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.     

Synthesis and thermoelectric performance of Li-doped NiO ceramics

Ni_1?xLi_xO (x = 0, 0.03, 0.06, 0.09) powders were prepared by sol–gel method combined with sintering procedure using Ni(CH₃COO)₂·4H₂O and citric acid as the raw materials and alcohol as solvent. The crystal structures of the samples were investigated by X-ray diffraction and Raman spectroscopy. The thermoelectric properties, such as the electrical conductivity, the Seebeck coefficient and the thermal conductivity were measured. The results showed that all the samples are p-type semiconductors. The electrical conductivity increases with the increase of the temperature, which indicates that the substitution of Li⁺ for Ni²⁺ can increase the concentrations and mobility of the carriers. The thermal conductivity decreases remarkably with the increase of the Li doping content, which indicates that Li doping can enhance the scattering of phonon. However, the Seebeck coefficient will decline with the increase of the Li doping content. As results of the increase of electrical conductivity and reduction of thermal conductivity, Li doping can increase the figure of merit (ZT) of NiO, the ZT value reach 0.049 at 770 K for Ni_1?xLi_xO with x = 0.06.     

Sinterability,microstructures and electrical properties of Ni/Sm-doped ceria cermet processed with nanometer-sized particles

Ni/Sm-doped ceria (SDC) cermet was prepared from two types of NiO/SDC mixed powders: Type A—Mechanical mixing of NiO and SDC powders of micrometer-sized porous secondary particles containing loosely packed nanometer-sized primary particles. The starting powders were synthesized by calcining the oxalate precursor formed by adding the mixed nitrate solution of Ce and Sm or Ni nitrate solution into oxalic acid solution. Type B—Infiltration of Ni(NO₃)₂ solution into the SDC porous secondary particles subsequently freeze-dried. Type B powder gave denser NiO/SDC secondary particles with higher specific surface area than Type A powder. The above two types powders were sintered in air at 1100–1300 °C and annealed in the H₂/Ar or H₂/H₂O atmosphere at 400–700 °C. Increased NiO content reduced the sinterability of Type A powder but the bulk density of Type B powder compact showed a maximum at 34 vol.% NiO (25 vol.% Ni). Type B cermet was superior to Type A cermet in achieving fine-grained microstructure and a homogeneous distribution of Ni and SDC grains. The electrical resistance of the produced cermet decreased drastically at 15 vol.% Ni for Type B and at 20 vol.% Ni for Type A.     

Synthesis and electrical properties of Ce1−xGdxO2−x/2 (x = 0.05–0.3) solid solutions prepared by a citrate–nitrate combustion method

Ce_1?xGd_xO_2?x/2 (GDC) powders with different Gd³⁺ contents (x = 0.05–0.3) were prepared by a simple citrate–nitrate combustion method. The influence of the Gd³⁺ doping content on the crystal structure and the electrical properties of GDC were examined. Many analysis techniques such as thermal analysis, X-ray diffraction, nitrogen adsorption analysis, scanning electron microscopy and AC impedance analysis were employed to characterize the GDC powders. The crystallization of the GDC solid solution occurred below 350 °C. The GDC powders calcined at 800 °C showed a typical cubic fluorite structure. The lattice parameter of GDC exhibited a linear relationship with the Gd³⁺ content. As compared with that sintered at other temperatures, the GDC pellet that sintered at 1300 °C had a high relative density of 97%, and showed finer microstructure. The conductivity of GDC was firstly increased and then decreased with the increase of the Gd³⁺ content. The sintered GDC sample with the Gd³⁺ content of 0.25 exhibited the highest conductivity of 1.27 × 10^?2 S cm^?1 at 600 °C.     

Fabrication and evaluation of NiO/Y2O3-stabilized-ZrO2 hollow fibers for anode-supported micro-tubular solid oxide fuel cells

In this work NiO/3 mol% Y₂O₃–ZrO₂ (3YSZ) and NiO/8 mol% Y₂O₃–ZrO₂ (8YSZ) hollow fibers were prepared by phase-inversion. The effect of different kinds of YSZ (3YSZ and 8YSZ) on the porosity, electrical conductivity, shrinkage and flexural strength of the hollow fibers were systematically evaluated. When compared with Ni–8YSZ the porosity and shrinkage of Ni–3YSZ hollow fibers increases while the electrical conductivity decreases, while at the same time also exhibiting enhanced flexural strength. Single cells with Ni–3YSZ and Ni–8YSZ hollow fibers as the supported anode were successfully fabricated showing maximum power densities of 0.53 and 0.67 W cm⁻² at 800 °C, respectively. Furthermore, in order to improve the cell performance, a Ni–8YSZ anode functional layer was added between the electrolyte and Ni–YSZ hollow fiber. Here enhanced peak power densities of 0.79 and 0.73 W cm⁻² were achieved at 800 °C for single cells with Ni–3YSZ and Ni–8YSZ hollow fibers, respectively.     

Effect of composition on the structural development and electrical conductivity of NiO-GDC composites obtained by one-step synthesis

NiO-C_0.9Gd_0.1O_1.95 (NiO-GDC) composites obtained using a chemical route (one-step synthesis) were characterized by thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy (between 300 and 650 °C in air). Rietveld refinement of XRD data indicated that synthesized powders are ultrafine and the crystallite size of the GDC phase decreases with increasing NiO content. The relative density of sintered samples is influenced by the NiO content, but easily brought to values above 95% after sintering at 1450–1500 °C. NiO-GDC composites exhibited homogeneous phase distribution and grain size often lower than 1 µm. With 30–40 wt% NiO this phase dominates the overall electrical conductivity of NiO-GDC. The combination of grain size, conductivity and microstructural characteristics shows the efficacy of the adopted processing route to obtain high quality Ni-GDC cermet precursors.     

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.     

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.     

One-step synthesis of Li-doped NiO as high-performance anode material for lithium ion batteries

The poor electronic conductivity and huge volume expansion of NiO are the vital barriers when used as anode for lithium ion batteries. In order to solve above issues, Li-doped NiO are prepared by a facile one-step ultrasonic spray pyrolysis method. The effects of Li doping on the morphology, structure and chemical composition of the Li-doped NiO powders are extensively studied. When used as lithium ion batteries anode, it is demonstrated that the doping of Li has significant positive effect on improving the electrochemical performance. After 100 cycles at 400 mA g⁻¹, The Li-doped NiO samples deliver a discharge capacity of 907 mAh g⁻¹, much more than that of un-doped sample (736 mAh g⁻¹). The improved electrochemical performances can be ascribed to the improved p-type conductivity and lower impedance, which are confirmed by Rietveld refinement, X-ray photoelectron spectroscopy and electron impedance spectroscopy.     

Electrochemical performance of intermediate temperature micro-tubular solid oxide fuel cells using porous ceria barrier layers

We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce_0.9Gd_0.1O_2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr_0.92Y_0.16O_2.08; LSCF: La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H₂ as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm⁻² at 650 °C and about 700 mW cm⁻² at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.     

Electrochemical performance of Ni1−xFex–Ce0.8Gd0.2O1.9 cermet anodes for solid oxide fuel cells using hydrocarbon fuel

Ni_1?xFe_x bimetallic-based cermet anodes were investigated for hydrocarbon-fueled solid oxide fuel cells. Ni_1?xFe_x–Ce_0.8Gd_0.2O_1.9 cermet anodes were synthesized using a glycine nitrate process, and their electrical conductivity and the amount of carbon deposits were found to decrease with increasing Fe content. The anode polarization resistance for the CH₄ fuel was significantly reduced by Fe alloying, which was strongly related to the carbon deposition behavior. The maximum power density of the single cell with Ni_0.85Fe_0.15–Ce_0.8Gd_0.2O_1.9 in CH₄ at 800 °C was 0.27 W/cm². Fe alloying significantly improved the electrochemical performance of solid oxide fuel cells in CH₄ fuel by suppressing carbon deposition.     

Synthesis of La1−xSrxMO3 (M = Mn,Fe, Co,Ni) nanopowders by alanine-combustion technique

La_1?xSr_xMO₃ (M = Mn, Fe, Co, Ni, x = 0–0.3) powders were obtained by solution combustion technique using metal nitrates and α-alanine. The as-prepared powders, resulted by the combustion reaction, were annealed at different temperatures to investigate the evolution of crystalline phases. For the strontium-doped lanthanum-based perovskites, higher annealing temperatures than for the corresponding pure lanthanum-based perovskites are needed to obtain single-phase compounds depending on M-site metal and strontium content. The oxide powders were investigated by FT-IR spectra, X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific area measurements. Based on our results we propose different mechanisms for La_1?xSr_xMO₃ (M = Mn, Fe, Ni, x = 0–0.3) obtaining, depending on the intermediary compounds formed in the combustion reaction or during the thermal treatment of the as-prepared powders.     

Effect of NiO additive on microstructure,mechanical behavior and electrical properties of 0.2PZN–0.8PZT ceramics

A NiO-added Pb((Zn_1/3Nb_2/3)_0.20(Zr_0.50Ti_0.50)_0.80)O₃ system is prepared and investigated. The results reveal that Ni doping induces a phase transformation from the morphotropic phase boundary to the tetragonal phase side. Above the solubility limit of 0.3 wt% in NiO form, excess Ni ions segregate at the grain boundaries and triple junctions, which facilitate the formation of a liquid phase with excess PbO and lead to remarkable grain growth. The mechanical behavior (Vickers hardness (H_v) and fracture toughness (K_IC)) can be tailored by controlling the content of additive; this is accompanied by a transition in the fracture mode changed from transgranular without NiO additive to intergranular with 1.0 wt% NiO additive. Moreover, the NiO addition weakens the dielectric relaxor behavior and improves the piezoelectric properties simultaneously. The 0.2PZN–0.8PZT with 0.5 wt% NiO addition shows good transduction coefficient (d₃₃·g₃₃ = 10,050 × 10^?15 m²/N) and large fracture toughness (K_IC = 1.35 MPa m^1/2).     

Electrolyte materials for solid oxide fuel cells derived from metal complexes: Gadolinia-doped ceria

Gadolinia doped ceria (GDC) powders with different gadolinium contents were successfully prepared by the thermal decomposition of ceria complexes. All the calcined powder samples were found to be ceria-based solid-solutions having a fluorite-type structure. The powders were cold-isostatically pressed and sintered in air at 1500 °C for 5 h to attain a sintered density of about 90% of its theoretical value. The electrical conductivity of the GDC pellets in air was studied as a function of temperature in the 225–700 °C range, by using two-probe electrochemical impedance spectroscopy measurements. The highest total conductivity (σ_600 °C = 0.025 S/cm) was found for the Ce_0.85Gd_0.15O_1.925 composition.     

Characterization of core-shell structured Ni@GDC anode materials synthesized by ultrasonic spray pyrolysis for solid oxide fuel cells

Core-shell structured NiO@GDC powders with NiO cores and GDC shells were synthesized by ultrasonic spray pyrolysis (USP) with a four-zone furnace. The morphology of the as-synthesized powders can be modified by controlling parameters such as the precursor pH, carrier gas flow rate, and zone temperature. At high carrier gas flow rates, the as-synthesized core-shell structured NiO@GDC powders have raisin-like morphology with a rough surface; this is due to fast gas exhaustion and insufficient particle ordering. The core-shell structured Ni@GDC anode showed considerable electrochemical performance enhancement compared to the conventionally-mixed Ni-GDC anode. The polarization resistance (R_p) of conventionally-mixed Ni-GDC anodes increases gradually as a function of the operation time. Alternatively, the core-shell structured Ni@GDC anode synthesized by USP does not exhibit any significant performance degradation, even after 500 h of operation. This is the case because the rigid GDC ceramic shell in the core-shell structured Ni@GDC may restrain Ni aggregation.     

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.     

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.     

Ionic–gelation synthesis of gadolinium doped ceria (Ce0.8Gd0.2O1.90) nanocomposite powder using sodium-alginate

Nanocomposite powders of gadolinium-doped ceria (GDC, Ce_0.8Gd_0.2O_1.9) were synthesized via thermal treatment of the gel formed by contacting ionic solutions of sodium alginate as the jelling template and metal (gadolinium/cerium) nitrates as the starting material. The influence of calcination temperature and sodium alginate loading fraction on the properties of the synthesized GDC nanocomposite powders was investigated. Characterization was performed by energy dispersive X-ray spectroscopy, powder X-ray diffraction, thermogravimetric analysis, Field Emission Scanning Electron Microscopy, Fourier transformed infrared spectroscopy and nitrogen adsorption/desorption analysis. It was observed that the particle size and the surface area of the produced GDC nanocomposite powders are dominantly controlled by the calcination temperature, while the effect of sodium alginate loading fraction is limited by the range of the calcination temperature. In this study, the smallest mesoporous GDC nanocomposite powder with cubic fluorite structure (8 nm crystallite size and 3.05±0.005 m²/g surface area) was synthesized using 2 wt% of sodium alginate at a calcination temperature of 550 °C (for 4 h). The results of this study could help to perceive the influence of the basic processing variables on the particle size and the other physiochemical properties of GDC nanocomposite powders produced by the ionic-gelation method.     

Electrochromic properties of Al doped B-subsituted NiO films prepared by sol–gel

In this paper, Al doped B-substituted NiO films were prepared by sol–gel method. The effect of the Al content on the structure of the Al_xB_0.15NiO films were studied with X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical and EC properties were examined by cyclic voltammetric (CV) measurements and UV–Vis spectrophotometry, respectively. Al doping could prevent the crystallization of the films, which exhibited much better electrochemical and electrochromic properties than undoped samples. The bleached state absorbance could be significantly lowered when the Al added. EC efficiencies measured at λ = 500 nm of the films with different Al doping content reach ～30 cm² C^?1, with a change in transmittance up to 70%.     

Enhanced electrochemical activity and long-term stability of Ni–YSZ anode derived from NiO–YSZ interdispersed composite particles

Nickel oxide–yttira stabilized zirconia (NiO–YSZ) interdispersed composite (IC) particles were prepared by a mechanochemical processing using NiO and YSZ nanoparticles. Transmission electron microscopy (TEM) revealed that primally particles of YSZ (75 nm) and NiO (160 nm) were presented alternatively in the composite particles. Specific surface area (SSA) decreased from 8.6 to 7.1 m²/g during the mechanochemical processing. The SSA reduction suggested that the chemically bound NiO/YSZ hetero-interfaces were formed during the processing. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) visualized that the anode made from the IC particles consisted of three-dimensional textured structure of fine Ni and YSZ networks (grain size of them was approximately 500 nm) with 34 vol% of porosity. The anode demonstrated not only low polarization of 152 mV at 1 A/cm² even under the operation at 700 °C but also long-term stability for 920 h.