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Recent Advances in Materials for Solid Oxide Cells

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (30 June 2016) | Viewed by 48786

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Special Issue Editor

Dr. Norbert H. Menzler

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Guest Editor

Forschungszentrum Jülich GmbH, Institute of Energy and Climate Research (IEK), IEK-1: Materials Synthesis and Processing, 52425 Jülich, Germany
Interests: solid oxide cells; ceramics; ceramics processing

Special Issue Information

Dear Colleagues,

Fuel cells, either low-temperature or high-temperature types, are on the way to market entry. Especially in the field of distributed energy conversion, as for household applications or stand-alone systems in the 1–250kW range, many companies have recently globally launched products which are now commercially available or which will be available within the next two years. Additionally, application fields like auxiliary power units for trucks, trains, ships or airplanes came up. In these fields, first system prototypes are operating on-board. High-temperature fuel cells, based on solid electrolytes, have special advantages with respect to fuel flexibility and efficiency.

As the “classical” solid oxide fuel cells are now introduced into the market segments, other, even more challenging, applications of solid oxide cells are of R&D interest. Worth naming are solid electrolysers to either generate a fuel (hydrogen or carbon-based fuels) or to act as intermediate power storage for volatile renewable energy generators, high-temperature batteries which use a fuel cell-electrolyser system as energy converting mediator, and low-temperature applications to even enter transportation applications.

These new application areas require novel materials, microstructures, cells, and stacks, which have to be addressed in the near future. Examples are: (i) by using a Solid Oxide Fuel Cells (SOFC) as electrolyser (SOEC) the fuel compositions differ greatly from fuel cell mode, e.g., high water vapor pressure or co-electrolysis of water/carbon monoxide; to question is how these different parameters affect the materials integrity and long-term stability; (ii) if an SOFC/SOEC system should be used as high-temperature battery: how to integrate a relevant type of storage (e.g., hydrogen tank or metal/metal oxide system) and to investigate the influence of charging-discharging cycles on the cells performance and microstructure; (iii) new, very low application temperatures (well below 500 °C) need novel materials for the electrolyte and the electrodes to reduce ohmic and polarization resistances.

This Special Issue highlights novel materials and microstructure developments in all aspects of Solid Oxide Cells used as fuel cells, electrolysers, or batteries.

Dr. Norbert H. Menzler
Guest Editor

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Keywords

Fuel Cells
High-Temperature Fuel Cells
Electrolysers
Materials
Electrolyte
Electrodes

Published Papers (7 papers)

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Research

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10753 KiB

Open AccessArticle

Operation of Thin-Film Electrolyte Metal-Supported Solid Oxide Fuel Cells in Lightweight and Stationary Stacks: Material and Microstructural Aspects

by Daniel Roehrens, Ute Packbier, Qingping Fang, Ludger Blum, Doris Sebold, Martin Bram and Norbert Menzler

Materials 2016, 9(9), 762; https://doi.org/10.3390/ma9090762 - 08 Sep 2016

Cited by 12 | Viewed by 6761

Abstract

In this study we report on the development and operational data of a metal-supported solid oxide fuel cell with a thin film electrolyte under varying conditions. The metal-ceramic structure was developed for a mobile auxiliary power unit and offers power densities of 1 W/cm² at 800 °C, as well as robustness under mechanical, thermal and chemical stresses. A dense and thin yttria-doped zirconia layer was applied to a nanoporous nickel/zirconia anode using a scalable adapted gas-flow sputter process, which allowed the homogeneous coating of areas up to 100 cm². The cell performance is presented for single cells and for stack operation, both in lightweight and stationary stack designs. The results from short-term operation indicate that this cell technology may be a very suitable alternative for mobile applications. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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4675 KiB

Open AccessFeature PaperArticle

Constrained Sintering in Fabrication of Solid Oxide Fuel Cells

by Hae-Weon Lee, Mansoo Park, Jongsup Hong, Hyoungchul Kim, Kyung Joong Yoon, Ji-Won Son, Jong-Ho Lee and Byung-Kook Kim

Materials 2016, 9(8), 675; https://doi.org/10.3390/ma9080675 - 09 Aug 2016

Cited by 13 | Viewed by 5464

Abstract

Solid oxide fuel cells (SOFCs) are inevitably affected by the tensile stress field imposed by the rigid substrate during constrained sintering, which strongly affects microstructural evolution and flaw generation in the fabrication process and subsequent operation. In the case of sintering a composite cathode, one component acts as a continuous matrix phase while the other acts as a dispersed phase depending upon the initial composition and packing structure. The clustering of dispersed particles in the matrix has significant effects on the final microstructure, and strong rigidity of the clusters covering the entire cathode volume is desirable to obtain stable pore structure. The local constraints developed around the dispersed particles and their clusters effectively suppress generation of major process flaws, and microstructural features such as triple phase boundary and porosity could be readily controlled by adjusting the content and size of the dispersed particles. However, in the fabrication of the dense electrolyte layer via the chemical solution deposition route using slow-sintering nanoparticles dispersed in a sol matrix, the rigidity of the cluster should be minimized for the fine matrix to continuously densify, and special care should be taken in selecting the size of the dispersed particles to optimize the thermodynamic stability criteria of the grain size and film thickness. The principles of constrained sintering presented in this paper could be used as basic guidelines for realizing the ideal microstructure of SOFCs. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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4757 KiB

Open AccessArticle

The Sulphur Poisoning Behaviour of Gadolinia Doped Ceria Model Systems in Reducing Atmospheres

by Matthias Gerstl, Andreas Nenning, Riza Iskandar, Veronika Rojek-Wöckner, Martin Bram, Herbert Hutter and Alexander Karl Opitz

Materials 2016, 9(8), 649; https://doi.org/10.3390/ma9080649 - 02 Aug 2016

Cited by 21 | Viewed by 5499

Abstract

An array of analytical methods including surface area determination by gas adsorption using the Brunauer, Emmett, Teller (BET) method, combustion analysis, XRD, ToF-SIMS, TEM and impedance spectroscopy has been used to investigate the interaction of gadolinia doped ceria (GDC) with hydrogen sulphide containing reducing atmospheres. It is shown that sulphur is incorporated into the GDC bulk and might lead to phase changes. Additionally, high concentrations of silicon are found on the surface of model composite microelectrodes. Based on these data, a model is proposed to explain the multi-facetted electrochemical degradation behaviour encountered during long term electrochemical measurements. While electrochemical bulk properties of GDC stay largely unaffected, the surface polarisation resistance is dramatically changed, due to silicon segregation and reaction with adsorbed sulphur. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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5291 KiB

Open AccessArticle

Novel Mg-Doped SrMoO₃ Perovskites Designed as Anode Materials for Solid Oxide Fuel Cells

by Vanessa Cascos, José Antonio Alonso and María Teresa Fernández-Díaz

Materials 2016, 9(7), 588; https://doi.org/10.3390/ma9070588 - 19 Jul 2016

Cited by 17 | Viewed by 6100

Abstract

SrMo_1−xM_xO_3−δ (M = Fe and Cr, x = 0.1 and 0.2) oxides have been recently described as excellent anode materials for solid oxide fuel cells at intermediate temperatures (IT-SOFC) with LSGM as the electrolyte. In this work, we have improved their properties by doping with aliovalent Mg ions at the B-site of the parent SrMoO₃ perovskite. SrMo_1−xMg_xO₃₋_δ (x = 0.1, 0.2) oxides have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers near 900 mW/cm⁻² at 850 °C using pure H₂ as fuel. We have studied its crystal structure with an “in situ” neutron power diffraction (NPD) experiment at temperatures as high as 800 °C, emulating the working conditions of an SOFC. Adequately high oxygen deficiencies, observed by NPD, together with elevated disk-shaped anisotropic displacement factors suggest a high ionic conductivity at the working temperatures. Furthermore, thermal expansion measurements, chemical compatibility with the LSGM electrolyte, electronic conductivity and reversibility upon cycling in oxidizing-reducing atmospheres have been carried out to find out the correlation between the excellent performance as an anode and the structural features. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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2925 KiB

Open AccessArticle

Nb⁵⁺-Doped SrCoO_3−δ Perovskites as Potential Cathodes for Solid-Oxide Fuel Cells

by Vanessa Cascos, José Antonio Alonso and María Teresa Fernández-Díaz

Materials 2016, 9(7), 579; https://doi.org/10.3390/ma9070579 - 15 Jul 2016

Cited by 22 | Viewed by 6372

Abstract

SrCoO_3−δ outperforms as cathode material in solid-oxide fuel cells (SOFC) when the three-dimensional (3C-type) perovskite structure is stabilized by the inclusion of highly-charged transition-metal ions at the octahedral positions. In a previous work we studied the Nb incorporation at the Co positions in the SrCo_1−xNb_xO_3−δ system, in which the stabilization of a tetragonal P4/mmm perovskite superstructure was described for the x = 0.05 composition. In the present study we extend this investigation to the x = 0.10–0.15 range, also observing the formation of the tetragonal P4/mmm structure instead of the unwanted hexagonal phase corresponding to the 2H polytype. We also investigated the effect of Nb⁵⁺ doping on the thermal, electrical, and electrochemical properties of SrCo_1−xNb_xO_3−δ (x = 0.1 and 0.15) perovskite oxides performing as cathodes in SOFC. In comparison with the undoped hexagonal SrCoO_3−δ phase, the resulting compounds present high thermal stability and an increase of the electrical conductivity. The single-cell tests for these compositions (x = 0.10 and 0.15) with La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM) as electrolyte and SrMo_0.8Fe_0.2CoO_3−δ as anode gave maximum power densities of 693 and 550 mW∙cm⁻² at 850 °C respectively, using pure H₂ as fuel and air as oxidant. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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Review

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6526 KiB

Open AccessReview

Influence of Electrode Design and Contacting Layers on Performance of Electrolyte Supported SOFC/SOEC Single Cells

by Mihails Kusnezoff, Nikolai Trofimenko, Martin Müller and Alexander Michaelis

Materials 2016, 9(11), 906; https://doi.org/10.3390/ma9110906 - 08 Nov 2016

Cited by 64 | Viewed by 8905

Abstract

The solid oxide cell is a basis for highly efficient and reversible electrochemical energy conversion. A single cell based on a planar electrolyte substrate as support (ESC) is often utilized for SOFC/SOEC stack manufacturing and fulfills necessary requirements for application in small, medium and large scale fuel cell and electrolysis systems. Thickness of the electrolyte substrate, and its ionic conductivity limits the power density of the ESC. To improve the performance of this cell type in SOFC/SOEC mode, alternative fuel electrodes, on the basis of Ni/CGO as well as electrolytes with reduced thickness, have been applied. Furthermore, different interlayers on the air side have been tested to avoid the electrode delamination and to reduce the cell degradation in electrolysis mode. Finally, the influence of the contacting layer on cell performance, especially for cells with an ultrathin electrolyte and thin electrode layers, has been investigated. It has been found that Ni/CGO outperform traditional Ni/8YSZ electrodes and the introduction of a ScSZ interlayer substantially reduces the degradation rate of ESC in electrolysis mode. Furthermore, it was demonstrated that, for thin electrodes, the application of contacting layers with good conductivity and adhesion to current collectors improves performance significantly. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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7768 KiB

Open AccessReview

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

by Nicola H. Perry and Tatsumi Ishihara

Materials 2016, 9(10), 858; https://doi.org/10.3390/ma9100858 - 21 Oct 2016

Cited by 43 | Viewed by 8539

Abstract

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I²CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. Full article

(This article belongs to the Special Issue Recent Advances in Materials for Solid Oxide Cells)

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