Synthesis of NiO-Deposited YSZ Composite Powders by Urea Hydrolysis

The urea hydrolysis method was used to prepare NiO-deposited YSZ composite powders. First, micrometer-sized YSZ particles were fabricated, and then the nanosized NiO particles were deposited on the surface of the YSZ particles. The microstructure of composite powders and the sintered bulk were further characterized with the aid of XRD, SEM, and TEM. The results indicated that the mesoporous and microsheet-like Ni(OH)₂· x H₂O ( x =0–1) crystals were deposited on the surface of YSZ particles. As the concentration of Ni²⁺ ion in the stock solution increased, the deposited NiO content and thickness of NiO layer on the YSZ particle surface also increased. In addition, the YSZ particle size showed significant influence on the microstructure and conductivity of Ni/YSZ cermet anode produced by NiO-deposited YSZ composite powders. Such NiO-deposited YSZ composite powders can be easily sintered to form a continuous NiO network.     

Preparation of Matrix-Type Nickel Oxide/Samarium-Doped Ceria Composite Particles by Spray Pyrolysis

Matrix-type nickel oxide (NiO)/samarium-doped ceria (SDC) composite particles, in which NiO and SDC nano-particles were homogeneously dispersed, were synthesized by spray pyrolysis (SP) for an anode precursor of intermediate-temperature solid oxide fuel cells (IT-SOFCs). SP of an aqueous solution containing Ni, Ce, and Sm salts resulted in capsule-type composite particles that had NiO enveloped with SDC. The capsule-type composite particles actually prevent Ni aggregation between particles, but they cannot have a large contact area between nickel (Ni) and SDC. A matrix-type composite particle is expected to have a large contact area because the matrix-type composite is comprised of nanometer-sized Ni and SDC particles. An adequate addition of ethylene glycol successfully resulted in matrix-type NiO/SDC composite particles. The matrix-type composite particles also showed higher anode performance than the capsule-type composite particles in these experiments and they were effective as precursors of high-performance IT-SOFC anodes.     

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.     

Synthesis of CoO/Ni Composite Powders for Molten Carbonate Fuel Cells

CoO/Ni composite particles were prepared by the advanced mechanical-coating method called Mechanofusion™. These composite particles were composed of nickel particles uniformly covered with fine CoO particles. A new cathode structure for molten carbonate fuel cells (MCFCs), where the NiO core was coated with an outer layer of lithiated cobalt and nickel solid-solution oxide (Li(Co,Ni) oxide), was formed by oxidation and lithiation using these CoO/Ni composite particles. The solubility of nickel in this Li(Co,Ni) oxide layer into carbonate melt decreased to two-thirds of that of NiO when used as a cathode for MCFCs.     

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.     

阳极Ni–YSZ添加CeO2对固体氧化物燃料电池性能的影响

采用直接加入CeO2粉和通过Ce（NO3）3溶液包裹NiO粉2种方式对阳极Ni–氧化钇稳定型氧化锆（yttria stabilized zirconia,YSZ）进行修饰,分别研究其对固体氧化物燃料电池（solid oxide fuel cell,SOFC）性能的影响,并与不添加CeO2的电池进行对比研究。以氢气为燃料气、在750℃对单电池进行电性能测试,采用X射线衍射仪、场发射扫描电镜和能谱仪对阳极的物相组成和断面形貌进行表征,通过透射电镜观察CeO2对NiO颗粒的包裹形貌。结果表明：通过Ce（NO3）3包裹NiO粉的方法所制备的电池,最大功率密度为0.938W/cm2。其添加的CeO2能有效地阻止Ni颗粒烧结,增强Ni在YSZ网络结构表面的分散,提高电池性能。     

Electrochemical Performance of a Ni and YSZ Composite Synthesised by Ultrasonic Spray Pyrolysis as an Anode for SOFCs

The electrochemical performance of an anode material for a solid oxide fuel cell (SOFC) depends highly on microstructure in addition to composition. In this study, a NiO–yttria‐stabilised zirconia (NiO–YSZ) composite with a highly dispersed microstructure and large pore volume/surface area has been synthesised by ultrasonic spray pyrolysis (USP) and its electrochemical characteristics has been investigated. For comparison, the electrochemical performance of a conventional NiO–YSZ is also evaluated. The power density of the zirconia electrolyte‐supported SOFC with the synthesised anode is ∼392 mW cm^–2 at 900 °C and that of the SOFC with the conventional NiO–YSZ anode is ∼315 mW cm^–2. The improvement is ∼24%. This result demonstrates that the synthesised NiO–YSZ is a potential alternative anode material for SOFCs fabricated with a zirconia solid electrolyte.     

The sonochemical preparation of a mesoporous NiO/yttria stabilized zirconia composite

A sonochemical process for the fabrication of the mesoporous composite NiO/yttria stabilized zirconia (YSZ) is described. Its surface area after the extraction of the surfactant is 193 m²/g for a sample containing 40 atom-% Ni. The main advantages of the sonochemical method, as compared with previous works, are the short reaction time (6 h) and that there is no requirement for the glycolation of the nickel, yttrium, and zirconium ions. The reduction of NiO/YSZ to the corresponding Ni/YSZ is also reported.     

Quasi-static compression behavior of nickel oxide,nickel oxide:zirconia,nickel:zirconia and nickel foams

An effective material for use in shock mitigation should spread the deflection of the shock wave over a longer period of time and should minimize the force felt by the object under impact. Ductile or brittle cellular materials are currently gaining importance due to their unique high energy absorption characteristics. Reticulated cellular foam structures of nickel oxide (NiO) and nickel oxide:zirconia (NiO:YSZ 60:40 percentage by wt.) were fabricated by polymeric sponge replication process. These foams are reduced under hydrogen atmosphere to produce metallic nickel (Ni) and nickel:zirconia (Ni:YSZ) cermet foams, respectively. X-ray diffraction studies on the struts confirmed the corresponding phase formation. Further, the volume fraction of the solid in foam is estimated through image analysis. All the foams are subjected to uni-axial compression and the stress–strain curves were recorded. A comparative evaluation of progressive deformation behavior at room temperature was also carried out. Stress–strain curve of the nickel foam shows distinctly three regimes under compression, a deformation regime showing a linear dependence in the strain with stress. This is followed by a second region showing a plateau corresponding to the energy absorption resulting from the permanent plastic deformation while retaining the integrity and finally densification region through the wall collapse resulting in the maximum compressive strength. Stress–strain curves of all other foams such as NiO, NiO:YSZ and Ni:YSZ has demonstrated a similar fracture behavior under compression which caused not only by unstable crack propagation originating from a single crack, but also by merging of many cracks leading to the formation of the crushed zone. Compressive strength is found to be a strong function of solid fraction supporting the load and percentage porosity of NiO foams. Estimation of relative energy absorption has exhibited higher energy absorption irrespective of the material of construction at higher strain rates.     

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.     

Toughening and strengthening zirconia through the addition of a transient solid solution additive

A very small amount of nickel oxide (NiO), 0.18 mol%, could dissolve into yttria-stabilized zirconia (YSZ) during sintering in air at elevated temperature. The presence of Ni solutes enhances both the densification and grain growth of YSZ specimens. By heat-treating the NiO-doped YSZ specimen in a reducing atmosphere, nano-sized Ni particles are produced at the grain boundaries. The NiO thus acts as a transient solid solution additive for the YSZ-Ni nanocomposite. The formation of Ni nano-particles introduces an extra ferromagnetic performance into the YSZ specimen. Furthermore, the toughness and strength of YSZ are enhanced respectively by 120% and 40%. The toughness enhancement shows strong dependence on the size of ZrO₂ grains. Nevertheless, the strengthening is contributed by many factors.     

Characterization of Nickel Ions in Nickel‐Doped Yttria‐Stabilized Zirconia

The distribution of Ni²⁺ ions in NiO‐doped 10YSZ powder is examined with Superconducting Quantum Interference Device magnetometry, a technique that is able to distinguish between randomly distributed Ni²⁺ ions in solid solution and ordered Ni²⁺ ions within NiO with high precision. Very high purity powders containing 0.01, 0.1, 0.5, and 1.0 mol% NiO in 10YSZ (all levels below the solid solubility limit of NiO in 10YSZ) were made from acetate precursors and a modified EDTA (ethylenediaminetetraacetic acid)‐citrate synthesis method. The powders were calcined in air at either 873 or 1273 K. The 873 K calcination leads to single phase YSZ particles about 10 nm in diameter, and almost all of the NiO dopant exists in complete solid solution. The 1273 K calcination leads to a larger YSZ particle size (55–95 nm), and also to the formation and/or growth of NiO particles, the amount of which depends on the length of time of calcination. Upon sintering the powders in air (1773 K, 1 h), the NiO dissolves back into 10YSZ. The results demonstrate that particle growth during calcination leads to the exsolution of Ni²⁺ ions to form NiO. This has important implications for the synthesis of NiO‐doped 10YSZ from chemical precursors.     

Microstructural characterization of spray-dried NiO-8YSZ particles as plasma sprayable anode materials for metal-supported solid oxide fuel cell

The plasma spray method is widely used to produce NiO-8YSZ (composed of nickel oxide (NiO) and 8 mol% yttria-stabilized zirconia) anode layers in metal-supported solid oxide fuel cell (SOFC). Flowability control of microsized particles is important for achieving consistent performance of the SOFC anode layer. When microsized particles are fabricated via spray drying and sintering, the most significant factors that influence flowability are their sizes, distribution, and surface conditions. Thus, the aim of this study is to analyze the fabrication conditions for microsized NiO-8YSZ cermet particles made from a nanoscale, sinterable NiO-8YSZ dispersion solution by using an appropriate spray-drying and sintering process. The characteristics of the as-sprayed and sintered NiO-8YSZ composite particles (such as size, distribution, roughness, and nanostructure) were analyzed via field emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS), particle size distribution (PSD), Brunauer–Emmett–Teller (BET) surface area, and atomic force microscopy (AFM). The as-sprayed microsized NiO-8YSZ particles became smaller and more uniformly distributed as the rotational speed used for spray drying increased. As a result of sintering, the extent of shrinkage of as-sprayed microsized NiO-8YSZ particles generated at high RPMs was lower than that of particles formed at low RPMs. No significant difference was observed in the distribution of the nanosized NiO and 8YSZ particles at different rotational speeds. Furthermore, the highest BET surface areas were observed for particles generated at 8000 RPM before sintering at 13.74 m²/g. After sintering, the highest BET surface area was 0.94 m²/g for particles generated at 16,000 RPM. Differences in nanostructure and surface roughness between as-sprayed and sintered microsized NiO-8YSZ particles were identified via AFM. This study is expected to provide important fundamental information useful for optimizing SOFC efficiency by promoting flowability control during the production of SOFC anodes via plasma spraying.     

Hardening effect induced by incorporation of SiC particles in nickel electrodeposits

Pure Ni and nickel matrix composite electrocoatings containing micron- and nano-SiC particles (1 μm and 20 nm respectively) were produced under direct and pulse current conditions from an additive-free Watts type bath. The effect of the particle size, codeposition percentage of SiC and type of imposed current on the microhardness as well as on the microstructure of the electrodeposits were investigated. Ni/SiC composite deposits prepared under either direct or pulse current conditions exhibited a considerable strengthening effect with respect to pure Ni coatings. The improved hardness of composite coatings was associated to specific structural modifications of Ni crystallites provoked by the adsorption of H⁺ on the surface of SiC particles, thus leading to a (211) texture mode of Ni crystal growth. Pulse electrodeposition significantly improved the hardness of the Ni/SiC composite coatings, especially at low duty cycles, in which grain refinement and higher SiC incorporation (vol. %) was achieved. The enhanced hardness of Ni/nano-SiC deposits, as compared to Ni/micron-SiC composites, was attributed to the increasing values of the number density of embedded SiC particles in the nickel matrix with decreasing particle size. In addition, the observed hardening effects of the SiC particles might be associated to the different embedding mechanisms of the particles, which could be characterized as inter-crystalline for micron-SiC and partially intra-crystalline for nano-SiC particles.     

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.     

浆料成分对NiO电极微观结构的影响

分别采用NiO浆料、Ni浆料和Ni/YSZ浆料制备NiO敏感电极.其中Ni/YSZ浆料是由在Ni浆料中添加15vol％ YSZ粉末制备的.结果表明,采用NiO浆料普通烧结得到的NiO电极致密且有裂纹;采用Ni浆料和Ni/YSZ浆料反应烧结分别制备的NiO电极和NiO/YSZ复合电极则疏松多孔且无裂纹.浆料中添加的YSZ不仅能够细化NiO电极晶粒,同时能增强电极和基底的界面附着,增加三相界面的数量和长度.     

Ni–Nb–O mixed oxides as highly active and selective catalysts for ethene production via ethane oxidative dehydrogenation. Part I: Characterization and catalytic performance

This work demonstrates the high potential of a new class of catalytic materials based on nickel for the oxidative dehydrogenation of ethane to ethylene. The developed bulk Ni–Nb–O mixed oxides exhibit high activity in ethane ODH and very high selectivity (∼90% ethene selectivity) at low reaction temperature, resulting in an overall ethene yield of 46% at 400 °C. Varying the Nb/Ni atomic ratio led to an optimum catalytic performance for catalysts with Nb/Ni ratio in the range 0.11–0.18. Detailed characterization of the materials with several techniques (XRD, SEM, TPR, TPD-NH₃, TPD-O₂, Raman, XPS, electrical conductivity) showed that the key component for the excellent catalytic behavior is the Ni–Nb solid solution formed upon the introduction of niobium in NiO, evidenced by the contraction of the NiO lattice constant, since even small amounts of Nb effectively converted NiO from a total oxidation catalyst (80% selectivity to CO₂) to a very efficient ethane ODH material. An upper maximum dissolution of Nb⁵⁺ cations in the NiO lattice was attained for Nb/Ni ratios ⩽0.18, with higher Nb contents leading to inhomogeneity and segregation of the NiO and Nb₂O₅ phases. A correlation between the specific surface activity of the catalysts and the surface exposed nickel content led to the conclusion that nickel sites constitute the active centers for the alkane activation, with niobium affecting mainly the selectivity to the olefin. The incorporation of Nb in the NiO lattice by either substitution of nickel atoms and/or filling of the cationic vacancies in the defective nonstoichiometric NiO surface led to a reduction of the materials nonstoichiometry, as indicated by TPD-O₂ and electrical conductivity measurements, and, consequently, of the electrophilic oxygen species (O⁻), which are abundant on NiO and are responsible for the total oxidation of ethane to carbon dioxide.     

Development of Ni–YSZ cermet anode for solid oxide fuel cells by electroless Ni coating

Nickel–Yttria-stabilized zirconia (Ni–YSZ) cermet (ceramic–metal composite) anodes have been prepared from a simple electroless Ni bath without hypophosphite. Ni–YSZ powder having varying amounts of Ni has been prepared. The effect of two different reducing agents has been evaluated with respect to stability of the bath. Hydrazine can be effectively used as a reducing agent up to 30 vol.% Ni. However beyond 30% Ni, the hydrazine bath loses its stability. Formaldehyde is found to be a very effective reducing agent for higher Ni concentration. The Ni–YSZ powder obtained is characterized by SEM and XRD. When the powder is oxidized for calculating actual amount of Ni deposited, it turns to complete green due to the formation of NiO. The XRD results also show distinct peaks of NiO. The powder is pressed and sintered in air and reduced in hydrogen atmosphere to convert NiO back to Ni. The sintered microstructure shows a well-defined network of Ni around YSZ particles and the fracture surface shows porosity. These features indicate the effectiveness of the technique in producing the essential microstructural elements necessary for effective functioning of the anode.     

Synthesis of NiO-YSZ composite particles for an electrode of solid oxide fuel cells by spray pyrolysis

NiO-YSZ (YSZ: Y₂O₃-stabilized ZrO₂) composite particles for a Ni-YSZ cermet anode in solid oxide fuel cells (SOFCs) were synthesized via spray pyrolysis (SP). The formation mechanism of the composite particles by this process was analyzed. The internal microstructure of the particles synthesized during SP processing was observed at each heating temperature of 200, 300, 400 and 1000 °C, and then the formation mechanism of the composite structure was discussed. As a result, it was found that NiO-YSZ composite particles were formed through the following steps. Firstly, during the evaporation stage up to 200 °C, a filled particle with Ni(CH₃COO)₂ and YSZ fine grains were formed from the atomized droplet containing Ni ion and dispersed YSZ sol by volume precipitation. Secondly, during the continuous thermolysis stage up to 400 °C, YSZ grains were formed and moved to the surface of the composite particle by the outgas and the oxidation of Ni(CH₃COO)₂. Finally, the NiO-YSZ composite particle that has NiO grains uniformly covered with fine YSZ grains was formed after the final sintering stage up to 1000 °C.     

Structure and conductivity of NiO/YSZ composite prepared via modified glycine-nitrate process at varying sintering temperatures

Nickel oxide and Yttria-stabilized zirconia (NiO/YSZ) composite is one of the most promising mixed conducting electrode materials in both solid oxide electrolysis cell and solid oxide fuel cell applications. In this study, 50 wt% NiO and 50 wt% YSZ composite was synthesized via a modified glycine-nitrate combustion process (GNP) and the effect of sintering temperatures (1100 °C, 1300 °C and 1500 °C) on its microstructure and electrical properties were investigated. TG/DTA and in-situ high temperature XRD revealed the thermal property behavior and the structural changes of the as-combusted precursor material. For all the samples sintered at different temperatures, room temperature XRD patterns revealed a distinct cubic phases of both YSZ and NiO while SEM images showed a porous microstructure. The total conductivities at 700 °C are 9.87 × 10⁻³, 5.26 × 10⁻³, 4.02 × 10⁻³ S/cm for the 1100, 1300, and 1500 °C with activation energies of 0.1722, 0.3555, and 0.3768 eV, respectively. Conductivity measurements of the different sintered samples revealed that the total conductivities as well as the activation energies are greatly affected by different sintering temperatures.