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Laboratorium Materiałów Funkcjonalnych ETI
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Year 2023
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Brownian Motion in Optical Tweezers, a Comparison between MD Simulations and Experimental Data in the Ballistic Regime
PublicationThe four most popular water models in molecular dynamics were studied in large-scale simulations of Brownian motion of colloidal particles in optical tweezers and then compared with experimental measurements in the same time scale. We present the most direct comparison of colloidal polystyrene particle diffusion in molecular dynamics simulations and experimental data on the same time scales in the ballistic regime. The four most...
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Comparison of Cu1.3Mn1.7O4 spinels doped with Ni or Fe and synthesized via wet chemistry and solid-state reaction methods, designed as potential coating materials for metallic interconnects
PublicationThe influence of the method applied to synthesize Cu-Mn-O spinel was evaluated. The methods selected for the investigation were EDTA gel processes and solid-state reaction synthesis. From the obtained powders, sinters were prepared and assessed in terms of their properties as potential coating materials. Additionally, the influence of Ni and Fe dopants was evaluated. The results show that the EDTA gel processes method seems to...
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Evaluation of electrosynthesized reduced graphene oxide–Ni/Fe/Co-based (oxy)hydroxide catalysts towards the oxygen evolution reaction
PublicationIn this work, the specific role of the addition of graphene oxide (GO) to state-of-the-art nickel–iron (NiFe) and cobalt–nickel–iron (CoNiFe) mixed oxides/hydroxides towards the oxygen evolution reaction (OER) is investigated. Morphology, structure, and OER catalytic activity of the catalysts with and without GO were studied. The catalysts were fabricated via a two-step electrodeposition. The first step included the deposition...
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Evaluation of structural and electrical properties of multicomponent spinel oxide thin films deposited via spray pyrolysis technique
PublicationThis work reports the preparation of (Mn,Co,Fe,Ni,Cr)3O4 high-entropy spinel oxide in the form of a ~ 500 nm thin film utilising a facile spray pyrolysis technique. The structural and electrical properties of the layers were characterised after exposure to temperatures in the range of 400–900 ◦C. The as-deposited layers were amorphous, and crystallised upon heat treatment at 500 ◦C. Microstructural analyses proved a homogeneous...
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Fabrication of wormhole-like YSZ and Ni-YSZ by the novel soft-hard template CTAB/NaCl-assisted route. Suppressing Ni coalescence in SOFC
PublicationA novel one-pot synthesis route leading to the formation of a wormhole-like structure was developed for the successful fabrication of porous YSZ and Ni-YSZ systems. This method involved co-precipitation in the presence of the micelle-forming agents CTAB/Pluronic P123 and crystallising NaCl. The obtained skeletons were mechanically stable and presented almost 50% uniform, open porosity without using any additional pore-formers....
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High-temperature Corrosion of ~ 30 Pct Porous FeCr Stainless Steels in Air: Long-Term Evaluation Up to Breakaway
PublicationIn this work, a long-term (up to 6000 hours) corrosion evaluation of three porous (~ 30 pct of initial porosity) ferritic iron-chromium alloys with different Cr contents (20, 22, and 27 wt pct of Cr) was carried out at 600 C, 700 C, 800 C, and 900 C in air. Mass gain measurements and SEM analyses revealed that at temperatures above 600 C, all alloys exhibit breakaway corrosion, whereas at 600 C, none of the alloys were heavily...
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Tailoring a low-energy ball milled MnCo2O4 spinel catalyst to boost oxygen evolution reaction performance
PublicationThe development of cost-efficient oxygen evolution reaction (OER) catalysts is one of the most important tasks facing modern techniques for hydrogen production. In this work, for the first time, a low-energy ball milling process of MnCo2O4 (MCO) spinel powders, with a mechanical modification time exceeding 1 day was used. After 6 days of ball-milling, the obtained overpotential of the electrocatalyst reached the value of 375 mV...
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Tuning of eg electron occupancy of MnCo2O4 spinel for oxygen evolution reaction by partial substitution of Co by Fe at octahedral sites
PublicationTo study the effect of partial Co substitution by Fe in the B site of MnCo2O4 spinel on its physicochemical and electrochemical properties, a series of MnCo2-xFexO4 powders (x=0.125; 0.250; 0.500; 0.750; 1.000) were synthesized by means of the sol-gel method. The produced powders were characterized by powder X ray diffraction (pXRD), scanning and transmission electron microscopy (SEM & TEM) coupled with energy dispersive spectroscopy...
Year 2022
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A dual-control strategy based on electrode material and electrolyte optimization to construct an asymmetric supercapacitor with high energy density
PublicationMetal-organic frames (MOFs) are regarded as excellent candidates for supercapacitors that have attracted much attention because of their diversity, adjustability and porosity. However, both poor structural stability in aqueous alkaline electrolytes and the low electrical conductivity of MOF materials constrain their practical implementation in supercapacitors. In this study, bimetallic CoNi-MOF were synthesized to enhance the electrical...
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Cu-Doped Layered Double Hydroxide Constructs the Performance-Enhanced Supercapacitor Via Band Gap Reduction and Defect Triggering
PublicationLayered double hydroxides (LDHs) are regarded as the excellent electrode materials for supercapacitors because of their high theoretical capacitance and abundance. However, the poor conductivity and limited reaction kinetics of LDHs restrict their practical application severely. Herein, Cu is chosen from groups VIII/IB/IIB as dopants for Co-based LDH (CuCo-LDH). The designed metal–organic framework-derived hierarchical CuCo-LDH...
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Effectiveness of a dual surface modification of metallic interconnects for application in energy conversion devices
PublicationA dual surface modification of an SOFC metallic interconnect with a Gd2O3 layer and an MnCo2O4 coating was evaluated. The tested samples were oxidized for 7000 h in air at 1073 K. Oxidation products were characterized using XRD, SEM-EDS, and confocal Raman imaging, and ASR was measured. The effect of gadolinium segregation at grain boundaries in Cr2O3 was evaluated using S/TEM-EDS. Area specific-resistance was measured and fuel...
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Effects of La0.8Sr0.2MnO3 and Ag electrodes on bismuth-oxide-based low-temperature solid electrolyte oxygen generators
PublicationIn this study, La0.8Sr0.2MnO3 (LSM) was used as the ceramic electrode in a (Bi1.50Y0.50)0.98Zr0.04O3+δ (BYO)-based solid electrolyte oxygen generator (SEOG) and its performance was compared with that of a previously studied high-fire Ag electrode. Among La0.6Sr0.4Co0.2Fe0.8O3, LaNi0.6Fe0.4O3, Cu1.4Mn1.6O4, and LSM materials, only LSM materials did not trigger any chemical reaction or interdiffusion with BYO at temperatures up to...
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Effects of Ni-NCAL and Ni–Ag electrodes on the cell performances of low-temperature solid oxide fuel cells with Sm0.2Ce0·8O2-δ electrolyte at various temperatures
PublicationThree low-temperature solid oxide fuel cells are built using Sm0.2Ce0·8O2-δ (SDC) as the electrolyte. Cell A is symmetrical and features Ni–LiNi0.8Co0·15Al0·05O2 (Ni–NCAL) electrodes, Cell B comprises a Ni–NCAL anode and a Ni–Ag cathode, and Cell C is fabricated using a Ni–NCAL cathode and a Ni–Ag anode. The ohmic resistance and polarization resistance (Rp) of Cells B and C are significantly higher than those of Cell A. The reduction...
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Electrolytic deposition of reactive element thin films on Crofer 22 APU and evaluation of the resulting high-temperature corrosion protection properties at 700 °C–900 °C
PublicationThis article presents electrolytic deposition of thin Rare Earth (RE) coatings on Crofer 22 APU stainless steel substrates for high temperature applications, such as interconnects in solid oxide cell stacks. The deposition of coatings based on yttrium-, gadolinium-, lanthanum-, and cerium nitrates is discussed. The high temperature corrosion properties of surface-modified steels were examined using thermogravimetry and electrical...
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Electrophoretic co-deposition of Mn1.5Co1.5O4, Fe2O3 and CuO: Unravelling the effect of simultaneous addition of Cu and Fe on the microstructural, thermo-mechanical and corrosion properties of in-situ modified spinel coatings for solid oxide cell interconnects
PublicationA systematic microstructural, thermo-mechanical and electrical characterization of simultaneous Fe–Cu doped Mn–Co spinel coatings processed by electrophoretic co-deposition on Crofer 22 APU is here reported and discussed. An innovative approach for the simultaneous electrophoretic deposition of three spinel precursors is designed, conceived and optimised, with the aim of outlining time- and energy-saving spinel modification routes....
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Glass-ceramic joining of Fe22Cr porous alloy to Crofer22APU: interfacial issues and mechanical properties
PublicationThis work deals with the joining of porous Fe22Cr ferritic stainless steel to a dense Crofer22APU plate by using a silica-based, Ba-containing glass-ceramic. The chemical and interfacial stability and the mechanical properties of the joints were evaluated before and after thermal ageing at 700 ◦C for 500hrs. The sintering behaviour of the glass was assessed by using heating stage microscopy (HSM) to study the influence of a porous...
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High-performance anode-supported solid oxide fuel cells with co-fired Sm0.2Ce0.8O2-δ/La0.8Sr0.2Ga0.8Mg0.2O3−δ/Sm0.2Ce0.8O2-δ sandwiched electrolyte
PublicationIn this study, intermediate-temperature solid oxide fuel cells (IT-SOFCs) with a nine-layer structure are constructed via a simple method based on the cost-effective tape casting-screen printing-co-firing process with the structure composed of a NiO-based four-layer anode, a Sm0.2Ce0·8O2-δ(SDC)/La0·8Sr0.2Ga0.8Mg0·2O3−δ (LSGM)/SDC tri-layer electrolyte, and an La0·6Sr0·4Co0·2Fe0·8O3-δ (LSCF)-based bi-layer cathode. The resultant...
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High-temperature Co-electrolysis of CO2/H2O and direct methanation over Co-impregnated SOEC. Bimetallic synergy between Co and Ni
PublicationTo study the synergy between the transition metals for enhancing the electrochemical and chemical activity, a series of SOECs were modified with a small amount of Co ions, namely 1.8, 3.6, and 5.4 wt% in the reduced state. The addition of βCD into the precursor solution allowed for extremely fine dispersion of Co species across the Ni-YSZ cermet structure. The sample containing 3.6 wt% Co reached an outstanding over 2.5-times-higher...
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Morphology changes in Fe-Cr porous alloys upon high-temperature oxidation quantified by X-ray tomographic microscopy
PublicationThe effect of high-temperature oxidation at 850 C (10 h, 30 h, 100 h) and 900 C (10 h) on porous (30 % porosity) ferritic stainless steel (Fe22Cr) has been investigated using synchrotron tomographic microscopy, which allowed for visualisation, separation and quantitative analysis of the metallic core, closed pores, open pores and oxide scale phase. The same regions within the samples were investigated before and after oxidation...
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Physical and sealing properties of BaO–Al2O3–SiO2–CaO–V2O5 glasses for solid oxide fuel cell applications
PublicationIn this study, the properties of BaO–Al2O3–SiO2 (SAB) glasses incorporated with CaO and V2O5 as the network modifier and additive, respectively, are evaluated. The electrical resistivities of the glasses decrease upon the addition of CaO but increase upon increasing their V2O5 content because the V5+ species lower the ionic mobility of the glasses. The addition of V2O5 improves the wettability of the glasses on the Crofer 22 APU...
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Physicochemical properties of Mn1.45Co1.45Cu0.1O4 spinel coating deposited on the Crofer 22 H ferritic steel and exposed to high-temperature oxidation under thermal cycling conditions
PublicationThe Crofer 22 H ferritic steel substrate was coated with an Mn1.45Co1.45Cu0.1O4 spinel by means of electrophoresis. After high-temperature oxidation under thermal cycling conditions, the physicochemical properties of the obtained system were evaluated. During 48-h cycles that involved heating the samples up to temperatures of either 750 or 800 °C, the oxidation kinetics of both coated and unmodified steel approximately obeyed...
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Preparation of methanation catalysts for high temperature SOEC by β-cyclodextrin-assisted impregnation of nano-CeO2 with transition metal oxides
PublicationThe aim of this work was to prepare and examine the catalytic activity of nanometric CeO2 decorated with transition metal oxides – Ni, Co, Cu, Fe and Mn – towards a high-temperature methanation process under SOEC CO2/H2O simulated co-electrolysis conditions. Samples were prepared using the wet impregnation method via the conventional process and with the addition of native cyclodextrin. The influence of β-cyclodextrin (βCD) onto...
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Tetrahedrally modified MnMe0.1Co1.9O4 (Me = Zn, Mg, Li) spinels for non-enzymatic glucose sensing
PublicationIn this work, tetrahedrally modified MnMe0.1Co1.9O4 (Me = Zn, Mg, Li) spinels were prepared via the sol–gel synthesis method with subsequent ball-milling fragmentation. The prepared samples were evaluated as glucose–sensing catalyst. The reference MnCo2O4 spinel exhibited a sensitivity of 49 µA mM−1 cm−2 and a nonlinearity error of 5.2% in the response range from 0.02 to 1 mM. The partial substitution of cobalt in the reference...
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Tuning Electrochemical Performance by Microstructural Optimization of the Nanocrystalline Functional Oxygen Electrode Layer for Solid Oxide Cells
PublicationFurther development of solid oxide fuel cell (SOFC) oxygen electrodes can be achieved through improvements in oxygen electrode design by microstructure miniaturisation alongside nanomaterials implementation. In this work, improved electrochemical performance of an La0.6Sr0.4Co0.2Fe0.8O3-d (LSCF) cathode was achieved by the controlled modification of the La0.6Sr0.4CoO3-d (LSC) nanocrystalline interlayer introduced between a porous...
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Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction Using Deep Eutectic Solvents (DESs) for Neutral Red Dye Spectrophotometric Determination
PublicationDeep eutectic solvents (DES), which have low toxicity and are low cost, biodegradable, and easily synthesized, were used for the extraction of neutral red (NR) dye before its spectrophotometric analysis. DES, containing choline chloride as a hydrogen bond acceptor and phenol as a hydrogen bond donor with a molar ratio of 1:2, was used for the extraction of NR dye from aqueous media. The possible interaction of different DESs with...
Year 2021
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Gigantic electro-chemo-mechanical properties of nanostructured praseodymium doped ceria
PublicationSome oxygen defective fluorites are non-Newnham electrostrictors, i.e., the electromechanical response does not depend on their dielectric properties. Here, we show gigantic electrostriction in nanocrystalline 25 mol% praseodymium doped ceria (PCO) bulk ceramics. The material was fabricated with a fieldassisted spark plasma sintering (SPS) process from high-purity nanoscale PCO powders (<20 nm). The SPS process consolidates the...
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Glass-ceramic sealants and steel interconnects: accelerated interfacial stability and reactivity tests at high temperature
PublicationHigh-temperature reactions between glass-ceramic sealants and Fe-Cr alloy interconnects may lead to the formation of undesirable phases, and consequently degradation of solid oxide fuel/electrolyser devices. In this work, three different glass-ceramic sealants (Na-containing, Ba-containing, Sr-containing compositions) and Fe22Cr stainless steel powders (raw and pre-oxidised) are considered in order to test their chemical reactivity...
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High temperature corrosion evaluation and lifetime prediction of porous Fe22Cr stainless steel in air in temperature range 700–900 °C
PublicationThis work describes a high temperature corrosion kinetics study of ~30% porous Fe22Cr alloys. The surface area of the alloy (~0.02 m2 g-1) has been determined by tomographic microscopy. The weight gain of the alloys was studied by isothermal thermogravimetry in the air for 100 hours at 700 - 900 °C. Breakaway oxidation was observed after oxidation at 850 °C (~100 hours) and 900 °C (~30 hours). The lifetime prediction shows the...
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High-performance NdSrCo2O5+δ–Ce0.8Gd0.2O2-δ composite cathodes for electrolyte-supported microtubular solid oxide fuel cells
PublicationNdSrCo2O5+δ (NSCO) is a perovskite with an electrical conductivity of 1551.3 S cm−1 at 500 °C and 921.7 S cm−1 at 800 °C and has a metal-like temperature dependence. This perovskite is used as the cathode material for Ce0.8Gd0.2O2-δ (GDC)-supported microtubular solid oxide fuel cells (MT-SOFCs). The MT-SOFCs fabricated in this study consist of a bilayer anode, comprising a NiO–GDC composite layer and a NiO layer, and a NSCO–GDC...
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Improvement of Oxygen Electrode Performance of Intermediate Temperature Solid Oxide Cells by Spray Pyrolysis Deposited Active Layers
PublicationIntermediate temperature solid oxide fuel cells oxygen electrodes are modified by active interfacial layers. Spray pyrolysis is used to produce thin (≈500 nm) layers of mixed ionic and electronic conductors: Sm0.5Sr0.5CoO3−δ (SSC), La0.6Sr0.4CoO3−δ (LSC), La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF), and Pr6O11 (PrOx) on the electrode–electrolyte interface. The influence of the annealing temperature on the electrode polarization (area specific...
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Influence of Gd deposition on the oxidation behavior and electrical properties of a layered system consisting of Crofer 22 APU and MnCo2O4 spinel
PublicationIn the study, the surface of the Crofer 22APU ferritic steel was modified with gadolinium oxide nanoparticles and a protective-conducting layer consisting of the MnCo2O4 spinel. This system was studied in the context of application in IT-SOFC interconnects. Four types of samples were studied: unmodified steel, steel coated with a manganese-cobalt spinel layer, steel modified with gadolinium oxide nanoparticles, and a system consisting...
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Manganese–Cobalt Based Spinel Coatings Processed by Electrophoretic Deposition Method: The Influence of Sintering on Degradation Issues of Solid Oxide Cell Oxygen Electrodes at 750 °C
PublicationThis paper seeks to examine how the Mn–Co spinel interconnect coating microstructure can influence Cr contamination in an oxygen electrode of intermediate temperature solid oxide cells, at an operating temperature of 750 °C. A Mn–Co spinel coating is processed on Crofer 22 APU substrates by electrophoretic deposition, and subsequently sintered, following both the one-step and two-step sintering, in order to obtain significantly...
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Mn-Co spinel coatings on Crofer 22 APU by electrophoretic deposition: Up scaling, performance in SOFC stack at 850 °C and compositional modifications
PublicationCeramic coatings for metallic interconnects play a key role in limiting corrosion and chromium evaporation in solid oxide cells. This study presents the upscaling of the electrophoretic deposition (EPD) technique to process Mn-Co spinels on real-dimension Crofer 22 APU interconnects and the test in a SOFC stack. Area specific resistance of long-term test conducted for 5000 h at 850 °C demonstrated that two-steps sintering has a...
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Recent advances on spinel-based protective coatings for solid oxide cell metallic interconnects produced by electrophoretic deposition
PublicationThe application of ceramic protective coatings to the metallic interconnects in solid oxide cells (SOCs) is a viable and effective method to limit interconnect degradation issues. This featured letter provides a critical overview of the main outcomes of current research on the use of the electrophoretic deposition (EPD) technique to produce protective coatings for SOC metallic interconnects, specifically focusing on different approaches...
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The Effect of Cobalt Incorporation into Nickel–Iron Oxide/(oxy)hydroxide Catalyst on Electrocatalytic Performance Toward Oxygen Evolution Reaction
PublicationThis work presents a study on the influence of the addition of cobalt into state-of-the-art nickel–iron (NiFe) mixed oxides/hydroxides/(oxy)hydroxides on their structural and morphological properties, and oxygen evolution reaction (OER) catalytic activity. A one-step electrodeposition process is performed without any additives to fabricate NiFe and x cobalt-doped nickel/iron (xCoNiFe) layer-double-hydroxide catalysts directly on...
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The effect of Fe on chemical stability and oxygen evolution performance of high surface area SrTix-1FexO3-δ mixed ionic-electronic conductors in alkaline media
PublicationDevelopment of environmentally friendly, high performing oxygen evolution reaction (OER) catalysts is an important research challenge. In this work, iron doped strontium titanates with a general formula SrTi1-xFexO3-δ (x = 0.35, 0.50, 0.70, 0.90, and 1.00) denoted as STFx, were synthesized via a solid state reaction technique and characterized in terms of oxygen evolution reaction electrocatalysis in an alkaline electrolyte (0.1...
Year 2020
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Effects of Ca2+, Mg2+, Na+, and K+ substitutions on the microstructure and electrical properties of GdCoO3 ceramics
PublicationGdCoO3-δ, Gd0.975Na0.025CoO3-δ, Gd0.98K0.02CoO3-δ, Gd0.98Ca0.02CoO3-δ, and GdCo0.99Mg0.01O3-δ ceramics were prepared via a solid-state reaction route. Among the dopants studied, substitution with Ca2+ slightly enhanced the densfication of GdCoO3 ceramics. All the lattice parameters of the doped ceramics were larger than those of pure GdCoO3-δ ceramic (a = 5.223 Å, b = 5.389 Å and c = 7.451 Å), and their cell volumes increased by...
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Structural and catalytic properties of ceria layers doped with transition metals for SOFCs fueled by biogas
PublicationThe aim of this paper was to investigate an influence of the nanocrystalline Ce0.8A0.2O2-δ (A = Mn, Fe, Co, Ni, Cu) materials on the direct internal reforming of biogas in SOFC. Structural analysis of fabricated compounds has been done. An in-situ analysis of a composition of outlet gases from operating SOFC was performed using FTIR spectroscopy with simultaneous electrical tests. It was found out, that type of dopant strongly...
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The Influence of the Electrodeposition Parameters on the Properties of Mn-Co-Based Nanofilms as Anode Materials for Alkaline Electrolysers
PublicationIn this work, the influence of the synthesis conditions on the structure, morphology, and electrocatalytic performance for the oxygen evolution reaction (OER) of Mn-Co-based films is studied. For this purpose, Mn-Co nanofilm is electrochemically synthesised in a one-step process on nickel foam in the presence of metal nitrates without any additives. The possible mechanism of the synthesis is proposed. The morphology and structure...
Year 2019
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9 - Solid oxide fuel and electrolysis cells
PublicationIn this chapter, the fundamental reactions, the geometrical designs, the material requirements, and the status of SOFCs and SOECs are presented. In the following seven chapters, the most important components of an SOC are described and the chapter ends with a summary and outlook. The described components are: (i) oxygen-ion conductors (electrolyte), (ii) anode materials for SOFCs (cathode in SOEC mode), (iii) cathode materials...
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Effects of Na+, K+ and B3+ Substitutions on the Electrical Properties of La10Si6O27 Ceramics
PublicationDoping of Na and K at La sites and of B at Si site in La10Si6O27 with oxyapatite structure and fabrication of their ceramics were made by solid-state reaction method. It was found that partial substitution of Na+ and K+ on La sites decreased the sinterability of the La10Si6O27 based ceramics, whereas partial substitution of B3+ on Si site imporved the sinterability. Na+ and K+ substitutions in La10-xNaxSi6O27-x and La10-xKxSi6O27-x...