismatch of its components, indicate that the major principal stress in the anode is tensile while the electrolyte and cathode are under compressive stresses. The stress in one component decreases with the increase of its thickness when the thicknesses of the other two components are fixed, and the decrease of the tensile stress in the anode will cause the increase of the compressive stresses in both the cathode and the electrolyte, and vice versa. The analysis also reveals that the anode is the part that is most susceptible to fracture since the tensile thermal stress is so high that it reaches to the fracture strength of the anode material. The Weibull statistic is employed to estimate the failure probability of the anode. The simulation results indicate that the anode failure probability decreases with the increase of the anode thickness and the decrease of the electrolyte thickness. To keep the anode failure probability less than 1E−06, the anode thickness should be greater than 0.7 mm for a cell with an electrolyte thickness of 10 μm and a cathode thickness of 20 μm.     

Solid oxide fuel cells with dense yttria-stabilized zirconia electrolyte membranes fabricated by a dry pressing process

Dense yttria-stabilized zirconia (YSZ) electrolyte films were successfully fabricated onto anode substrates using a modified dry pressing process. The film thickness was uniform, and could be readily controlled by the mass of the nanocrystalline YSZ powders. The electrolyte films adhered well to the anode substrates by controlling the anode composition. An anode-supported solid oxide fuel cell (SOFC) with a dense YSZ electrolyte film of 8 μm in thickness was operated at temperatures from 700 to 800 °C using humidified (3 vol% H₂O) hydrogen as fuel and air as oxidant. An open circuit voltage of 1.06 V and a maximum power density of 791 mW cm⁻² were achieved at 800 °C. The results indicate that the gas permeation through the electrolyte film was negligible, and that good performance can be obtained by this simple and cost-effective technique which can significantly reduce the fabrication cost of SOFCs.     

A novel design and performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack

A novel design of cone-shaped tubular segmented-in-series solid oxide fuel cell (SOFC) stack is presented in this paper. The cone-shaped tubular anode substrates are fabricated by slip casting technique and the yttria-stabilized zirconia (YSZ) electrolyte films are deposited onto the anode tubes by dip coating method. After sintering at 1400 °C for 4 h, a dense and crack-free YSZ film with a thickness of about 7 μm is successfully obtained. The single cell, NiO-YSZ/YSZ (7 μm)/LSM-YSZ, provides a maximum power density of 1.78 W cm⁻² at 800 °C, using moist hydrogen (75 ml min⁻¹) as fuel and ambient air as oxidant.A two-cell-stack based on the above-mentioned cone-shaped tubular anode-supported SOFC is fabricated. Its typical operating characteristics are investigated, particularly with respect to the thermal cycling test. The results show that the two-cell-stack has good thermo-mechanical properties and that the developed segmented-in-series SOFC stack is highly promising for portable applications.     

Performance and stability of SOFC anode fabricated from NiO–YSZ composite particles

Ni–YSZ cermet anodes for solid oxide fuel cells (SOFCs) were fabricated at various sintering temperatures from NiO–YSZ composite particles made by spray pyrolysis (SP) technique. NiO particles covered with fine YSZ (Y₂O₃ stabilized ZrO₂) particles were used as the composite particles, and the initial ratio of Ni and YSZ was set at 75:25 (mol%). As a result, the cermet anode sintered at 1350 °C showed the morphology in which fine YSZ grains were uniformly dispersed on the surface of Ni grain network. Electrical performance such as electrochemical activity and internal resistance of a Ni–YSZ cermet anode changed with sintering temperature. The anode fabricated at 1350 °C showed the highest electrical performance. Especially, a single cell voltage with the Ni–YSZ cermet anode kept very stable for 8000 h at 1000 °C in the SOFC operation condition of H₂—3% H₂O and air. The cermet anode after a long-term test had its initial morphology. It indicates that the Ni–YSZ cermet anode fabricated from NiO–YSZ composite particles is a very promising material for its practical use as SOFCs.     

Achieving high mechanical-strength CH4-based SOFCs by low-temperature sintering (1100 °C)

Despite much progress achieved in the past decades in the process of advancing the low-temperature sintering technologies for Solid oxide fuel cells (SOFCs), such as via the structure design of the electrode materials, the practical application of low-temperature sintered SOFCs (with disqualified mechanical strength) remains challenging. In this work, first, we demonstrate that the appropriate amount of CuO as sintering aids can successfully reduce the co-firing temperature of conventional micron size NiO-YSZ (yttrium-stabilized zirconia (Y₂O₃)_0.08–(ZrO₂)_0.92) anode from about 1400 °C to only 1100 °C. Second, the quantitative structure-activity relationship among the mechanical strength (low-temperature sintering ability) of anode cermets with the inclusion of CuO contents and the densification of YSZ electrolyte was synthetically evaluated, and the optimal Cu–NiO-YSZ anode composition demonstrates almost the equal mechanical strength when compared with the traditional NiO-YSZ anode (sintering at 1400 °C). At last, by comprehensive assessment, 8%Cu–52NiO-40YSZ (8%CuO–NiO-YSZ) shows excellent low-temperature sintering ability, high mechanical strength, optimal power output, and anti-carbon deposition when using as hydrocarbon-based anode for SOFCs.