Publications
51 results found
Long X, Boldrin P, Zhang Y, et al., 2022, Towards integrated gasification and fuel cell operation with carbon capture: Impact of fuel gas on anode materials, Fuel, Vol: 318, ISSN: 0016-2361
Integrated gasification fuel cell technology is a promising option for processing solid fuels, which would enable high efficiencies to be reached in small-scale power generation. Among the different fuel cell types, solid oxide fuel cells present a good temperature match with fluidised bed gasification as well as greater versatility in terms of the fuel gas composition they can handle. However, their resistance to impurities in the gas needs to be addressed. The main objective of this work is to assess the impact on typical materials used in fuel cell anodes of the gases produced from a gasifier operating with a N2-free gasification agent, which would make the system carbon-capture ready. A laboratory scale continuous pressurised fluidised bed reactor has been modified to study CO2 and steam (concentration up to 40 mol%.) gasification of lignite at 850 °C. A second stage fixed bed reactor has been specially designed and constructed to study degradation of two SOFC anode materials (nickel/yttrium–stabilised zirconium oxide (Ni/YSZ) and nickel/gadolinium-doped ceria (Ni/CGO)) after exposure to real fuel gas at 765 °C. Under these conditions, which did not involve any gas cleaning/conditioning between stages, carbon deposition on the surface of anode materials was much smaller than in previous studies that used model tar compounds as feeds. Fuel gas from CO2/H2O gasification tended to deposit less carbon and sulphur on tested anode materials, particularly on Ni/CGO, than that from CO2 gasification. The anode materials converted a significant fraction of the fed tar to gas.
Wehrle L, Wang Y, Boldrin P, et al., 2022, Optimizing solid oxide fuel cell performance to re-evaluate its role in the mobility sector, ACS Environmental Au, Vol: 2, Pages: 42-64, ISSN: 2694-2518
A sustainable, interconnected, and smart energy network in which hydrogen plays a major role cannot be dismissed as a utopia anymore. There are vast international and industrial ambitions to reach the envisioned system transformation, and the decarbonization of the mobility sector is a central pillar comprising a huge economic share. Solid oxide fuel cells (SOFCs) are one of the most promising technologies in the brigade of clean energy devices and have potentially wide applicability for transportation, due to their high efficiencies and impurity tolerance. To uncover future pathways to boost the cell’s performance, we propose a detailed multiscale modeling methodology to evaluate the direct impact of cell materials and morphologies on commercial-scale system performance. After acquiring intrinsic electrokinetics decoupled from mass and charge transport of different anode and cathode materials via a half-cell model, a full cell model is employed to identify the most promising electrode combination. Subsequently, a scale-up to the system level is performed by coupling a 3-D kW-stack model to the balance of plant components while focusing on morphological optimization of the membrane electrode assembly (MEA). On optimally tailoring the MEA, model results demonstrate that an advanced cell design comprising a Ni fiber-CGO matrix structured anode and a LSCF-infiltrated CGO cathode could reach a stack power density of 1.85 kW L–1 and a net system efficiency of 52.2% for operation at <700 °C, with manageable stack temperature gradients of <14 K cm–1. The model-optimized power density is substantially higher than those of commercial stacks and surpasses industrial targets for SOFC-based range extenders. Thus, with further cell and stack development targeting the performance limiting processes elucidated in the paper, commercial SOFCs could, alongside range extenders, also act as prime movers in larger scale transport applications such as trucks
Skinner S, Cavallaro A, Cali E, et al., 2021, Analysis of H2O-induced surface degradation in SrCoO3-derivatives and its impact on redox kinetics, Journal of Materials Chemistry A, Vol: 9, Pages: 24528-24538, ISSN: 2050-7488
Substituted SrCoO3 perovskites have been proposed as promising mixed ionic electronic conductors for a range of applications including intermediate temperature solid oxide fuel cells (IT-SOFCs), electrolysers and thermochemical water splitting reactors for H2 production. In this work we investigate the effect of sample exposure to water in substituted SrCoO3 powders and thin films and correlate it with the degradation of oxygen mobility and kinetics. SrCo0.95Sb0.05O3−δ (SCS) thin films have been deposited on different single crystal substrates by pulsed laser deposition (PLD). After water cleaning and post annealing at 300 °C, the sample surface presented an increase of the SrO-surface species as observed by ex situ X-ray Photoemission Spectroscopy (XPS) analysis. This increase in SrO at the sample surface has also been confirmed by the Low Energy Ion Scattering (LEIS) technique on both SCS thin film and powder. Thermochemical water splitting experiments on SCS and SrCo0.95Mo0.05O3−δ (SCM) powder revealed a phase degradation under water oxidising conditions at high temperature with the formation of the trigonal phase Sr6Co5O15. Transmission Electron Microscopy (TEM) analysis of SCS powder treated with water suggests that this phase degradation could already superficially start at Room Temperature (RT). By isotope exchange depth profile experiments on SCS thin films, we were able to quantify the oxygen diffusivity in this SCS surface decomposed layer (D* = 5.1 × 10−17 cm2 s−1 at 400 °C). In the specific case of bulk powder, the effect of water superficial decomposition translates into a lower oxidation and reduction kinetics as demonstrated by comparative thermogravimetric analysis (TGA) studies.
Boldrin P, Malko D, Mehmood A, et al., 2021, Deactivation, reactivation and super-activation of Fe-N/C oxygen reduction electrocatalysts: gas sorption, physical and electrochemical investigation using NO and O2, Applied Catalysis B: Environmental, Vol: 292, Pages: 1-12, ISSN: 0926-3373
We show that gaseous nitric oxide (NO) and oxygen (O2) are useful molecular probes to uncover complex surface processes in Fe-N/C catalysts. We unravel the difference between using gaseous NO in a temperature programmed desorption experiment and using NO (and progenitors) in an electrochemical experiment. Gas phase O2 adsorption is almost exclusively desorbed as CO2, and continued exposure to oxygen increases the amount of chemisorbed oxygen species on the surface. The oxidation state of the carbon surface is an important activity determining factor, and under normal “electrochemical” conditions many of the active sites are blocked. Only by treatment at 600 °C in Ar can we free those sites for oxygen adsorption, however under atmospheric storage, and especially during the oxygen reduction reaction (ORR), the surface quickly becomes deactivated with chemisorbed oxygen species and water. We demonstrate that the material can be super-activated by reductive electrochemical treatment, both in an electrochemical three electrode cell and in a fuel cell. The energy gained following the treatment is significantly larger than the energetic cost.
Ouyang M, Bertei A, Cooper SJ, et al., 2021, Model-guided design of a high performance and durability Ni nanofiber/ceria matrix solid oxide fuel cell electrode, Journal of Energy Chemistry, Vol: 56, Pages: 98-112, ISSN: 2095-4956
Mixed ionic electronic conductors (MIECs) have attracted increasing attention as anode materials for solid oxide fuel cells (SOFCs) and they hold great promise for lowering the operation temperature of SOFCs. However, there has been a lack of understanding of the performance-limiting factors and guidelines for rational design of composite metal-MIEC electrodes. Using a newly-developed approach based on 3D-tomography and electrochemical impedance spectroscopy, here for the first time we quantify the contribution of the dual-phase boundary (DPB) relative to the three-phase boundary (TPB) reaction pathway on real MIEC electrodes. A new design strategy is developed for Ni/gadolinium doped ceria (CGO) electrodes (a typical MIEC electrode) based on the quantitative analyses and a novel Ni/CGO fiber–matrix structure is proposed and fabricated by combining electrospinning and tape-casting methods using commercial powders. With only 11.5 vol% nickel, the designer Ni/CGO fiber–matrix electrode shows 32% and 67% lower polarization resistance than a nano-Ni impregnated CGO scaffold electrode and conventional cermet electrode respectively. The results in this paper demonstrate quantitatively using real electrode structures that enhancing DPB and hydrogen kinetics are more efficient strategies to enhance electrode performance than simply increasing TPB.
Chen J, Ouyang M, Boldrin P, et al., 2020, Understanding the coarsening and degradation in a nanoscale nickel gadolinia-doped-ceria electrode for high-temperature applications., ACS Applied Materials and Interfaces, Vol: 12, Pages: 47564-47573, ISSN: 1944-8244
Nanostructure engineering is an effective approach to enhance the electrochemical performance of energy devices. While the high surface area of nanoparticles greatly enlarges the density of reaction sites, it often also leads to relatively rapid degradation as the particles tend to coarsen to reduce their high surface energy. Therefore, a nickel/gadolinia-doped-ceria (CGO) cermet electrode is studied, with a novel porous nanostructure consisting of nanoscale Ni (100 nm) and CGO (50 nm) crystallites, cosintered from nanocomposite precursor agglomerate particles. This electrode combines both high performance and excellent durability, with a total area-specific resistance (ASR) of 0.11 Ω cm2 at 800 °C and a stable ASR with up to 170 h ageing in humidified 5% H2-N2. Post-test analysis by 3D tomography shows that nickel coarsens and is responsible for the initial increase in ASR. However, the subsequent electrochemical performance is stable because reaction at the double phase boundaries (DPBs) on the surfaces of nanoscale CGO becomes dominant and is resistant to ageing. At this stage, the coarsened Ni network is also stabilized by the surrounding nanostructure. The dominant role of the DPB reaction is supported quantitatively using a continuum model with geometrical parameters obtained from 3D tomography.
Chen J, Wang X, Boldrin P, et al., 2019, Hierarchical dual-porosity nanoscale nickel cermet electrode with high performance and stability, Nanoscale, Vol: 11, Pages: 17746-17758, ISSN: 2040-3364
Nano-structured metal-ceramic materials have attracted attention to improve performance in energy conversion applications. However, they have poor long-term stability at elevated temperatures due to coarsening of the metal nanoparticles. In this work we show that this can be mitigated by a novel design of the nano-structure of Ni cermet fuel electrodes for solid oxide cells. The strategy is to create a dual porosity microstructure, without the use of fugitive pore-formers, with micron-size pores to facilitate gas transport and nanoscale pores to control nano-particle coarsening. This has been achieved using a continuous hydrothermal synthesis and two-stage heat treatments to produce electrodes with micron size agglomerates of nano-structured porous Ni-Yttria-Stabilised-Zirconia (YSZ). This unique hierarchical microstructure combines enhanced electrochemical reaction in the high activity (triple phase boundary density 11 μm-2) nanoscale regions with faster gas diffusion in the micron-sized pores. The electrodes are aged at 800 °C in humidified 5% H2-N2 for up to 600 h. The electrochemical reaction resistance is initially 0.17 Ω cm2 but later reaches a steady long-term value of 0.15 Ω cm2. 3-D reconstruction of the electrodes after 10 h and 100 h of ageing reveals an increase in YSZ network connectivity and TPB percolation. This improvement is well-correlated to the 3-D tomography parameters using a physical model adapted from mixed conducting SOC air electrodes, which is also supported, for the first time, by numerical simulations of the microstructural evolution. These also reveal that in the long term, nickel coarsening is inhibited by the nanoscale entanglement of Ni and YSZ in the hierarchical microstructure.
Boldrin P, Brandon NP, 2019, Progress and outlook for solid oxide fuel cells for transportation applications, Nature Catalysis, Vol: 2, Pages: 571-577, ISSN: 2520-1158
With their high temperatures and brittle ceramic components, solid oxide fuel cells (SOFCs) might not seem the obvious fit for a power source for transportation applications. However, over recent years, advances in materials and cell design have begun to mitigate these issues, leading to the advantages of SOFCs such as fuel flexibility and high efficiency being exploited in vehicles. Here, we review these advances, look at the vehicles that SOFCs have already been used in, discuss the areas that need improvement for full commercial breakthrough and the ways in which catalysis can assist with these. In particular, we identify lifetime and degradation, fuel flexibility, efficiency and power density as key aspects for SOFCs’ improvement. Expertise from the catalysis landscape, ranging from surface science and computational materials design, to improvements in reforming catalysts and reformer design, are instrumental to this goal.
Chen J, Ouyang M, Boldrin P, et al., 2019, Fabrication and Characterisation of Nanoscale Ni-CGO Electrode from Nano-Composite Powders, ECS Transactions, Vol: 91, Pages: 1799-1805, ISSN: 1938-6737
Ouyang M, Boldrin P, Maher R, et al., 2019, A mechanistic study of the interactions between methane and nickel supported on doped ceria, Applied Catalysis B: Environmental, Vol: 248, Pages: 332-340, ISSN: 0926-3373
A novel combined method using modified methane pulses and in-situ Raman spectroscopy together with mass spectrometry is applied to impregnated Ni/gadolinium-doped ceria (CGO). The partial oxidation of methane is deduced to proceed via a Mars-van-Krevelen type mechanism composed of initial methane decomposition together with carbon oxidation by oxygen from CGO. The critical role of the ceria surface and the bulk oxygen in the reaction is defined in detail. Oxygen is a necessary reactant in the reaction, as well as inhibiting carbon deposition. Oxygen spill-over is the driving force for the carbon oxidation and the ceria surface oxygen is resupplied by bulk oxygen after depletion. Bulk migration of oxygen to the surface is the rate-determining step. We also demonstrate that the ceria oxygen stoichiometry significantly affects the type of reaction and the rate of reaction between methane and Ni/CGO: The total oxidation of methane happens only when the oxygen stoichiometry is high while the oxygen spill-over rate decreases with decreasing oxygen stoichiometry, which reduces the rate of carbon elimination and results in reduction in the rate of methane oxidation. This work lays out a comprehensive evaluation methodology and provides important insights for future design of methane oxidation catalysts for solid oxide fuel cells, and more widely for methane reforming with different oxidants (steam, CO2, NO2 etc).
Chen J, Ouyang M, Boldrin P, et al., 2019, Fabrication and Characterisation of Nanoscale Ni-CGO Electrode from Nano-Composite Powders, 16th International Symposium on Solid Oxide Fuel Cells (SOFC-XVI)
Ouyang M, Bertei A, Cooper S, et al., 2019, Design of Fibre Ni/CGO Anode and Model Interpretation, 16th International Symposium on Solid Oxide Fuel Cells (SOFC-XVI)
Stevenson GR, Boldrin P, Brandon NP, 2019, Liquid-based synthesis of nickel- And lanthanum- co-doped strontium titanates for use as anodes in all-ceramic solid oxide fuel cell anodes, Pages: 1761-1770, ISSN: 1938-6737
Nickel- lanthanum- co-doped compositions of strontium titanate have been synthesized and characterized by a scaleable liquid-based synthesis that may offer an alternative to conventional solid-state synthesis. La0.52Sr0.28Ti0.94Ni0.06O3 is synthesized from soluble precursors followed by calcination in air. The materials can be made phase pure at temperatures as low as 1250°C, as highlighted by X-ray diffraction, and nickel exsolves in hydrogen in the same way as solid-state-synthesized materials. The particle size can be varied by calcination temperature and ball milling between 2 µm and 20 µm. The material is then measured electrochemically by electrochemical impedance spectroscopy and 4-point DC conductivity. A reduction in particle size from 20 µm to 9 µm results in a large improvement in impedance response measured.
Ouyang M, Bertei A, Cooper SJ, et al., 2019, Design of fibre Ni/CGO anode and model interpretation, ECS Transactions, Vol: 91, Pages: 1721-1739, ISSN: 1938-6737
A new structure of Ni/gadolinium-doped ceria (CGO) is prepared by a highly tuneable and facile combination of electrospinning and tape-casting method. The structure consists of a network made by continuous Ni fibres and filled in with CGO matrices. When used as the anode of solid oxide fuel cell (SOFC), though it has a lower triple phase boundary (TPB) density, it exhibits better performance compared with impregnated and cermet Ni/CGO with higher nickel loading. An algorithm is developed to determine the ceria-pore double phase boundary (DPB) density with different distance from nickel phase. Using the results, the relative electrochemical reaction rate on DPB and TPB of three different electrodes are calculated and proves that fibre-matrices structure has the morphology advantage of efficiently making use of all ceria-pore DPB. The relative contribution of DPB and TPB in anode reaction of SOFC is quantified in the first time and the importance of DPB is further stressed. This work provides new inspirations in material design of SOFC/SOEC and develops a novel strategy to evaluate the performance of electrodes quantitatively.
Ruiz-Trejo E, Bertei A, Maserati A, et al., 2017, Oxygen Reduction, Transport and Separation in Low Silver Content Scandia-Stabilized Zirconia Composites, Journal of The Electrochemical Society, Vol: 164, Pages: F3045-F3054, ISSN: 1945-7111
Dense composites of silver and Sc-stabilized ZrO2 (Ag-ScSZ) are manufactured from ScSZ sub-micrometric particles coated with silver using Tollens’ reagent. A composite with 8.6 vol % of silver exhibits metallic conductivity of 186 S cm−1 and oxygen flux of 0.014 μmol cm−2 s−1 at 600°C for a 1-mm thick membrane when used as a pressure-driven separation membrane between air and argon. To gain insight into the role of oxygen transport in Ag and ScSZ, a dense non-percolating sample (Ag 4.7 vol%) is analyzed by impedance spectroscopy and the transport of oxygen through both phases is modelled. Oxygen transport takes place in both silver and ScSZ but it is still dominated by transport in the ionic conductor and therefore a large volume fraction of the ion conductor is beneficial for the separation. The oxygen transport in the silver clusters inside the composite is dominated by diffusion of neutral species and not by the charge transfer reaction at the interface between ScSZ and Ag, yet small silver particles on the surface improve the reduction of oxygen. Oxygen reduction is highly promoted by silver on the surface and there are no limitations of charge transfer at the interface between silver and ScSZ.
Ouyang M, Boldrin P, Brandon NP, 2017, Methane Pulse Study on Nickel Impregnated Gadolinium Doped Ceria, 15th International Symposium on Solid Oxide Fuel Cells (SOFC), Publisher: ELECTROCHEMICAL SOC INC, Pages: 1353-1366, ISSN: 1938-5862
Cooper SJ, brandon NP, 2017, Solid Oxide Fuel Cell Lifetime and Reliability, Solid Oxide Fuel Cell Lifetime and Reliability Critical Challenges in Fuel Cells, Editors: Ruiz-Trejo, BOLDRIN, Publisher: Academic Press, Pages: 1-15, ISBN: 9780128097243
For its holistic approach, this book can be used both as an introduction to these issues and a reference resource for all involved in research and application of solid oxide fuel cells, especially those developing understanding in ...
Boldrin D, Boldrin P, Ruiz-Trejo E, et al., 2017, Recovery of the intrinsic thermoelectric properties of CaMn0.98Nb0.02O3 in 2-terminal geometry using Ag infiltration, Acta Materialia, Vol: 133, Pages: 68-72, ISSN: 1359-6454
Oxide based thermoelectric (TE) materials offer several advantages over currently used intermetallic alloys due to their chemical and thermal stability at high temperatures, non-toxic elements, low cost and ease of manufacture. However, incorporation of oxides into thermoelectric generators (TEGs) is hindered by factors such as the requirement for polycrystalline materials over single crystals and the large electrode/ceramic contact resistances. The latter significantly limits the performance efficiency of a working TEG. Here we report the TE properties of Ag infiltrated polycrystalline CaMn0.98Nb0.02O3 ceramics. We demonstrate that by using this route the intrinsic TE properties of this material are fully recovered in 2-terminal geometry through Ag infiltration, thereby overcoming the electrode TEG contact problem. This synthetic route provides opportunities for bridging the performance gap between the intrinsic TE and TEG device properties of oxides.
Ouyang M, Boldrin P, Brandon NP, 2017, Methane Pulse Study on Nickel Impregnated Gadolinium Doped Ceria, 12th European SOFC & SOE Forum
Brandon NP, Ruiz-Trejo E, Boldrin P, 2017, Solid Oxide Fuel Cell Lifetime and Reliability: Critical Challenges in Fuel Cells, ISBN: 9780081011027
Solid Oxide Fuel Cell Lifetime and Reliability: Critical Challenges in Fuel Cells presents in one volume the most recent research that aims at solving key issues for the deployment of SOFC at a commercial scale and for a wider range of applications. To achieve that, authors from different regions and backgrounds address topics such as electrolytes, contaminants, redox cycling, gas-tight seals, and electrode microstructure. Lifetime issues for particular elements of the fuel cells, like cathodes, interconnects, and fuel processors, are covered as well as new materials. They also examine the balance of SOFC plants, correlations between structure and electrochemical performance, methods for analysis of performance and degradation assessment, and computational and statistical approaches to quantify degradation. For its holistic approach, this book can be used both as an introduction to these issues and a reference resource for all involved in research and application of solid oxide fuel cells, especially those developing understanding in industrial applications of the lifetime issues. This includes researchers in academia and industrial R&D, graduate students and professionals in energy engineering, electrochemistry, and materials sciences for energy applications. It might also be of particular interest to analysts who are looking into integrating SOFCs into energy systems. Brings together in a single volume leading research and expert thinking around the broad topic of SOFC lifetime and durability. Explores issues that affect solid oxide fuel cells elements, materials, and systems with a holistic approach. Provides a practical reference for overcoming some of the common failure mechanisms of SOFCs. Features coverage of integrating SOFCs into energy systems.
Cassidy M, Neagu D, Savaniu C, et al., 2017, New Materials for Improved Durability and Robustness in Solid Oxide Fuel Cell, SOLID OXIDE FUEL CELL LIFETIME AND RELIABILITY: CRITICAL CHALLENGES IN FUEL CELLS, Editors: Brandon, RuizTrejo, Boldrin, Publisher: ACADEMIC PRESS LTD-ELSEVIER SCIENCE LTD, Pages: 193-216, ISBN: 978-0-08-101102-7
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Tariq F, Ruiz-Trejo E, Bertei A, et al., 2017, Microstructural Degradation: Mechanisms, Quantification, Modeling and Design Strategies to Enhance the Durability of Solid Oxide Fuel Cell Electrodes, SOLID OXIDE FUEL CELL LIFETIME AND RELIABILITY: CRITICAL CHALLENGES IN FUEL CELLS, Editors: Brandon, RuizTrejo, Boldrin, Publisher: ACADEMIC PRESS LTD-ELSEVIER SCIENCE LTD, Pages: 79-99, ISBN: 978-0-08-101102-7
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Boldrin P, Ruiz Trejo E, Mermelstein J, et al., 2016, Strategies for carbon and sulfur tolerant solid oxide fuel cell materials, incorporating lessons from heterogeneous catalysis, Chemical Reviews, Vol: 116, Pages: 13633-13684, ISSN: 1520-6890
Solid oxide fuel cells (SOFCs) are a rapidly emerging energy technology for a low carbon world, providing high efficiency, potential to use carbonaceous fuels and compatibility with carbon capture and storage. However, current state-of-the-art materials have low tolerance to sulfur, a common contaminant of many fuels, and are vulnerable to deactivation due to carbon deposition when using carbon-containing compounds. In this review we first study the theoretical basis behind carbon and sulfur poisoning, before examining the strategies towards carbon and sulfur tolerance used so far in the SOFC literature. We then study the more extensive relevant heterogeneous catalysis literature for strategies and materials which could be incorporated into carbon and sulfur tolerant fuel cells.
Jamil Z, Ruiz-Trejo E, Boldrin P, et al., 2016, Anode fabrication for solid oxide fuel cells: Electroless and electrodeposition of nickel and silver into doped ceria scaffolds, International Journal of Hydrogen Energy, Vol: 41, Pages: 9627-9637, ISSN: 1879-3487
A novel fabrication method using electroless and electrodeposited Ni/Ag/GDC for SOFC anodes is presented. First a porous Ce0.9Gd0.1O2−x (GDC) scaffold was deposited on a YSZ electrolyte by screen printing and sintering. The scaffold was then metallized with silver using Tollens' reaction, followed by electrodeposition of nickel from a Watt's bath. The electrodes (Ni/Ag/GDC) were tested in both symmetrical and fuel cell configurations. The microstructures of the Ni/Ag/GDC anodes were analyzed using scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDX). Nano-particles of Ni formed in the porous GDC scaffold provided triple phase boundaries (TPB). The electronic conductivity of the Ni/Ag/GDC (3.5/24.7/71.8 vol%) electrode was good even at relatively low Ni volume fractions. The electrochemical performance was examined in different concentrations of humidified hydrogen (3% H2O) and over a range of temperatures (600–750 °C). The total area specific resistance (ASR) of the anode at 750 °C in humidified 97 vol% H2 was 1.12 Ω cm2, with low-frequency polarization (R_l) as the largest contributor. The electrodes were successfully integrated into a fuel cell and operated in both H2 and syngas.
Gallagher JR, Boldrin P, Combes GB, et al., 2016, The effect of Mg location on Co-Mg-Ru/γ-Al2O3 Fischer–Tropsch catalysts, Royal Society of London. Philosophical Transactions A. Mathematical, Physical and Engineering Sciences, Vol: 374, ISSN: 1364-503X
The effectiveness of Mg as a promoter of Co-Ru/γ-Al2O3 Fischer-Tropsch catalysts depends on how and when the Mg is added. When the Mg is impregnated into the support before the Co and Ru addition, some Mg is incorporated into the support in the form of MgxAl2O3+x if the material is calcined at 550°C or 800°C after the impregnation, while the remainder is present as amorphous MgO/MgCO3 phases. After subsequent Co-Ru impregnation MgxCo3-xO4 is formed which decomposes on reduction, leading to Co(0) particles intimately mixed with Mg, as shown by high-resolution transmission electron microscopy. The process of impregnating Co into an Mg-modified support results in dissolution of the amorphous Mg, and it is this Mg which is then incorporated into MgxCo3-xO4. Acid washing or higher temperature calcination after Mg impregnation can remove most of this amorphous Mg, resulting in lower values of x in MgxCo3-xO4. Catalytic testing of these materials reveals that Mg incorporation into the Co oxide phase is severely detrimental to the site-time yield, while Mg incorporation into the support may provide some enhancement of activity at high temperature.
Millan M, Lorente E, Boldrin P, et al., 2016, Integration of gasification and fuel cells: Interaction between the anode and contaminants in the syngas
Fouling due to carbon deposition on the fuel cell anode reduces the performance of the cell. • The addition of steam above S/C of 1 was found to reduce carbon deposition from tars but not fully suppress coke formation. • A combination of high S/C=ratio and current density may effectively inhibit carbon formation, maintaining cell performance. • Benzene and toluene represent a "worst-case scenario" as tar models and light fractions are more likely to produce carbon deposits.
Lomberg M, Boldrin P, Tariq F, et al., 2015, Additive manufacturing for solid oxide cell electrode fabrication, ECS Conference on Electrochemical Energy Conversion & Storage with SOFC-XIV, Publisher: Electrochemical Society, Pages: 2119-2127, ISSN: 1938-6737
Additive manufacturing can potentially offer a highly-defined electrode microstructure, as well as fast and reproducible electrode fabrication. Selective laser sintering is an additive manufacturing technique in which three-dimensional structures are created by bonding subsequent layers of powder using a laser. Although selective laser sintering can be applied to a wide range of materials, including metals and ceramics, the scientific and technical aspects of the manufacturing parameters and their impact on microstructural evolution during the process are not well understood. In the present study, a novel approach for electrode fabrication using selective laser sintering was evaluated by conducting a proof of concept study. A Ni-patterned fuel electrode was laser sintered on an yttria-stabilized zirconia substrate. The optimization process of laser parameters (laser sintering rate and laser power) and the electrochemical results of a full cell with a laser sintered electrode are presented. The challenges and prospects of using selective laser sintering for solid oxide cell fabrication are discussed.
Boldrin P, Ruiz Trejo E, Tighe C, et al., 2015, Impregnation of nanoparticle scaffolds for syngas-fed solid oxide fuel cell anodes, ECS Conference on Electrochemical Energy Conversion & Storage with SOFC-XIV, Publisher: Electrochemical Society, Pages: 1219-1227, ISSN: 1938-6737
A strategy for fabrication of solid oxide fuel cell anodes with improved porosity and lower sintering temperatures by impregnation of nanoparticle-containing porous scaffolds of ceria-gadolinia (CGO) has been developed. The CGO scaffolds are fabricated using a screen-printed ink containing nanoparticles and commercial particles of CGO and polymeric pore formers. Scanning electron microscopy and in situ ultra-small angle X-ray scattering show that incorporation of nanoparticles increases the porosity by allowing a reduction in sintering temperature. Electrochemical characterisation of symmetrical cells shows that the cells sintered at 1000°C possess similar electrode polarisation compared to those sintered at 1300°C. Button cell testing showed that reducing the sintering temperature produced cells which perform better at 700°C and below in hydrogen, and performed better at all temperatures using syngas. This approach has the potential to allow the use of a wider range of nanomaterials, giving a finer control over microstructure.
Ruiz-Trejo E, Boldrin P, Medley-Hallam JL, et al., 2015, Partial oxidation of methane using silver/gadolinia-doped ceria composite membranes, Chemical Engineering Science, Vol: 127, Pages: 269-275, ISSN: 1873-4405
Methane was partially oxidised to CO using oxygen permeated through a 1 mm thick silver/Ce0.9Gd0.1O2−x (Ag/CGO) composite membrane operating at 500–700 °C with air at 1 bar pressure. The membranes were fabricated by sintering ultrafine nanoparticles of gadolinia-doped ceria (<5 nm) coated with silver using Tollens׳ reaction. This unique combination led to dense composites with low content of silver (7 vol%), no reaction between the components and predominant metallic conductivity. When feeding 4% methane at 700 °C to a 1-mm thick Ag/CGO using Ni as reforming catalyst, the conversion reached 21% and the CO selectivity 92% with an estimated oxygen flux of 0.18 mL min−1 cm−2 (NTP). The samples were stable in carbon-containing atmospheres and under a large pO2 transmembrane pressure difference at temperatures below 700 °C for 48 h.
Boldrin P, Millan-Agorio M, Brandon NP, 2015, Effect of Sulfur- and Tar-Contaminated Syngas on Solid Oxide Fuel Cell Anode Materials, ENERGY & FUELS, Vol: 29, Pages: 442-446, ISSN: 0887-0624
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