Investigation of the Mechanical Stability of Micro‐Solid Oxide Fuel Cell Membranes Using Scanning Laser Vibrometry

Scanning laser vibrometry was used to investigate the mechanical stability of free‐standing micro‐solid oxide fuel cell (micro‐SOFC) membranes. Arrays of square‐shaped 460 nm thin micro‐SOFC membranes were fabricated on silicon substrates using pulsed laser deposition for the yttria‐stabilized zirconia electrolyte and magnetron sputtering for the platinum electrodes. Resonance frequency, displacement and acceleration measurements were carried out using interferometry analysis of the membrane reflection. The resonance frequencies scale with the reciprocal of the membrane length. At the resonance, the 390 × 390 μm² micro‐SOFC membranes exhibit an out‐of‐plane displacement of ca. 1.2 μm only. All free‐standing micro‐SOFC membranes survive the resonant vibration without rupturing. These results are promising for the failure‐free implementation of micro‐SOFC in portable electronic devices.     

Microstructure and Microfabrication Considerations for Self‐Supported On‐Chip Ultra‐Thin Micro‐Solid Oxide Fuel Cell Membranes

La_0.6Sr_0.4Co_0.8Fe_0.2O_{3 – δ} (LSCF) has been sputtered on bare Si and Si₃N₄ and yttria‐stabilised zirconia (YSZ) thin films to investigate annealing temperature‐ and thickness‐dependent microstructure and functional properties, as well as their implications for designing failure‐resistant micro‐solid oxide fuel cell (μSOFC) membranes. The LSCF thin films crystallise in the 400–450 °C range; however, after annealing in the 600–700 °C range, cracks are observed. The formation of cracks is also thickness‐dependent. High electrical conductivity, ∼520 Scm^–1 at 600 °C, and low activation energy, ∼0.13 eV, in the 400–600 °C range, are still maintained for LSCF films as thin as 27 nm. Based on these studies, a strong correlation between microstructure and electrical conductivity has been observed and an annealing temperature‐thickness design space that is complementary to temperature‐stress design space has been proposed for designing reliable membranes using sputtered LSCF thin films. Microfabrication approaches that maintain the highest possible surface and interface quality of heterostructured membranes have been carefully examined. By taking advantage of the microstructure, microfabrication and geometrical structural considerations, we were able to successfully fabricate large‐area, self‐supported membranes. These results are also relevant to conventional or grid‐supported SOFC membranes using ultrathin nanocrystalline cathodes and μSOFCs using cathode thin films other than LSCF.     

Integration of Spin‐Coated Nanoparticulate‐Based La0.6Sr0.4CoO3–δ Cathodes into Micro‐Solid Oxide Fuel Cell Membranes

Thin cathodes for micro‐solid oxide fuel cells (micro‐SOFCs) are fabricated by spin‐coating a suspension of La_0.6Sr_0.4CoO_3–δ (LSC) nanoparticulates obtained by salt‐assisted spray pyrolysis. The resulting 250 nm thin LSC layers exhibit a three‐dimensional porous microstructure with a grain size of around 45 nm and can be integrated onto free‐standing 3 mol.% yttria‐stabilized‐zirconia (3YSZ) electrolyte membranes with high survival rates. Weakly buckled micro‐SOFC membranes enable a homogeneous distribution of the LSC dispersion on the electrolyte, whereas the steep slopes of strongly buckled membranes do not allow for a perfect LSC coverage. A micro‐SOFC membrane consisting of an LSC cathode on a weakly buckled 3YSZ electrolyte and a sputtered Pt anode has an open‐circuit voltage of 1.05 V and delivers a maximum power density of 12 mW cm^–2 at 500 °C.     

Ethanol/water mixture pervaporation performance of b‐oriented silicalite‐1 membranes made by gel‐free secondary growth

b‐oriented silicalite‐1 membranes on porous silica supports were synthesized using gel‐free secondary growth. The porous silica supports were made by pressing crushed quartz fibers followed by sintering and polishing, and further modified by slip‐coating three layers of Stöber silica particles (1000, 350, and 50 nm). The b‐oriented seed layers were prepared by rubbing silicalite‐1 particles (2 μm × 0.8 μm × 3 μm along a‐, b‐, and c‐axis, respectively) after depositing a polymeric layer on the support. After silicalite‐1 seed deposition, a final coating of spherical silica particles was applied. Well‐intergrown, μm‐thick, b‐oriented membranes were obtained, which, after calcination, exhibited ethanol permselectivity in ethanol/water mixture pervaporation. At 60°C and for ～5 wt % ethanol/water mixtures, the best membrane exhibited overall pervaporation separation factor of 85 (corresponding to membrane intrinsic selectivity of 7.7) and total flux of 2.1 kg/(m²·h). This performance is comparable to the best performing MFI membranes reported in the literature. © 2015 American Institute of Chemical Engineers AIChE J, 62: 556–563, 2016     

Development of a novel proton conducting fuel cell based on a Ni‐YSZ support

A new proton conducting fuel cell design based on the BZCYYb electrolyte is studied in this research. In high‐performance YSZ‐based SOFCs, the Ni‐YSZ support plays a key role in providing required electrical properties and robust mechanical behavior. In this study, this well‐established Ni‐YSZ support is used to maintain the proton conducting fuel cell integrity. The cell is in a Ni‐YSZ (375 μm support)/Ni‐BZCYYb (20 μm anode functional layer)/BZCYYb (10 μm electrolyte)/LSCF‐BZCYYb (25 μm cathode) configuration. Maximum power density values of 166, 218, and 285 mW/cm² have been obtained at 600°C, 650°C, and 700°C, respectively. AC impedance spectroscopy results show values of 2.17, 1.23, and 0.76 Ω·cm² at these temperatures where the main resistance contributor above 600°C is ohmic resistance. Very fine NiO and YSZ powders were used to achieve a suitable sintering shrinkage which can enhance the electrolyte sintering. During cosintering of the support and BZCYYb electrolyte layers, the higher shrinkage of the support layer led to compressive stress in the electrolyte, thereby enhancing its densification. The promising results of the current study show that a new generation of proton conducting fuel cells based on the chemically and mechanically robust Ni‐YSZ support can be developed which can improve long‐term performance and reduce fabrication costs of proton conducting fuel cells.     

Freestanding Micro‐SOFCs with Electrodes Prepared by Electrostatic Spray Deposition

We report a freestanding micro solid oxide fuel cell with both the anode and cathode deposited using electrostatic spray deposition (ESD) technique. The cell is consisted of dense yittria‐stabilized zirconia (YSZ) electrolyte (100 nm thick), porous lanthanum strontium manganite (LSM)–YSZ cathode (∼3 μm thick), and porous NiO‐YSZ anode (∼3 μm thick). LSM‐YSZ and NiO‐YSZ composite powders were initially prepared by glycine nitrate process and super‐critical fluid processes, respectively, and both cathode and anode layers were deposited by the ESD. The resulting freestanding micro cell exhibited an open circuit voltage close to the theoretical value of 1.09 V, and a maximum power density of 41.3 mWcm^–2 at 640 °C.     

Phase Evolution upon Aging of Air‐Plasma Sprayed t′‐Zirconia Coatings: I—Synchrotron X‐Ray Diffraction

Phase evolution accompanying the isothermal aging of free‐standing air‐plasma sprayed (APS) 7–8 wt% yttria‐stabilized zirconia (8YSZ) thermal barrier coatings (TBCs) is described. Aging was carried out at temperatures ranging from 982°C to 1482°C in air. The high‐temperature kinetics of the phase evolution from the metastable t′ phase into a mixture of transformable Y‐rich (cubic) and Y‐lean (tetragonal) phases are documented through ambient temperature X‐ray diffraction (XRD) characterization. A Hollomon–Jaffe parameter (HJP), T[27 + ln(t)], was used to satisfactorily normalize the extent of phase decomposition over the full range of times and temperatures. Comparison to vapor deposited TBCs reveal potential differences in the destabilization mechanism in APS coatings. Furthermore, the lattice parameters extracted from Rietveld refinement of the XRD patterns were used to deduce the stabilizer concentrations of the respective phases, which suggest a retrograde tetragonal solvus over the temperature range studied. In concert with a complementary microstructural study presented in Part II, this effort offers new insights into the mechanisms governing the phase evolution and raises implications for the high‐temperature use of 8YSZ ceramics.     

NI/NI‐YSZ Current Collector/Anode Dual Layer Hollow Fibers for Micro‐Tubular Solid Oxide Fuel Cells

A co‐extrusion technique was employed to fabricate a novel dual layer NiO/NiO‐YSZ hollow fiber (HF) precursor which was then co‐sintered at 1,400 °C and reduced at 700 °C to form, respectively, a meshed porous inner Ni current collector and outer Ni‐YSZ anode layers for SOFC applications. The inner thin and highly porous “mesh‐like” pure Ni layer of approximately 50 μm in thickness functions as a current collector in micro‐tubular solid oxide fuel cell (SOFC), aiming at highly efficient current collection with low fuel diffusion resistance, while the thicker outer Ni‐YSZ layer of 260 μm acts as an anode, providing also major mechanical strength to the dual‐layer HF. Achieved morphology consisted of short finger‐like voids originating from the inner lumen of the HF, and a sponge‐like structure filling most of the Ni‐YSZ anode layer, which is considered to be suitable macrostructure for anode SOFC system. The electrical conductivity of the meshed porous inner Ni layer is measured to be 77.5 × 10⁵ S m^–1. This result is significantly higher than previous reported results on single layer Ni‐YSZ HFs, which performs not only as a catalyst for the oxidation reaction, but also as a current collector. These results highlight the advantages of this novel dual‐layer HF design as a new and highly efficient way of collecting current from the lumen of micro‐tubular SOFC.     

Performance Evaluation of Solid Oxide Fuel Cells with Thin Film Electrolyte Fabricated by Binder‐Assisted Slurry Casting

A gas‐tight yttria‐stabilized zirconia (YSZ) electrolyte film was fabricated on porous NiO–YSZ anode substrates by a binder‐assisted slurry casting technique. The scanning electron microscope (SEM) results showed that the YSZ film was relatively dense with a thickness of 10 μm. La_0.8Sr_0.2MnO₃ (LSM)–YSZ was applied to cathode using a screen‐print technique and the single fuel cells were tested in a temperature range from 600 to 800 °C. An open circuit voltage (OCV) of over 1.0 V was observed. The maximum power densities at 600, 700, and 800 °C were 0.13, 0.44, and 1.1 W cm^–2, respectively.     

Influence of Deposition Temperature of GDC Interlayer Deposited by RF Magnetron Sputtering on Anode‐Supported SOFC

Gadolinia‐doped ceria (GDC) film, as a barrier layer to prevent chemical reaction between yttria‐stabilized zirconia (YSZ) electrolyte and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ (BSCF)–GDC cathode, is deposited by radio frequency (RF) magnetron sputtering on YSZ electrolyte, and the influence of deposition temperature on Ni–YSZ/YSZ/GDC/BSCF–GDC single cell performance is investigated. The SEM results show that the GDC film deposited at 30 °C exhibits a porous structure, whereas the GDC film deposited at 400 °C has a dense structure. The single cells show excellent performance when the deposition temperature is above 250 °C, whereas the single cells show poor performance when the deposition temperature is below 200 °C. The large difference in cell performance occurs from their large difference in polarization resistance. The porous structure of GDC interlayer, which cannot well prevent the reaction between BSCF and YSZ, is responsible for the poor performance of the cells with GDC interlayer deposited at a temperature below 200 °C.     

Characterization of a Cu‐La0.75Sr0.25Cr0.5Mn0.5O3 ‐CeO2/La0.75Sr0.25Cr0.5Mn0.5O3‐YSZ/Ni‐ScSZ Three‐Layer Structure Anode in Thin Film Solid Oxide Fuel Cell Running on Methane Fuel

Anodes for Solid Oxide Fuel Cell that is capable of directly using hydrocarbon without external reforming have been of great interest recently. In this paper, a three‐layer structure anode running on methane is fabricated by tape casting and screen printing method. The slurry of catalyst layer Cu‐LSCM‐CeO₂ (with weight ratios of 1.5:7.0:1.5, 2.0:7.0:1.0, 2.15:7.0:0.85 and 2.25:7.0:0.75, weight ratios of Cu/CeO₂ is 1:1, 2:1, 2.5:1 and 3:1, respectively) is screen‐printed on LSCM‐YSZ support layer and Ni‐ScSZ active layer. Thus, LSCM‐YSZ/Ni‐ScSZ anodes with Cu‐LSCM‐CeO₂ catalyst layer (denoted as LSCM‐YSZ1010, LSCM‐YSZ2010, LSCM‐YSZ2510 and LSCM‐YSZ3010, respectively) are obtained. Single cells with three‐layer structure anode are also fabricated and measured, of which the maximum power density reaches 491 and 670 mW cm⁻² for the cell with LSCM‐YSZ2510 anode running on methane at 750 °C and 800 °C, respectively. No significant degradation in performance has been observed after 240h of cell testing when LSCM‐YSZ2510 anode is exposed to methane at 750 °C. Very little carbon deposition is detected on the anode, suggesting that carbon deposition is limited during cell operation. Consequently, Cu‐LSCM‐CeO₂ catalyst layer on the surface of LSCM‐YSZ support layer makes it possible to have good stability for long‐term operation in methane due to very little carbon deposition.     

Preparation and properties of polyimide solvent‐resistant nanofiltration membrane obtained by a two‐step method

This study investigated the preparation of polyimide solvent‐resistant nanofiltration membranes by a two‐step method (casting the membrane first and then crosslinking by the thermal imidization method). The influences of polymer concentration, thickness of membranes, temperature of the imidization, phase inversion time and thermal imidization procedure were studied. The membranes with the highest rejection rate of Fast Green FCF (molecular weight 808.86 g mol^?1) were prepared in the following conditions: polymer concentration 13 wt%, phase inversion time 1 h, membrane thickness 150 µm and thermal imidization procedure 200 °C for 2.5 h, 250 °C for 2 h and 300 °C for 2 h in a vacuum environment; the heating rate was 5 °C min^?1. The membrane was stable in most of the solvents tested and the fluxes of some common solvents were equal to or higher than a number of commercial solvent‐resistant nanofiltration membranes. A much higher rejection of dyes in water than in methanol was observed in the filtration experiments and a new way to explain it was developed. Copyright © 2011 Society of Chemical Industry     

Stress Modulation and Ferroelectric Properties of Nanograined PbTiO3 Thick Films on the Different Substrates Fabricated by Aerosol Deposition

Nanograined PbTiO₃ (PT) thick films were deposited on Si, yttria‐stabilized zirconia (YSZ), and Ni substrates using an aerosol deposition (AD) method at room temperature. The AD PT thick films on each different substrate were annealed at 500°C and 700°C for 1 h to increase the crystallinity. The stresses in the PT film were modulated by controlling the difference in the coefficient of thermal expansion (CTE) between the films and substrates during the thermal annealing process. The morphology of the AD PT films was examined from the polycrystalline dense structure (thickness ~8 μm), and the changes in the crystallographic phase, in‐plane stresses, and ferroelectric properties in annealed films were investigated. In‐plane stress analysis showed that the PT films annealed at 500°C and 700°C on each substrate exhibited compressive stress. Owing to the effects of compressive stress in the PT film, the film showed less tetragonality (c/a ratio) and enhanced ferroelectric behaviors. The change in the polarization–electric field (P–E) hysteresis loop of the PT films was explained by the stress induced from CTE mismatch between the films and substrates.     

Electromechanical properties of CaZrO3 modified (K,Na)NbO3‐based lead‐free piezoceramics under uniaxial stress conditions

Piezoelectric actuators are typically preloaded with a modest mechanical compressive stress during actuation to reduce cracking and allow for operation in the dynamic range. In addition, actuators are required to carry out mechanical work during operation, resulting in a nonlinear relationship between stress and actuation voltage. In fact, mechanical loading can significantly impact the electromechanical performance of lead‐free piezoelectrics. Herein, we report the dependence of electromechanical properties of CaZrO₃ modified (K,Na)NbO₃‐based lead‐free piezoceramics on uniaxial compressive stress, comparing to their lead‐based counterparts. It is demonstrated that increased non‐180° domain switching enhances the strain output at a moderate stress of approximately ?50 MPa from room temperature to 150°C. Larger uniaxial stress, however, is found to suppress ferroelectric domain switching, resulting in the continuous strain and polarization decrease.     

Temperature‐dependent permeability of polyelectrolyte complex capsule membranes having N‐isopropylacrylamide domains

As a microcapsule with temperature sensitivity, poly(methacrylic acid)–polyethylenimine complex capsules containing N‐isopropylacrylamide units were designed. Two kinds of copolymers of methacrylic acid and N‐isopropylacrylamide were synthesized by free‐radical copolymerization. Partly crosslinked poly(methacrylic acid)–polyethylenimine complex capsules containing the methacrylic acid–N‐isopropylacrylamide copolymers were prepared at 40 or 25°C. The permeation of phenylethylene glycol through the capsule membranes was investigated. Permeability of the capsules prepared at 25°C increased monotonously with increasing temperature from 10 to 50°C. Permeability of the capsules prepared at 40°C also increased with increasing temperature up to 25°C but decreased above 30°C. Also, the degree of swelling of the membranes prepared at 40°C decreased above 30°C. Differential scanning calorimetry measurement showed that N‐isopropylacrylamide units underwent more efficient transition in the capsule membranes prepared at 40°C than in the membranes prepared at 25°C. The capsule membranes prepared at 40°C might have domains in which N‐isopropylacrylamide units are concentrated, whereas these units should distribute uniformly in the capsule membranes made at 25°C. Such a difference in distribution of N‐isopropylacrylamide units might result in the different permeation property of the capsule membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2703–2710, 2000     

Compressive strength of fly‐ash‐based geopolymer concrete at elevated temperatures

This paper presents the compressive strength of fly‐ash‐based geopolymer concretes at elevated temperatures of 200, 400, 600 and 800 °C. The source material used in the geopolymer concrete in this study is low‐calcium fly ash according to ASTM C618 class F classification and is activated by sodium silicate (Na₂SiO₃) and sodium hydroxide (NaOH) solutions. The effects of molarities of NaOH, coarse aggregate sizes, duration of steam curing and extra added water on the compressive strength of geopolymer concrete at elevated temperatures are also presented. The results show that the fly‐ash‐based geopolymer concretes exhibited steady loss of its original compressive strength at all elevated temperatures up to 400 °C regardless of molarities and coarse aggregate sizes. At 600 °C, all geopolymer concretes exhibited increase of compressive strength relative to 400 °C. However, it is lower than that measured at ambient temperature. Similar behaviour is also observed at 800 °C, where the compressive strength of all geopolymer concretes are lower than that at ambient temperature, with only exception of geopolymer concrete containing 10 m NaOH. The compressive strength in the latter increased at 600 and 800 °C. The geopolymer concretes containing higher molarity of NaOH solution (e.g. 13 and 16 m ) exhibit greater loss of compressive strength at 800 °C than that of 10 m NaOH. The geopolymer concrete containing smaller size coarse aggregate retains most of the original compressive strength of geopolymer concrete at elevated temperatures. The addition of extra water adversely affects the compressive strength of geopolymer concretes at all elevated temperatures. However, the extended steam curing improves the compressive strength at elevated temperatures. The Eurocode EN1994:2005 to predict the compressive strength of fly‐ash‐based geopolymer concretes at elevated temperatures agrees well with the measured values up to 400 °C. Copyright © 2014 John Wiley & Sons, Ltd.     

High‐temperature stability of YSZ and MSZ ceramic materials in CaF2–MgF2–MgO molten salt system

The high‐temperature stability of YSZ and MSZ specimens was investigated in CaF₂–MgF₂–MgO molten salt at 1200°C. YSZ was mostly composed of m‐ZrO₂ and a small part of YF₃ in the early stages. The formation of YF₃ was attributed to the chemical reaction between Y₂O₃ and MgF₂, which can lead to the leaching of Y₂O₃ from YSZ. With an increase in exposure time, the degraded surface was coarser, and considerable amount of cracks, pores, and spallations were formed. Furthermore, no Y₂O₃ was found up to 120 μm of the YSZ bulk in the early stages. MSZ was composed of t‐ZrO₂ after 24 hours. However, the volume fraction of m‐ZrO₂ was 72% after 72 hours, and CaZrO₃ was formed by the chemical reaction between CaO and ZrO₂ after 168 hours. In addition, the volume fraction of m‐ZrO₂ was 60% in 2.5 wt% MgO and 49% in 10 wt% MgO. In 5 wt% MgO, CaZrO₃ was formed. We demonstrate that the high‐temperature stability of MSZ was better than that of YSZ, and that 10 wt% MgO was much more stable than the other concentrations of MgO.     

Direct Applicability of La0.6Sr0.4CoO3 – δ Thin Film Cathode to Yttria Stabilised Zirconia Electrolytes at T ≤ 650 °C

For investigating the direct applicability of highly active cobalt containing cathodes on YSZ electrolytes at a lower processing and operating temperature range (T ≤ 650 °C), we fabricated a thin film lanthanum strontium cobalt oxide (LSC) cathode on an yttria stabilised zirconia (YSZ)‐based solid oxide fuel cell (SOFC) via pulsed laser deposition (PLD). Its electrochemical performance (5.9 mW cm^–2 at 0.7 V, 650 °C) was significantly inferior to that (595 mW cm^–2 at 0.7 V, 650 °C) of an SOFC with a thin (t ∼ 200 nm) gadolinium doped ceria (GDC) buffer layer in between the LSC thin film cathode and the YSZ electrolyte. It implies that even though the cathode processing and cell operating temperatures were strictly controlled not to exceed 650 °C, the direct application of LSC on YSZ should be avoided. The origin of the cell performance deterioration is thoroughly studied by glancing angle X‐ray diffraction (GAXRD) and transmission electron microscopy (TEM), and the decomposition of the cathode and diffusion of La and Sr into YSZ were observed when LSC directly contacted YSZ.     

Redox Tolerance of Thin and Thick Ni/YSZ Anodes of Electrolyte‐Supported Single‐Chamber Solid Oxide Fuel Cells under Methane Oxidation Conditions

Redox tolerance of 50 and 500 μm thick Ni/YSZ (yttria‐stabilized zirconia) anodes supported on YSZ electrolytes were studied under single‐chamber solid oxide fuel cell conditions. Open circuit voltage, electrochemical impedance spectra, and discharge curves of the cells were measured under different methane/oxygen ratios at 700 °C. For the cell with the thin anode, a significant degradation accompanying oscillatory behaviors was observed, whereas the cell based on the thick anode was much more stable under the same conditions. In situ local anode resistance (R_s) results indicated that the Ni/NiO redox cycling was responsible for the oscillatory behaviors, and the cell degradation was primarily caused by the Ni reoxidation. Reoxidation of the thick anode took place at a low methane/oxygen ratio, but the anode can be recovered to its original state by switching to a methane‐rich environment. On the contrary, the thin anode was unable to be regenerated after the oxidation. Microstructure damage of the anode was attributed to its irreversible degradation.     

Development and Fabrication of a New Concept Planar‐tubular Solid Oxide Fuel Cell (PT‐SOFC)

The paper reports a new concept of planar‐tubular solid oxide fuel cell (PT‐SOFC). Emphasis is on the fabrication of the required complex configuration of Ni‐yttria‐stabilised zirconia (YSZ) porous anode support by tert‐butyl alcohol (TBA) based gelcasting, particularly the effects of solid loading, amounts of monomers and dispersant on the rheological behaviour of suspension, the shrinkage of a wet gelcast green body upon drying, and the properties of final sample after sintering at 1350 °C and reduction from NiO‐YSZ to Ni‐YSZ. The results show that the gelcasting is a powerful method for preparation of the required complex configuration anode support. The anode support resulted from an optimised suspension with the solid loading of 25 vol% has uniform microstructure with 37% porosity, bending strength of 44 MPa and conductivity of 300 S cm^—1 at 700 °C, meeting the requirements for an anode support of SOFC. Based on the as‐prepared anode support, PT‐SOFC single cell of Ni‐YSZ/YSZ/LSCF has been fabricated by slurry coating and co‐sintering technique. The cell peak power density reaches 63, 106 and 141 mW cm^—2 at 700, 750 and 800 °C, respectively, using hydrogen as fuel and ambient air as oxidant.