Design and Optimization of Composite Electrodes in Solid Oxide Cells

The performance of solid oxide cells (SOCs) heavily relies on the population of three‐phase boundaries (TPBs) in the composite electrodes. In this study, SOC composite electrodes are described by percolating binary particle aggregates that are constructed from random loose packing models and classical sintering theories. Summed perimeters of the sintering necks represent the total TPB lengths. A case study has been carried out on lanthanum strontium manganite (LSM)–yttria‐stabilized zirconia (YSZ) composite electrodes. By employing three‐dimensional data that are converted from relevant two‐dimensional data, the TPB length of baseline LSM–YSZ electrodes investigated in this study is 35.4 μm μm^–3. The parametric and sensitivity analyses show the changes of TPB lengths in functions of the weight fraction of powders, particle size and particle size ratio of powders, void fraction of electrodes, and density of materials. In the case of baseline LSM–YSZ electrodes, proper electrode design and optimization would result in 2–3 times of the enlargement of TPBs. Technical guidelines on the design and optimization of SOC composite electrodes are proposed.     

Planar Metal‐Supported SOFC with Novel Cermet Anode

Metal‐supported solid oxide fuel cells are expected to offer several potential advantages over conventional anode (Ni‐YSZ) supported cells. For example, increased resistance against mechanical and thermal stresses and a reduction in material costs. When Ni‐YSZ based anodes are used in metal supported SOFC, elements from the active anode layer may inter‐diffuse with the metallic support during sintering. This work illustrates how the inter‐diffusion problem can be circumvented by using an alternative anode design based on porous and electronically conducting layers, into which electrocatalytically active materials are infiltrated after sintering. The paper presents the electrochemical performance and durability of the novel planar metal‐supported SOFC design. The electrode performance on symmetrical cells has also been evaluated. The novel cell and anode design shows a promising performance and durability at a broad range of temperatures and is especially suitable for intermediate temperature operation at around 650 °C.     

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.     

Performance evolution of NiO/yttria-stabilized zirconia anodes fabricated at different compaction pressures

Nickel oxide (NiO)/yttria-stabilized zirconia (YSZ) anode substrates were fabricated at four compaction pressures, 70, 200, 500 and 1000 MPa, the particle size distributions of NiO and YSZ were investigated with the powders treated at different compaction pressures, and the effects of compaction pressure on the performance of anodes with and without pore-formers were investigated by studying the effects of compaction pressure on the sintering shrinkage, compaction density, sintered density and electrical conductivity of anodes and the performance of cells. Experimental results demonstrated that the mismatch in the sintering shrinkages of YSZ films and the anodes compacted at 70 and 1000 MPa caused gas leakage across the films and thus a higher local temperature than the furnace temperature. The single cell with the anode using pore-former and compacted at 500 MPa exhibited the best output performance of 2.66 W cm⁻² at 800 °C.     

Effect of alumina addition on initial sintering of cubic ZrO2 (8YSZ)

The effect of 0–10 wt% alumina addition on the initial sintering of 8 mol% Y₂O₃ cubic ZrO₂ (8YSZ) was studied. Activation energy and initial stage of sintering mechanism were analyzed in order to understand the effect of the alumina in the sintering process. The analysis was carried out using the analytical method for constant rate heating (CRH). The activation energy decreased from 716 to 599 kJ/mol for undoped 8YSZ to 2.16 wt% of alumina–8YSZ, respectively. The mechanism for the initial stage of sintering for <2.16% Alumina–8YSZ changed from grain boundary diffusion (GBD) to volumetric diffusion (VD). With 10 wt% of alumina, the activation energy increased to 854 kJ/mol which was thought due to the change in the initial stage of sintering mechanism from VD to GBD.     

Synthesis and characterisation of macroporous Yttria Stabilised Zirconia (YSZ) using polystyrene spheres as templates

Yttria Stabilised Zirconia (YSZ) is commonly used as an oxygen sensor and an oxygen pump in automotive and industrial applications, and is a choice electrolyte for Solid Oxide Fuel Cell (SOFC) technology. YSZ is also a major component of the SOFC electrodes, and is commonly mixed with 50% volume NiO to create a Ni/YSZ cermet anode. In both the adsorption and fuel cell applications homogeneous control of the porosity of YZS is important. Templating methods provide well ordered macroporous structures and have been used to prepare ordered, macroporous YSZ from metal nitrate precursors using polystyrene spheres of 1 μm as templates. Ordered three-dimensional structures were synthesised and the effects of sintering temperatures of 650–1400 °C on pore size, particle size and pore wall thickness were examined. Ordered porosity was maintained at all temperatures, though some structural degradation and sintering was observed at 1400 °C. This study demonstrated that templated porosity is maintained well above the conventional sintering temperature of the electrodes, and higher than previous studies reported. The stability of these structures at high temperatures makes this fabrication technique a promising alternative to conventional methods of synthesising porous materials.     

Synthesis and mechanical and tribological characterization of alumina–yttria stabilized zirconia (YSZ) nanocomposites with YSZ synthesized by means of an aqueous solution–gel method or a hydrothermal route

In the present study, yttria stabilized zirconia (YSZ) nanoparticles, prepared by means of an aqueous solution–gel method or a hydrothermal route, are incorporated in a matrix of submicron alumina particles by wet mechanical milling. The microstructural characteristics and the mechanical and tribological properties of the obtained alumina–YSZ nanocomposites are evaluated as a function of different processing conditions like milling time, YSZ amount, sintering procedure and synthesis method of YSZ.     

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.     

Microstructure evaluation of sintered combustion-derived fine powder NiO–YSZ

Citrate–nitrate combustion synthesis was used for the preparation of NiO–YSZ. The main advantage of the preparation method used was reflected in the fact that after the synthesis both phases NiO and YSZ were randomly distributed on a nanometre level. The prepared NiO–YSZ powder composites were shaped, sintered and reduced to Ni–YSZ and subsequently submitted to microstructure investigations. Relative sintered densities higher than 90% were obtained at sintering temperatures as low as 1200 °C. A sintering temperature 1200 °C was also recognized as the preparation temperature that provided the smallest Ni grains in the final Ni–YSZ cermet with an average Ni-particle diameter as low as 0.27 μm.     

Microstructure tailoring of the nickel–yttria stabilised zirconia (Ni–YSZ) cermet hollow fibres

Nickel–yttria stabilised zirconia (Ni–YSZ) hollow fibres have been prepared by the phase inversion/sintering technique followed by a reduction process with hydrogen. This work is particularly focussed on tailoring the microstructure and the properties of hollow fibres by ethanol addition into the spinning hollow fibre suspension. Microstructure evolution change is demonstrated by increasing the amount of ethanol from 0 to 35 wt% e.g. the hollow fibre cross-section is modified from a sponge-like structure sandwiched by two thin finger-like layers to the sponge-like structure only. Higher ethanol content translates to denser hollow fibres. This trend also correlates with the shrinkage, mechanical strength and electrical conductivity of the hollow fibres. As the ethanol content is increased, shrinkage reduces, mechanical strength improves and electrical conductivity increases. The Ni–YSZ hollow fibres made from suspensions containing 15–25 wt% ethanol are considered the best option as anode supports for micro-tubular solid oxide fuel cells in terms of their median porosity values, since insufficient porosity would hinder the fuel and product transport, whereas excessive porosity would deteriorate the mechanical strength of the fibres.     

Thin film yttria-stabilized zirconia electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs) by chemical solution deposition

A 500 nm thick thin film YSZ (yttria-stabilized zirconia) electrolyte was successfully fabricated on a conventionally processed anode substrate by spin coating of chemical solution containing slow-sintering YSZ nanoparticles with the particle size of 20 nm and subsequent sintering at 1100 °C. Incorporation of YSZ nanoparticles was effective for suppressing the differential densification of ultrafine precursor powder by mitigating the prevailing bi-axial constraining stress of the rigid substrate with numerous local multi-axial stress fields around them. In particular, adding 5 vol% YSZ nanoparticles resulted in a dense and uniform thin film electrolyte with narrow grain size distribution, and fine residual pores in isolated state. The thin film YSZ electrolyte placed on a rigid anode substrate with the GDC (gadolinia-doped ceria) and LSC (La_0.6Sr_0.4CoO_3?δ) layers deposited by PLD (pulsed laser deposition) processes revealed that it had fairly good gas tightness relevant to a SOFC (solid oxide fuel cell) electrolyte and maintained its structural integrity during fabrication and operation processes. In fact, the open circuit voltage was 1.07 V and maximum power density was 425 mW/cm² at 600 °C, which demonstrates that the chemical solution route can be a viable means for reducing electrolyte thickness for low- to intermediate-temperature SOFCs.     

Three-dimensional random resistor-network model for solid oxide fuel cell composite electrodes

A three-dimensional reconstruction of solid oxide fuel cell (SOFC) composite electrodes was developed to evaluate the performance and further investigate the effect of microstructure on the performance of SOFC electrodes. Porosity of the electrode is controlled by adding pore former particles (spheres) to the electrode and ignoring them in analysis step. To enhance connectivity between particles and increase the length of triple-phase boundary (TPB), sintering process is mimicked by enlarging particles to certain degree after settling them inside the packing. Geometrical characteristics such as length of TBP and active contact area as well as porosity can easily be calculated using the current model. Electrochemical process is simulated using resistor-network model and complete Butler-Volmer equation is used to deal with charge transfer process on TBP. The model shows that TPBs are not uniformly distributed across the electrode and location of TPBs as well as amount of electrochemical reaction is not uniform. Effects of electrode thickness, particle size ratio, electron and ion conductor conductivities and rate of electrochemical reaction on overall electrochemical performance of electrode are investigated.     

Infiltration of SOFC Stacks: Evaluation of the Electrochemical Performance Enhancement and the Underlying Changes in the Microstructure

Experimental SOFC stacks with 10 SOFCs (LSM‐YSZ/YSZ/Ni‐YSZ) were infiltrated with CGO and Ni‐CGO on the air and fuel side, respectively in an attempt to counter degradation and improve the output. The electrochemical performance of each cell was characterized (i) before infiltration, (ii) after infiltration on the cathode side, and (iii) after the infiltration of the anode side. A significant performance enhancement was observed after the infiltration with CGO on the cathode, while the infiltration of the anode side with Ni‐CGO had no significant effect on the electrochemical performance. After testing the cells were characterized by SEM and TEM/EELS. A thin layer of CGO nanoparticles around the LSM‐YSZ back bone structure was found after infiltration. On the anode side nano sized Ni particles were found embedded in a CGO layer formed around the Ni‐YSZ structure. EELS analysis showed that the oxidation state of the Ce ions is identical on the air and the fuel side.     

Interaction of a ceria‐based anode functional layer with a stabilized zirconia electrolyte: Considerations from a materials perspective

We report on the materials interaction of gadolinium‐doped ceria (GDC) and yttria‐stabilized zirconia (YSZ) in the context of high‐temperature sintering during manufacturing of anode supported solid oxide fuel cells (AS–SOFC). While ceria‐based anodes are expected to show superior electrochemical performance and enhanced sulfur and coking tolerance in comparison to zirconia‐based anodes, we demonstrate that the incorporation of a Ni–GDC anode into an ASC with YSZ electrolyte decreases the performance of the ASC by approximately 50% compared to the standard Ni–YSZ cell. The performance loss is attributed to interdiffusion of ceria and zirconia during cell fabrication, which is investigated using powder mixtures and demonstrated to be more severe in the presence of NiO. We examine the physical properties of a GDC–YSZ mixed phase under reducing conditions in detail regarding ionic and electronic conductivity as well as reducibility, and discuss the expected impact of cation intermixing between anode and electrolyte.     

Effect of Nickel Oxide/Yttria-Stabilized Zirconia Anode Precursor Sintering Temperature on the Properties of Solid Oxide Fuel Cells

An NiO/yttria-stabilized zirconia (YSZ) layer sintered at temperatures between 1100° and 1500°C onto dense YSZ electrolyte foils forms the precursor structure for a porous Ni/YSZ cermet anode for solid oxide fuel cells. Conflicting requirements for the electrochemical performance and mechanical strength of such cells are investigated. A minimum polarization resistance of 0.09 Ω^.cm²at 1000°C in moist hydrogen is obtained for sintering temperatures of 1300°–1400°C. The mechanical strength of the cells decreases with increased sintering temperature because of the formation of channel cracks in the electrode layers, originating in a thermal expansion coefficient mismatch between the layers.     

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.     

Preparation of Anode/Electrolyte Ceramic Composites by Coextrusion of Pastes

Anode/electrolyte two-layer ceramic composites for tubular solid oxide fuel cells were prepared through coextrusion of multiple pastes containing a water-based binder (an aqueous solution of hydroxypropyl methylcellulose). The multibillet extrusion (MBE) technique was found to be effective in achieving the anode/electrolyte composite pipes. Furthermore, it is possible to reduce the wall thickness of both anode and electrolyte layers by raising the extrusion ratio of each layer. The extrusion pressure and binder content required to obtain sound extrudates decreased with an increase in the fraction of nickel oxide in an anode layer. It is feasible to decrease the difference in the sintering shrinkage between the anode and electrolyte layers by incorporating calcined coarse yttria-stabilized zirconia (YSZ) powder in the electrolyte layer. The incorporation of coarse YSZ powder in an anode is effective in forming a continuous NiO network within the YSZ matrix.     

Influence of the synthesis process on the features of Y2O3-stabilized ZrO2 powders obtained by the sol–gel method

Y₂O₃-stabilized ZrO₂ (YSZ) powders have been prepared by the sol–gel method using different synthesis parameters. Specifically, zirconium n-propoxide was dissolved in propanol at pH 0.5 or 5 (provided by HNO₃), with or without acetic acid in the hydrolysis medium. Subsequently, the YSZ powders obtained by gelation and drying of these solutions was characterized using scanning and transmission electron microscopies, X-ray diffractometry, and N₂-adsorption. Compacts made from these YSZ powders which were then sintered were also analyzed. It was found that the pH of the hydrolysis medium has a notable influence on the microstructure, morphology, color, crystallinity, and sintering behavior process of these YSZ sol–gel powders. It was also found that the use of acetic acid also affects the YSZ powder features, and results in compacts with higher residual porosity after sintering. Finally, the compacts prepared from the YSZ powders obtained at pH 5 and without acetic acid exhibit the greatest sinterability.     

Fabrication of seven cells in single tubular solid oxide fuel cell using multi-pass extrusion process

A solid oxide fuel cell (SOFC) with high specific electrolyte surface area was fabricated using the multi-pass extrusion process. The cell configuration was NiO-YSZ/YSZ/LSM. In this design, one tube contained 7 individual fuel cells. The outer diameter of the tube was 5 mm and 4.1–4.2 mm after extrusion and sintering, respectively. The length of the cell was optimized to 3–5 cm with continuous channels of 400–450 μm in diameter. The porous microstructures of the anode and the cathode and the dense microstructure of the electrolyte were observed by scanning electron microscopy. The relative density of the electrolyte was >96% and the thickness was 15–20 μm. The XRD profiles indicated no undesirable phases after co-sintering at 1300 °C.     

Solid-state sintering of core-shell ceramic powders fabricated by particle atomic layer deposition

The properties of technical ceramics are highly dependent on their microstructure, which evolves during sintering. Sintering is the process by which ceramic parts are subjected to high temperatures to activate chemical diffusion and the consumption of porosity. During the initial stage of sintering, interparticle necks between neighboring particles form and subsequently increase in size, consuming porosity as the particle centers move closer together. To experimentally determine how this process depends on particle surface composition, particle atomic layer deposition (ALD) was used to deposit a thin film of amorphous aluminum oxide (Al₂O₃) onto yttria-stabilized tetragonal zirconia (3YSZ) particles, producing core-shell structured powders. The uniformity of the Al₂O₃ film was confirmed with transmission electron microscopy and energy dispersive spectroscopy. Scanning electron microscopy was used to observe microstructural evolution during sintering, and the dihedral angles of Al₂O₃ and 3YSZ grains were measured to determine the ratio of interfacial energies between the 3YSZ|3YSZ, 3YSZ|Al₂O₃, and Al₂O₃|Al₂O₃ interfaces. Analysis of the densification kinetics revealed that the initial stage of densification is dependent on the material at the surface of the particles (ie, the Al₂O₃ film) and is controlled by the diffusion of Al³⁺ cations through Al₂O₃. Once the Al₂O₃ film has coalesced, the sintering behavior is controlled by the densification of the core material (3YSZ). Thus, core-shell powders fabricated by particle ALD sinter by a two-step process where the kinetics are dependent on the material present at interparticle contacts.