Chemical and thermomechanical compatibility between Ni–GDC anode and electrolytes based on ceria

The scope of the present work is to study the thermal and chemical compatibility between a Ni–Ce_0.9Gd_0.1O_1.95 cermet, with 39 vol.% Ni, and two electrolytes based on Ce_0.9Gd_0.1O_1.95 (GDC). The cermet was synthesized as a composite NiO–Ce_0.9Gd_0.1O_1.95 by a polymeric organic complex solution method and subsequently reduced to Ni–Ce_0.9Gd_0.1O_1.95 cermet. The GDC electrolytes were prepared by: (a) chemical precipitation process with nitrates as precursors and (NH₄)OH as precipitant agent and (b) from a commercial submicronic powder modified with 1.0 wt.% Bi₂O₃ for improving the sintering mechanism.The anode was fixed on the electrolyte by isostatic pressing of powders and the obtained sandwich was cosintered between 1350 and 1400 °C for 2 h to obtain dense electrolytes with high ionic conductivity along with well-developed anode/electrolyte interfaces of solid oxide fuel cells. The cosintered anode/electrolyte interfaces were characterized by using scanning electron microscopy. The study of the possible diffusion of nickel from the anode into the electrolyte was performed by EDAX analysis. The reaction products formed into cosintered materials were determined by X-ray diffraction (XRD). It is found that the anode is compatible with both electrolytes up to 1400 °C without formation of new phases at these temperatures even during prolonged treatments.     

Effect of variation of NiO on properties of NiO/GDC (gadolinium doped ceria) nano-composites

In the present work, systematic study of series of NiO_x GDC_(1?x) where x = 0.1–0.6; has been reported for the first time. For the synthesis of homogeneous NiO–GDC nanocomposite powders, the nano-powders of NiO and Ce_0.9Gd_0.1O_1.95 (GDC10) synthesized by solution combustion synthesis were mixed in mol % proportion. NiO–GDC nanocomposite can be reduced in situ to form Ni–GDC cermet anode. Hence the Ni–GDC cermet anode combines the catalytic activity and high electronic conduction property of Ni and ionic conductivity of GDC. Nano-crystalline constituents in the NiO–GDC nano composite are believed to give better anodic performance than microcrystalline constituents. Hence the efficient study of the atomistic structure and the accurate characterization of the structural parameters, such as crystallite size and internal strains, are of considerable interest. Therefore the NiO_x–GDC10_1?x nanocomposite powders were characterized by XRD and FTIR spectroscopy. Further these powders were pelletized, sintered and characterized by FE-SEM and d.c. conductivity.     

Anode-supported SOFCs based on Sm0.2Ce0.8O2−δ electrolyte thin-films fabricated by co-pressing using microwave combustion synthesized powders

Decreasing the electrolyte thickness is an effective approach to improve solid oxide fuel cells (SOFCs) performance for intermediate-temperature applications. Sm_0.2Ce_0.8O_2−δ (SDC) powders with low apparent density of 32±0.3 mg cm⁻³ are synthesized by microwave combustion method, and SDC electrolyte films as thin as ~10 μm are fabricated by co-pressing the powders onto a porous NiO–SDC anode substrate. Dense SDC electrolyte thin films with grain size of 300–800 nm are achieved at a low co-firing temperature of 1200 °C. Single cells based on SDC thin films show peak power densities of 0.86 W cm⁻² at 650 °C using 3 vol% humidified H₂ as fuel and ambient air as oxidant. Both the thin thickness of electrolyte films and ultra-fine grained anode structure make contributions to the improved cell performance.     

Spark plasma assisted carbothermal reduction-nitridation synthesis of (Ti,W, Mo)(C,N)-(Ni,Co) powders

Ultrafine (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders were rapidly synthesized from various metal oxides, mainly anatase-TiO₂, by spark plasma assisted carbothermal reduction-nitridation (SPCRN) at low temperature. The phase evolution of the SPCRN reaction was investigated using X-ray diffraction (XRD) and the microstructure of the product powders was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). NiO, Co₃O₄ and MoO₃ were converted to Ni, Co and Mo₂C by CR reaction at temperatures below 900 °C. WO₃ was successively transformed from W₂C to WC by CR reaction up to 1100 °C. Finally, at up to 1350 °C, (Ti, W, Mo)(C, N) formed into the sequence of TiO₂, Ti₄O₇, Ti₃O₅, Ti(O, N), Ti(C, N), (Ti, W)(C, N) and (Ti, W, Mo)(C, N). The crystal structure of (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders was analyzed by the Rietveld method and transmission electron microscopy (TEM). The findings demonstrated that the pure (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders with grain size of below 0.5 µm were synthesized from metal oxides by SPCRN reaction at 1400 °C for 10 min.     

Characterization of IT-SOFC non-symmetrical anode sintered through conventional furnace and microwave

This work investigated the mechanical and electrical properties of NiO–SDC/SDC anode sintered by two different methods: in a microwave at about 1200 °C for 1 h and in a conventional furnace at 1200 °C with a holding time of 1 h (total sintering time of 21 h). Nano-powders Sm_0.2Ce_0.8O_1.9 (SDC) and NiO were mixed using a high-energy ball mill, followed by the co-pressing technique at a compaction pressure of 400 MPa. No binder was used between the layers. The electrical behaviors of all sintered samples were studied using electrochemical impedance spectra in the frequency range of 0.01–10⁵ Hz under 97% H₂–3% H₂O, an amplitude of 10 mV, and at high temperature range of 600–800 °C. Results indicate that the non-symmetrical NiO–SDC/SDC anode achieved through microwave sintering has finer grain size and higher electrochemical performance. However, hardness and Young׳s modulus increased in the samples sintered through a conventional furnace.     

Effect of microstructure on the electrochemical performance of Ni-ScSZ anodes

The effects of NiO powder morphology and sintering temperature on the microstructure and the electrochemical performance of Nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet anodes for solid oxide fuel cells (SOFCs) were investigated. The particle size and agglomeration of the starting powders were found to affect both the microstructure and electrochemical performance of the Ni-ScSZ cermet anodes. The lowest polarization resistance, 0.690 Ω cm² at 700 °C, was measured for the Ni-ScSZ anode prepared with fine NiO powder (~0.5 µm grain size). This was attributed to the increase in the number of reaction sites afforded by the small grains and well-dispersed Ni and ScSZ phases. The effect of the anode sintering temperature was also found to affect the anode microstructure, adhesion with the electrolyte, and consequently anode polarization resistance. The lowest polarization resistance was observed for the anode sintered at 1400 °C and this was 3–5 times lower than the corresponding values for anodes sintered at lower temperatures.     

Preparation of ultra-fine Sm0.2Ce0.8O1.9 powder by a novel solid state reaction and fabrication of dense Sm0.2Ce0.8O1.9 electrolyte film

A novel solid state reaction was adopted to prepare Sm_0.2Ce_0.8O_1.9 (SDC) powder. A mixed oxalate Sm_0.2Ce_0.8(C₂O₄)_1.5·2H₂O was synthesized by milling a mixture of cerium acetate hydrate, samarium acetate hydrate, and oxalic acid for 5 h at room temperature. An ultra-fine SDC powder with the primary particle size of 5.5 nm was obtained at 300 °C. The ultra-low temperature for the formation of SDC phase was due to the atomic level mixture of the Sm³⁺ and Ce⁴⁺ ions. The crystal sizes of SDC powders at 300 °C, 550 °C, 800 °C, and 1050 °C were 5.5 nm, 11.4 nm, 24.1 nm and 37.5 nm, respectively. The sintering curves showed that the powder calcined at lower temperature was easier to be sintered owning to its smaller particle size. A solid oxide electrolytic cell (SOEC), comprising porous La_0.8Sr_0.2Cu_0.1Fe_0.9O_3−δ (LSCF) for substrate, LSCF–SDC for active electrode, SDC for electrolyte, and LSCF–SDC for symmetric electrode, was fabricated by dip-coating and co-sintering techniques. An extremely dense SDC film with the thickness of 20 μm was obtained at only 1200 °C, which was about 100–300 °C lower than the literatures׳ reports. The designed SOEC was proved to work effectively for decomposing NO (3500 ppm, balanced in N₂), 80% NO can be decomposed at 600 °C.     

Mechanical properties of (TixW1−x)C–Co cermet prepared by carbothermal reduction of high energy ball milled TiO2–WO3–C

A series of solid–solution carbides, (Ti_xW_1−x)C (x=0.9, 0.8, 0.7, 0.6), was prepared by the high-energy milling of TiO₂–WO₃–C mixtures via subsequent carbothermal reduction. With high-energy milling, only the size reduction of the constituent powders was apparent without any chemical reaction. The milled mixture powder was transformed to a single–phase (Ti_xW_1−x)C solid solution by heat treatment in a vacuum at 1200 °C. (Ti_xW_1−x)C–Co cermets were consolidated by isothermal sintering at 1300, 1400, and 1500 °C. The powders were fully densified by liquid-phase sintering at 1500 °C because the Co melted at 1430 °C. The mechanical properties of the (Ti_xW_1−x)C–Co cermet (H_v: ~24 GPa) were significantly better than those of the conventional WC–Co (H_v: ~13 GPa) or TiC–Co cermets (H_v: ~16 GPa). The use of a solid–solution carbide instead of conventional WC almost doubled its hardness values without a loss of toughness. It is indicated that the improved hardness of the (Ti_xW_1−x)C–Co cermet originates from the high hardness of (Ti_xW_1−x)C, and the solid–solution carbide would be a valuable substitute for conventional carbide cermets.     

Tape casting of new electrolyte and anode materials for SOFCs operated at intermediate temperature

An important task in SOFC research is the reduction of the operating temperature to 700 °C, to avoid premature ageing of the cell components and the use of expensive interconnect materials. This requires the development of new electrolytes and electrodes materials.Oxyapatite electrolytes have recently attracted considerable attention and we have already reported some interesting performances for the La₉Sr₁Si₆O_26.5 composition (σ = 8.8 × 10⁻³ S cm⁻¹ at 700 °C) [Beaudet Savignat, S., Lima, A., Barthet, C. and Henry, A., In Proceedings of the International Symposium Solide Oxide Fuel Cells VIII, Vol. 2003–2007, pp. 372–378].This study was centered on the manufacturing of an apatite electrolyte and a Ni/apatite cermet anode by the tape casting process, with a view to the development of anode/electrolyte 1/2 cells.Slurries compositions were first optimized to adjust green tapes characteristics. Secondly, we focused on the binder burnout and the sintering. Dense electrolytes were synthesized. The influence of the particle size of the apatite powder, with a fixed NiO powder particle size, and the influence of the addition of pyrolyzable organic particles on the sintering and the microstructure of the anode material were studied.     

Effect of NiO addition on properties of bulk yttria-doped ceria sintered from their spray pyrolyzed powder

Since a nickel-containing anode (Ni content of generally >40 vol%) and electrolytes are commonly co-fired at high temperature (>1200 °C) in solid oxide fuel cell (SOFC) manufacturing, if Ni diffuses toward the electrolyte, the effects of the NiO on the properties of the electrolyte become relatively important. In the present study, nickel was added directly into the electrolyte ceramic, 10 mol% yttria-doped ceria (10YDC), during powder preparation to investigate the effects of the presence of NiO on the related properties of YDC electrolyte. 10YDC ceramics were sintered from spray pyrolyzed powders with various amounts of nickel addition (≤15 at%). The phase of the resulting powders was identified as a mixture of YDC and NiO after calcination in air. The grain size of as-pyrolyzed YDC particles decreased as NiO addition increased; however, the grain size of sintered YDC composite was increased by a small addition of NiO. NiO is believed to dissolve in YDC at high temperature, but it exhibits negligible solubility at room temperature. The excess NiO tended to segregate at the grain boundaries and thereby retard the grain growth in YDC matrices. The ac impedance data revealed that the precipitated NiO may reduce the conduction activation energy of the YDC electrolyte, increasing the conductivity of the YDC composite.     

Performance evaluation of Sm0.5Sr0.5CoO3−δ fibers with embedded Sm0.2Ce0.8O1.9 particles as a solid oxide fuel cell composite cathode

Sm_0.2Ce_0.8O_1.9 (SDC)–embedded Sm_0.5Sr_0.5CoO_3?δ (SSC) composite fibers were successfully fabricated by electrospinning using commercial SDC nanopowders and an SSC precursor gel containing polyvinyl alcohol (PVA) and hydrated metal nitrate. After calcination of the composite fibers at 800 °C, the fibers of 300 ± 80 nm in diameter with a well-developed SSC cubic-perovskite structure and fluorite SDC were successfully obtained. An anode-supported single cell composed of NiO–Gd_0.2Ce_0.8O_1.9 (GDC)/GDC/SSC–SDC fibers was fabricated, and its electrochemical performance was evaluated. The maximum power densities were 1250 and 360 mW/cm² at 700 and 550 °C, respectively, which we ascribe to the excellent properties of the SSC fibers with embedded SDC particles such as a highly porous and continuous structure promoting mass transport and a charge transfer reaction.     

Rate enhancement of hydrogen generation through the reaction of magnesium hydride with water by MgO addition and ball milling

The variations of the amount of hydrogen generated with the kind of powders and the condition of the magnesium and magnesium hydride powders were investigated. By the reaction of Al, TiH₂ and unmilled and milled Mg powders with water, the H₂ generation rates were very low and the quantities of H₂ generated were extremely small. The quantity of H₂ generated by the reaction of unmilled MgH₂ powder with water was greater than those generated by the reactions of Al, TiH₂, and unmilled and milled Mg powders with water. The MgH₂ powder milled for 2 h, with finer particles, generated much more H₂ by its reaction with water than unmilled MgH₂ powder. The MgH₂ + 5%MgO powder milled for 2 h generated much more H₂ by its reaction with water than the Al, TiH₂, unmilled Mg, milled Mg, unmilled MgH₂, and milled MgH₂ powders.     

Comparison of Co/MgO and Ni/MgO catalysts for the steam reforming of naphthalene as a model compound of tar derived from biomass gasification

The catalytic performances of 12 wt.% Co/MgO catalyst pre-calcined at 873 K and of Ni catalysts for the steam reforming of naphthalene were investigated. The results of characterizations (TPR, XRD, and CO adsorption) for Ni catalysts showed that Ni metal particles were formed over the catalysts pre-calcined at 873 K with high Ni loading via reduction of NiO–MgO phases. A few Ni metal particles were obtained over the catalysts pre-calcined at 1173 K with all Ni loading values.The catalytic performance data showed that Co/MgO catalyst had higher activity (conv., 23%, 3 h) than any kinds of Ni/MgO catalysts tested in this study, under lower steam/carbon mole ratio (0.6) and higher concentration of fed naphthalene (3.5 mol%) than those used in the other works. The steam reforming of naphthalene proceeded when there was a stoichiometric ratio between the carbon atoms of naphthalene and H₂O over Co catalyst; however, the activation of excess H₂O happened over the Ni catalyst and this phenomenon can lead to having lower activity than Co catalyst. We concluded that these observations should be attributed to different catalytic performances between Co/MgO and Ni/MgO catalysts.     

Hydrothermal synthesis of nanocrystalline BaSnO3 using a SnO2·xH2O sol

A BaSnO₃ powder with a crystallite size of 27.6 nm has been prepared through a hydrothermal reaction of a peptised SnO₂·xH₂O and Ba(OH)₂ at 250 °C and the following crystallization of this hydrothermal product at 330 °C. The peptisation of the SnO₂·xH₂O gel is dependent on the pH value. Through peptisation the mean particle size of SnO₂·xH₂O in the aqueous solution has been decreased by a factor of 100 to 8 nm. A limited agglomeration in the sol-prepared powder has been observed under the microscope. The structure evolution and crystallisation behaviours of the sol-prepared powders were investigated by TG-DTA, IR and XRD. The BaSn(OH)₆ phase in the as-prepared powder transforms into an amorphous phase at 260 °C, from which the BaSnO₃ particles nucleate and grow with an increase in temperature. The single-phase BaSnO₃ powder has been obtained at a temperature as low as 330 °C. This sol-prepared powder is more sinter-reactive than the gel-prepared powder and can be sintered to a ceramic with 90.7% of the theoretic density.     

Aqueous processing of Ce0.8Sm0.2O1.9 green tapes

An aqueous tape casting of Ce_0.8Sm_0.2O_1.9 (SDC) ceramics was developed using poly(acrylic acid) (PAA) as dispersant, poly(vinyl alcohol) (PVA) as binder, poly(ethylene glycol) (PEG) as plasticizer, and deionized water as solvent. Surface properties of SDC powder with and without PAA dispersant were characterized by electrokinetic measurements. The rheology of the SDC slurries was evaluated with a rotary viscometer. The zeta potential measurement showed that the isoelectric point (IEP) for SDC powders in the absence of dispersant corresponds to a pH value of 3.66. The experimental results showed that the pH value greatly affects the rheology of the slurry. The optimum content to get a stable dispersed slurry is 2 wt% PAA in pH value range of 9–10. In presence of 2 wt% PAA dispersant, 55 wt% SDC powders exhibited shear thinning behavior, indicating that SDC slurry was homogenous and well stabilized. Homogeneous, smooth, and defect-free green tapes were successfully obtained by an appropriate slurry formula.     

Aluminum diboride synthesis from elemental powders by mechanical alloying and annealing

In this study, AlB₂ powders were synthesized by using a combined method of mechanical alloying (MA) and annealing of elemental aluminum (Al) and boron (B) powders. Milling was performed in a planetary ball-mill (Fritsch? Pulverisette 7 Premium Line) up to 15 h under argon (Ar) atmosphere. Annealing process was carried out in a tube furnace at 650 °C for 6 h under Ar atmosphere. The effects of MA durations on the annealing process and AlB₂ formation were investigated. The conversion of Al and B powders to AlB₂ starts after only MA for 3 h or after MA for 1 h and subsequent annealing. A slight formation of AlB₁₂ occurs at 242 °C for as-blended powders and it shifts to about 272 °C for MA’d powders. Al–B powder blends MA’d for 9 h and annealed have AlB₂ particles in size between 35 and 75 nm in the presence of Al₁₃Fe₄, Fe₃B and Fe₂B contaminations.     

Synthesis,characterization and use of synthesized fine zirconium diboride as an additive for densification of commercial zirconium diboride powder

Zirconium diboride (ZrB₂) was synthesized by a solution-based technique using zirconyl chloride (ZrOCl₂·8H₂O, ZOO), boric acid (H₃BO₃, BA) and gum karaya (GK) as the sources of zirconium, boron and carbon, respectively. The initial formation temperature of ZrB₂ was 1200 °C and complete conversion was achieved by 1400 °C. Preceramic precursors and as-synthesized ZrB₂ powders were characterized by XRD, TG-DTA, SEM, TEM, EDX and compared with commercial ZrB₂ powder made by carbothermic reduction. FT-IR of as-synthesized dried preceramic precursor revealed the formation of Zr–O–C and Zr–O–B whereas SEM showed agglomerated spherical particles with mean diameter of <1 µm. Commercial ZrB₂ and as-synthesized fine ZrB₂ powder were spark plasma sintered (SPS) at 1900 °C for 10 min. Addition of 10 wt% of synthesized fine powder improved the fired density from 87% to 93% of theoretical. A significant cost benefit arises for the utilization of cheap synthesized fine powder as an additive for the densification of the more expensive commercial powder.     

Microstructure and mechanical properties of hot pressed Al2O3/SiC nanocomposites

Al₂O₃/SiC micro/nano composites containing different volume fractions (5, 10, 15, and 20 vol.%) of SiC were prepared by mixing a sub-micron alumina powder with respective amounts of either micro- or nano-sized silicon carbide powders. The powder mixtures were hot pressed 1 h at 1740 °C and 30 MPa in the atmosphere of Ar. The effect of SiC addition on the microstructure and mechanical properties, i.e. hardness, fracture toughness, and room temperature flexural strength were investigated. The flexural strength increased with increasing volume fraction of silicon carbide particles. The maximum flexural strength (655 ± 90 MPa) was achieved for the composite containing 20 vol.% of coarse-grained SiC, which is more than twice as high as in the Al₂O₃ reference. Hardness and fracture toughness were also moderately improved. The observed improvement of mechanical properties is mainly attributed to alumina matrix grain refinement and grain boundary reinforcement.     

CO2-tolerant Ni-La5.5WO11.25-δ dual-phase membranes with enhanced H2 permeability

Enhancing the ambi-polar conductivity of the ceramic hydrogen permeable membrane by introducing an electron conductive metallic phase is quite effective, which is helpful for the hydrogen permeation flux improvement. To develop CO₂-tolerant hydrogen permeable membranes with better hydrogen permeability, Ni-La_5.5WO_11.25-δ (Ni-LWO) cermet membranes are fabricated. The alkaline earth metal-free ceramic LWO is used as the main proton-conductive phase and Ni is used as the main electron-conductive phase. The Ni-LWO membrane exhibits good chemical stability in CO₂-containing atmosphere since its hydrogen permeability maintains well in the measurement for about 180 h. Compared with the LWO ceramic membrane, the hydrogen permeability of the Ni-LWO membrane has been improved significantly. The Ni/LWO ratio has great impact on the performance of the cermet membrane. Meanwhile, among all the dual-phase Ni-LWO membranes with different Ni/LWO volume ratios, the membrane with 60 vol% Ni shows the highest hydrogen permeation flux of 0.18 ml min⁻¹ cm⁻² at 1000 °C when the feed gas contains 50% H₂.     

Phase evolution and crystallization in Si–B–C–N ceramics derived from a polyborosilazane precursor: microstructural characterization

Amorphous Si–B–C–N ceramic powder samples obtained by thermolysis of polyborosilazane {B[C₂H₄Si(H)NH]₃}_n were isothermally annealed at different temperatures (1400–1800 °C) and hold-times (3, 10, 30, 100 h). Scanning electron microscopy (SEM) of annealed powders as well as polished cross sections of large powder particles from selected samples were carried out to study surface morphology, crystallization and associated microstructural changes. Microstructural and phase evolution were additionally investigated using high-resolution transmission electron microscopy (HRTEM) and energy filtering TEM (EFTEM). Higher surface areas of the powders were found to promote vapor-phase decomposition reactions resulting in SiC whisker growth. In coarser powders the influence of surface is manifested as a skin-core effect, where the ‘skin’ has undergone a higher degree of decomposition accompanied by an increased SiC crystal growth, compared to the ‘core.’ Crystallization of SiC occurs already at 1400 °C, although Si₃N₄ crystallization occurs only at 1700 °C, after more than 3 h of annealing.