Special Issue "Ceramic Membranes for Fuel Cell Applications and Hydrogen Production"

A special issue of Membranes (ISSN 2077-0375). This special issue belongs to the section "Membrane Engineering and Applications".

Deadline for manuscript submissions: closed (31 December 2019).

Special Issue Editor

Dr. Sandrine Ricote
Website
Guest Editor
Department of Mechanical Engineering, Colorado School of Mines, 1500 Illinois Street, CO80401 Golden, CO, USA
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleagues,

You are warmly invited to submit your original work or a review article to this Special Issue of Membranes entitled “Ceramic Membranes for Fuel Cell Applications and Hydrogen Production”.

Over the last few decades, researchers have investigated two types of fuel cells based on ceramic membranes: Solid Oxide Fuel Cells (SOFCs) and Protonic Ceramic Fuel Cells (PCFCs). The progress has led to a decrease in the operating temperature, from 1000 to below 700 °C, a significant improvement in performance, as well as a noteworthy increase in lifetime. Ceramic-based membranes have also been developed for hydrogen production using electrolysis or gas separation. With recent discoveries and technological advances, ceramic membranes represent an alternative path for the generation of renewable energy.

The aim of this Special Issue is to provide an overview of the latest results obtained in the field and to highlight possible research directions to further advance the development of these technologies.

We are looking forward to receiving your work for this Special Issue

Prof. Sandrine Ricote
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Membranes is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • gas separation
  • fuel cell
  • ceramic membrane
  • electrolysis
  • oxygen transport membrane
  • hydrogen transport membrane

Published Papers (7 papers)

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Research

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Open AccessArticle
A Novel Laser 3D Printing Method for the Advanced Manufacturing of Protonic Ceramics
Membranes 2020, 10(5), 98; https://doi.org/10.3390/membranes10050098 - 12 May 2020
Cited by 1
Abstract
Protonic ceramics (PCs) with high proton conductivity at intermediate temperatures (300–600 °C) have attracted many applications in energy conversion and storage devices such as PC fuel/electrolysis cells, PC membrane reactors, hydrogen pump, hydrogen or water-permeable membranes, and gas sensors. One of the essential [...] Read more.
Protonic ceramics (PCs) with high proton conductivity at intermediate temperatures (300–600 °C) have attracted many applications in energy conversion and storage devices such as PC fuel/electrolysis cells, PC membrane reactors, hydrogen pump, hydrogen or water-permeable membranes, and gas sensors. One of the essential steps for fulfilling the practical utilization of these intermediate-temperature PC energy devices is the successful development of advanced manufacturing methods for cost-effectively and rapidly fabricating them with high energy density and efficiency in a customized demand. In this work, we developed a new laser 3D printing (L3DP) technique by integrating digital microextrusion-based 3D printing and precise and rapid laser processing (sintering, drying, cutting, and polishing), which showed the capability of manufacturing PCs with desired complex geometries, crystal structures, and microstructures. The L3DP method allowed the fabrication of PC parts such as pellets, cylinders, cones, films, straight/lobed tubes with sealed endings, microchannel membranes, and half cells for assembling PC energy devices. The preliminary measurement of the L3DP electrolyte film showed a high proton conductivity of ≈7 × 10−3 S/cm. This L3DP technique not only demonstrated the potential to bring the PCs into practical use but also made it possible for the rapid direct digital manufacturing of ceramic-based devices. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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Open AccessArticle
Inkjet Printed Y-Substituted Barium Zirconate Layers as Electrolyte Membrane for Thin Film Electrochemical Devices
Membranes 2019, 9(10), 131; https://doi.org/10.3390/membranes9100131 - 11 Oct 2019
Abstract
In this work, the inkjet printing of proton conducting Y-substituted barium zirconate (BZY) thin films was studied. Two different kinds of precursor inks, namely a rather molecular BZY precursor solution and a BZY nanoparticle dispersion, have been synthesized and initially investigated with regard [...] Read more.
In this work, the inkjet printing of proton conducting Y-substituted barium zirconate (BZY) thin films was studied. Two different kinds of precursor inks, namely a rather molecular BZY precursor solution and a BZY nanoparticle dispersion, have been synthesized and initially investigated with regard to their decomposition and phase formation behavior by thermal analysis, X-ray diffraction, and scanning electron microscopy. Their wetting behavior and rheological properties have been determined in order to evaluate their fundamental suitability for the inkjet process. Crystalline films have been already obtained at 700 °C, which is significantly lower compared to conventional solid-state synthesis. Increasing the temperature up to 1000 °C results in higher crystal quality. Permittivity measurements gave values of around 36 that are in good agreement with the literature while also proving the integrity of the materials. A modification of the as-synthesized BZY stock solution and nanoparticle dispersion by dilution with propionic acid improved the jetability of both inks and yielded homogeneous BZY coatings from both inks. In order to study the electrochemical properties of BZY films derived from the two printed inks, BZY coatings on sapphire substrates were prepared and characterized by electrochemical impedance spectroscopy. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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Open AccessArticle
Channelized Substrates Made from BaZr0.75Ce0.05Y0.2O3−d Proton-Conducting Ceramic Polymer Clay
Membranes 2019, 9(10), 130; https://doi.org/10.3390/membranes9100130 - 09 Oct 2019
Abstract
A novel process for producing thick protonic ceramics for use in hydrogen separation membrane reactors is demonstrated. Polymer clay bodies based on polyvinyl acetate (PVA) and mineral oil were formulated, and they permitted parts with complex architectures to be prepared by simple, low-pressure [...] Read more.
A novel process for producing thick protonic ceramics for use in hydrogen separation membrane reactors is demonstrated. Polymer clay bodies based on polyvinyl acetate (PVA) and mineral oil were formulated, and they permitted parts with complex architectures to be prepared by simple, low-pressure molding in the unfired, “green” state. Ceramic proton conductors based on doped barium zirconate/cerate, made by solid-state reactive sintering, are particularly well-suited for the polymer clay process. In this work, the ceramic proton conductor, BZCY755 (BaZr0.75Ce0.05Y0.2O3−d) was fabricated into a variety of shapes and sizes. Test coupons were produced to confirm that the polymer clay route leads to a high-quality ceramic material suitable for the demanding environment of high-temperature membrane reactors. It has been demonstrated that protonic ceramic specimens with the requisite properties are easily prepared at the laboratory scale. The polymer clay fabrication route opens up the possibility of high-volume, low-cost manufacturing at a commercial scale, by a process similar to how dinnerware and sanitary porcelain are produced today. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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Open AccessArticle
Factors Limiting the Apparent Hydrogen Flux in Asymmetric Tubular Cercer Membranes Based on La27W3.5Mo1.5O55.5−δ and La0.87Sr0.13CrO3−δ
Membranes 2019, 9(10), 126; https://doi.org/10.3390/membranes9100126 - 24 Sep 2019
Abstract
Asymmetric tubular ceramic–ceramic (cercer) membranes based on La27W3.5Mo1.5O55.5−δ-La0.87Sr0.13CrO3−δ were fabricated by a two-step firing method making use of water-based extrusion and dip-coating. The performance of the membranes was [...] Read more.
Asymmetric tubular ceramic–ceramic (cercer) membranes based on La27W3.5Mo1.5O55.5−δ-La0.87Sr0.13CrO3−δ were fabricated by a two-step firing method making use of water-based extrusion and dip-coating. The performance of the membranes was characterized by measuring the hydrogen permeation flux and water splitting with dry and wet sweep gases, respectively. To explore the limiting factors for hydrogen and oxygen transport in the asymmetric membrane architecture, the effect of different gas flows and switching the feed and sweep sides of the membrane on the apparent hydrogen permeability was investigated. A dusty gas model was used to simulate the gas gradient inside the porous support, which was combined with Wagner diffusion calculations of the dense membrane layer to assess the overall transport across the asymmetric membrane. In addition, the stability of the membrane was investigated by means of flux measurements over a period of 400 h. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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Open AccessArticle
Thermoelectric Behavior of BaZr0.9Y0.1O3−d Proton Conducting Electrolyte
Membranes 2019, 9(9), 120; https://doi.org/10.3390/membranes9090120 - 13 Sep 2019
Cited by 1
Abstract
BaZr0.9Y0.1O3-δ (BZY10), a promising proton conducting material, exhibits p-type conduction under oxidative conditions. Holes in BZY10 are of the small polaron type. However, there is no clear understanding at which places in the lattice they are localized. The [...] Read more.
BaZr0.9Y0.1O3-δ (BZY10), a promising proton conducting material, exhibits p-type conduction under oxidative conditions. Holes in BZY10 are of the small polaron type. However, there is no clear understanding at which places in the lattice they are localized. The main objectives of this work were, therefore, to discuss the nature of electronic defects in BZY10 on the basis of the combined measurements of the thermo-EMF and conductivity. Total electrical conductivity and Seebeck coefficient of BZY10 were simultaneously studied depending on partial pressures of oxygen (pO2), water (pH2O) and temperature (T). The model equation for total conductivity and Seebeck coefficient derived on the basis of the proposed defect chemical approach was successfully fitted to the experimental data. Transference numbers of all the charge carriers in BZY10 were calculated. The heat of transport of oxide ions was found to be about one half the activation energy of their mobility, while that of protons was almost equal to the activation energy of their mobility. The results of the Seebeck coefficient modeling indicate that cation impurities, rather than oxygen sites, should be considered as a place of hole localization. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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Open AccessArticle
Correlation between Concentrations of Ni and Y in Y-Doped BaZrO3 Electrolyte in Co-Sintered Cells: A Case of Controlled NiO Activity by Using MgO-NiO Solid Solution as Anode Substrate
Membranes 2019, 9(8), 95; https://doi.org/10.3390/membranes9080095 - 02 Aug 2019
Cited by 1
Abstract
BaZr0.8Y0.2O3-δ (BZY20) is promising to be applied as an electrolyte in fuel cells, electrolysis cells, etc. However, when a half cell composed of a BZY20 electrolyte layer and a BZY20-NiO composite anode substrate is co-sintered (1400–1600 °C), Ni [...] Read more.
BaZr0.8Y0.2O3-δ (BZY20) is promising to be applied as an electrolyte in fuel cells, electrolysis cells, etc. However, when a half cell composed of a BZY20 electrolyte layer and a BZY20-NiO composite anode substrate is co-sintered (1400–1600 °C), Ni diffuses from the anode substrate into the electrolyte layer. Y content in the electrolyte layer decreases dramatically, since BZY20 cannot be equilibrated with NiO at such high temperature. Such Ni diffusion and Y loss are detrimental to the electrochemical performance of the electrolyte layer. In this work, we added MgO-NiO solid solution into the anode substrate to adjust the NiO activity (aNiO) during the co-sintering process, and used three different co-sintering methods to control the BaO activity (aBaO). The results revealed that by decreasing aNiO in the system, the as-co-sintered electrolyte layer had the composition shifting towards the direction of high Y and low Ni cation ratios. A clear correlation between the intra-grain concentration of Ni and Y was confirmed. In other words, to prepare the electrolyte with the same Y cation ratio, the Ni diffusion into the electrolyte layer can be suppressed by using the MgO-NiO solid solution with a high MgO ratio and a low Ni ratio. Moreover, by increasing aBaO, we found that the Y cation ratio increased and approached the nominal value of the pristine BZY20, when Mg1−xNixO (x = 0.3 and 0.5) was used. In summary, both aNiO and aBaO play important roles in governing the composition of the electrolyte layer prepared by the co-sintering process. To evaluate the quality of the electrolyte layer, both the intra-grain Y and Ni concentrations should be carefully checked. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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Review

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Open AccessReview
Electrochemical Synthesis of Ammonia: Recent Efforts and Future Outlook
Membranes 2019, 9(9), 112; https://doi.org/10.3390/membranes9090112 - 30 Aug 2019
Cited by 4
Abstract
Ammonia is a key chemical produced in huge quantities worldwide. Its primary industrial production is via the Haber-Bosch method; a process requiring high temperatures and pressures, and consuming large amounts of energy. In the past two decades, several alternatives to the existing process [...] Read more.
Ammonia is a key chemical produced in huge quantities worldwide. Its primary industrial production is via the Haber-Bosch method; a process requiring high temperatures and pressures, and consuming large amounts of energy. In the past two decades, several alternatives to the existing process have been proposed, including the electrochemical synthesis. The present paper reviews literature concerning this approach and the experimental research carried out in aqueous, molten salt, or solid electrolyte cells, over the past three years. The electrochemical systems are grouped, described, and discussed according to the operating temperature, which is determined by the electrolyte used, and their performance is valuated. The problems which need to be addressed further in order to scale-up the electrochemical synthesis of ammonia to the industrial level are examined. Full article
(This article belongs to the Special Issue Ceramic Membranes for Fuel Cell Applications and Hydrogen Production)
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