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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Sintering of BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) with/without SrTiO3 Dopant

The perovskite composition, BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta), displays excellent protonic conduction at high temperatures making it a desirable candidate for hydrogen separation membranes. This paper reports on the sintering behavior of BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) powders doped with SrTiO3. Two methods were used to synthesize BaCe(sub 0.85)Y(sub 0.15)O(sub 3-delta) powders: (1) solid state reaction and (2) wet chemical co-precipitation. Co-precipitated powder crystallized into the perovskite phase at 1000 C for 4 hrs. Complete reaction and crystallization of the perovskite phase by solid state was achieved by calcining at 1200 C for 24 hrs. Solid state synthesis produced a coarser powder with an average particle size of 1.3 microns and surface area of 0.74 sq m/g. Co-precipitation produced a finer powder with a average particle size of 65 nm and surface area of 14.9 sq m/g. Powders were doped with 1, 2, 5, and 10 mole % SrTiO3. Samples were sintered at 1450 C, 1550 C and 1650 C. SrTiO3 enhances sintering, optimal dopant level is different for powders synthesized by solid state and co-precipitation. Both powders exhibit similar grain growth behavior. Dopant levels of 5 and 10 mole % SrTiO3 significantly enhances the grain size.

Dynys, F.↗
NASA NTRS2006

Pulsed Laser Deposition of BaCe(sub 0.85)Y(sub 0.15)0(sub 3) FILMS

Pulsed laser deposition has been used to grow nanostructured BaCe(sub 0.85)Y(sub 0.15)0(sub 3) films. The objective is to enhance protonic conduction by reduction of membrane thickness. Sintered samples and laser targets were prepared by sintering BaCe(sub 0.85)Y(sub 0.15)O(sub 3) powders derived by solid state synthesis. Films 2 to 6 m thick were deposited by KrF excimer laser on Si and porous Al2O3 substrates. Nanocrystalline films were fabricated at deposition temperatures of 600-800 C deg at O2 pressure of 30 mTorr and laser fluence of 1.2 J/cm square. Films were characterized by x-ray diffraction, scanning electron microscopy and electrical impedance spectroscopy. Dense single phase BaCe(sub 0.85)Y((sub 0.15) 0(sub 3) films with a columnar growth morphology is observed, preferred crystal growth was found to be dependent upon deposition temperature and substrate type. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 C deg to 900 C deg in moist argon. Electrical conduction of the fabricated films was 1 to 4 orders of magnitude lower than the sintered bulk samples. With respect to the film growth direction, activation energy for electrical conduction is 3 times higher in the perpendicular direction than the parallel direction.

Dynys, F. W.↗
DOE OSTI2020

Materials Data on BaCe(SnS3)2 by Materials Project

BaCe(SnS3)2 crystallizes in the orthorhombic Pmc2_1 space group. The structure is three-dimensional. there are two inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 9-coordinate geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.17–3.65 Å. In the second Ba2+ site, Ba2+ is bonded in a distorted q6 geometry to nine S2- atoms. There are a spread of Ba–S bond distances ranging from 3.27–3.53 Å. There are two inequivalent Ce4+ sites. In the first Ce4+ site, Ce4+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Ce–S bond distances ranging from 2.86–3.04 Å. In the second Ce4+ site, Ce4+ is bonded in a 8-coordinate geometry to eight S2- atoms. There are a spread of Ce–S bond distances ranging from 2.87–3.23 Å. There are four inequivalent Sn3+ sites. In the first Sn3+ site, Sn3+ is bonded to five S2- atoms to form distorted SnS5 square pyramids that share corners with two equivalent SnS5 trigonal bipyramids, edges with two equivalent SnS6 octahedra, and edges with two equivalent SnS5 square pyramids. There are a spread of Sn–S bond distances ranging from 2.78–3.01 Å. In the second Sn3+ site, Sn3+ is bonded to six S2- atoms to form SnS6 octahedra that share edges with two equivalent SnS6 octahedra and edges with two equivalent SnS5 square pyramids. There are a spread of Sn–S bond distances ranging from 2.57–2.69 Å. In the third Sn3+ site, Sn3+ is bonded to five S2- atoms to form corner-sharing SnS5 trigonal bipyramids. There are a spread of Sn–S bond distances ranging from 2.48–2.57 Å. In the fourth Sn3+ site, Sn3+ is bonded to five S2- atoms to form corner-sharing SnS5 trigonal bipyramids. There are a spread of Sn–S bond distances ranging from 2.44–2.61 Å. There are twelve inequivalent S2- sites. In the first S2- site, S2- is bonded to two equivalent Ba2+ and three Sn3+ atoms to form distorted SBa2Sn3 square pyramids that share corners with eight SBa2Ce2Sn square pyramids, edges with five SBa2Sn3 square pyramids, and a faceface with one SBa2Ce2Sn square pyramid. In the second S2- site, S2- is bonded to two equivalent Ba2+, two equivalent Ce4+, and one Sn3+ atom to form distorted SBa2Ce2Sn square pyramids that share corners with nine SBa2Sn3 square pyramids, edges with five SBa2Sn3 square pyramids, and a faceface with one SBa2Ce2Sn square pyramid. In the third S2- site, S2- is bonded to two equivalent Ba2+, two equivalent Ce4+, and one Sn3+ atom to form distorted SBa2Ce2Sn square pyramids that share corners with eight SBa2Sn3 square pyramids, edges with five SBa2Ce2Sn square pyramids, and a faceface with one SBa2Sn3 square pyramid. In the fourth S2- site, S2- is bonded in a trigonal non-coplanar geometry to two equivalent Ce4+ and one Sn3+ atom. In the fifth S2- site, S2- is bonded in a 5-coordinate geometry to two equivalent Ba2+, one Ce4+, and two equivalent Sn3+ atoms. In the sixth S2- site, S2- is bonded in a distorted see-saw-like geometry to one Ce4+ and three Sn3+ atoms. In the seventh S2- site, S2- is bonded in a 4-coordinate geometry to one Ba2+, one Ce4+, and two equivalent Sn3+ atoms. In the eighth S2- site, S2- is bonded in a 2-coordinate geometry to one Ba2+, one Ce4+, and two equivalent Sn3+ atoms. In the ninth S2- site, S2- is bonded to two equivalent Ba2+, two equivalent Ce4+, and one Sn3+ atom to form a mixture of distorted corner and edge-sharing SBa2Ce2Sn square pyramids. In the tenth S2- site, S2- is bonded to two equivalent Ba2+, two equivalent Ce4+, and one Sn3+ atom to form a mixture of distorted corner, edge, and face-sharing SBa2Ce2Sn square pyramids. In the eleventh S2- site, S2- is bonded to two equivalent Ba2+ and three Sn3+ atoms to form a mixture of corner and edge-sharing SBa2Sn3 square pyramids. In the twelfth S2- site, S2- is bonded to two equivalent Ba2+, two equivalent Ce4+, and one Sn3+ atom to form distorted SBa2Ce2Sn square pyramids that share corners with ten SBa2Sn3 square pyramids, edges with five SBa2Ce2Sn square pyramids, and faces with two SBa2Ce2Sn square pyramids.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Probing Electronic and Structural Transformations during Thermal Reduction of the Promising Water Splitting Perovskite BaCe 0.25 Mn 0.75 O 3

Here, in this report, we investigate the thermal reduction of the octahedral perovskite BaCe 0.25 Mn 0.75 O 3 (BCM) using in situ electron energy loss spectroscopy (EELS) in an aberration-corrected transmission electron microscope (TEM). The 12R-polytype of BCM is known to demonstrate high solar thermochemical hydrogen production capacity. In situ EELS measurements show that Mn is the active redox cation in BCM, undergoing thermal reduction from Mn 4+ to Mn 3+ during heating to 700 °C inside the TEM under a high vacuum. The progressive reduction of Mn 4+ during oxygen vacancy (O v ) formation was monitored as a function of temperature. Additionally, atomic-resolution scanning transmission electron microscopy identified two different types of twin boundaries present in the oxidized and reduced form of 12R-BCM, respectively. These two types of twin boundaries were shown, via computational modeling, to modulate the site-specific O v formation energies in 12R-BCM. It is concluded that these types of atomic defects provide sites more energetically favorable for O v formation during thermal reduction.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Investigating the Electronic Structure of Prospective Water-Splitting Oxide BaCe 0.25 Mn 0.75 O 3-δ before and after Thermal Reduction

BaCe 0.25 Mn 0.75 O 3-δ (BCM), a non-stoichiometric oxide with a layered perovskite-like crystal structure, has recently emerged as a prospective contender for application in renewable energy harvesting by solar thermochemical hydrogen generation. Using solar-thermal energy and a reducing environment, oxygen vacancies can be created in high-temperature BCM, and the reduced crystal so obtained can, in turn, produce H 2 by stripping oxygen from H 2 O. Therefore, a first step toward understanding the working mechanism and optimizing the performance of BCM is a thorough and comparative analysis of the electronic structure of the pristine and the reduced material. In this paper, we probe the electronic structure of BCM using the combined effort of first-principles calculations and experimental O K-edge X-ray absorption spectroscopy (XAS). The computed projected density of states (PDOS) and orbital plots are used to propose a simplified model for orbital mixing between the oxygen and metal atoms. With the help of state-of-the-art simulations, we are able to find the origins of the XAS peaks and categorize them on the basis of contribution from Ce and Mn. For the reduced crystal, the calculations show that the change in electron density resulting from the reduction is strongly localized around the oxygen vacancy. Experimental measurements reveal a marked lowering of the first O K-edge peak in the reduced crystal. Using theoretical analysis, this is shown to result from lifting of spin degeneracy in the absorption peaks as well as from a diminished O 2p contribution to the frontier unoccupied orbitals, in accordance with the tight binding scheme. The simulated results serve as a reference for the extent of spectral change as a function of the percentage of oxygen vacancies in the reduced crystal. Here, our study paves the way for the investigation of the working mechanism of BCM and for computational and experimental efforts aimed at design and discovery of efficient water-splitting oxides.

08 HYDROGEN↗
DOE OSTI2022

Synthesis and structure of high-purity BaCe 0.25 Mn 0.75 O 3 : an improved material for thermochemical water splitting

Solar thermochemical hydrogen production (STCH) via redox-active metal oxides is an approach for direct solar-driven hydrogen generation typically using a high-temperature redox cycle involving refractory oxides and steam. Typical cycles involve high-temperature reduction of oxides to form oxygen vacancies, followed by lower temperature reaction between oxygen vacancies and steam where the oxide is re-oxidized and the steam is reduced to hydrogen. Only a few materials have demonstrated reversible cycling under the typically harsh STCH conditions (e.g. 1500°C reduction, 900°C re-oxidation) and critical questions remain on the true reversibility of non-stoichiometric multi-cation oxide systems, significantly hampered by the lack of single-phase samples for these material systems. To date, most STCH processes have relied on CeO 2 as a benchmark active material, but more recently, the 12R phase of BaCe 0.25 Mn 0.75 O 3 (BCM) has demonstrated greater hydrogen-generation potential at lower peak temperatures. However, previous reports of 12R-BCM have included large fractions, > 10 wt%, of secondary phases, which complicate analysis of the stability and performance. A comprehensive understanding of the redox mechanism and reversibility of the process in BCM can only be achieved with nearly single-phase samples which, to date, have been difficult to produce. Here two approaches to BCM synthesis are reported: solid state and sol–gel-based routes. It is demonstrated that both routes can be tuned to produce the 12R structure with > 97 wt% yield when annealed ≥1450°C. Herein synchrotron-based diffraction measurements of rhombohedral 12R-BCM enabled characterization of the anisotropy between thermal expansion along the c-axis and within the ab plane. The impact of high-temperature redox cycling on the stability and phase fraction of the 12R-BCM polytype was also investigated. Our results offer two viable routes for synthesis of high-purity 12R-BCM critically needed for evaluating the efficacy of BCM as a STCH material and validate its ability to split water at lower temperatures over extended numbers of redox cycles.

08 HYDROGEN↗
DOE OSTI2022

Insight of BaCe 0.5 Fe 0.5 O 3– δ twin perovskite oxide composite for solid oxide electrochemical cells

One-pot synthesized twin perovskite oxide composite of BaCe 0.5 Fe 0.5 O 3–δ (BCF), comprising cubic and orthorhombic perovskite phases, shows triple-conducting properties for promising solid oxide electrochemical cells. Phase composition evolution of BCF under various conditions was systematically investigated, revealing that the cubic perovskite phase could be fully/partially reduced into the orthorhombic phase under certain conditions. The reduction happened between the two phases at the interface, leading to the microstructure change. As a result, the corresponding apparent conducting properties also changed due to the difference between predominant conduction properties for each phase. Based on the revealed phase composition, microstructure, and electrochemical properties changes, a deep understanding of BCF's application in different conditions (oxidizing atmospheres, reducing/oxidizing gradients, cathodic conditions, and anodic conditions) was achieved. Triple-conducting property (H + /O 2– /e – ), fast open-circuit voltage response (~16–~470 mV) for gradients change, and improved single-cell performance (~31% lower polarization resistance at 600°C) were comprehensively demonstrated. Besides, the performance was analyzed under anodic conditions, which showed that the microstructure and phase change significantly affected the anodic behavior.

08 HYDROGEN↗
DOE OSTI2023

Understanding Chemo-Mechanical Stability of Protonic Ceramic Cells Through Electronic Conduction in the BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ Electrolyte

BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3-δ (BCZYYb) is a promising ceramic electrolyte for reversible protonic ceramic cells. It is reported that BCZYYb-based cells show excellent long-term durability, particularly in the electrolysis mode, in contrast to the cells based on the conventional electrolyte yttria-stabilized zirconia. In this study, we investigate the chemo-mechanical stability behavior (a low tendency of delamination) of the BCZYYb-based protonic ceramic cells in terms of local electronic conduction in the electrolyte. The local electronic conductivity of the BCZYYb electrolyte is determined using Pt-probe-embedded cells near each electrode interface. The BCZYYb electrolyte exhibits sufficient p-type conductivity (∼10 −3 S cm −1 ) near the oxygen electrode (corresponding p O 2 : 5.27–21 × 10 −2 atm) and n-type conductivity (∼10 −4 S cm −1 ) near the hydrogen electrode (corresponding p O 2 : 0.99–1.30 × 10 −24 atm) at 600 °C. A standard cell is prepared and tested over long-term in the fuel cell (at positive and negative voltages) and electrolysis modes. The cell exhibits stable performance without delamination or cracks in both operating modes, owing to local electronic conduction.

Electrochemistry↗
NASA NTRS2004

Sintering of BaCe(0.85)Y(0.15)O3-(Beta) With/Without SrTiO Dopant

The sintering behavior of BaCe(0.85)Y(0.15)O3-(Beta) doped with SrTiO is described. Complete reaction and crystallization of perovskite phase by solid state was achieved by calcining at 1200 degrees C for 24 hours.Smaples were sintered at 1450 degrees C, 1550 degrees C, and 1650 degrees C. SrTiOsub3 enhanced sintering, while optimal dopant level was different for powders synthesized by solid state and co-precipitation. Both powders exhibit similar grain growth behavior.

Dynys, Fred↗
DOE OSTI2020

Materials Data on BaCe by Materials Project

BaCe1 crystallizes in the orthorhombic Amm2 space group. The structure is three-dimensional. Ba is bonded to six equivalent Ba and six equivalent Ce atoms to form BaBa6Ce6 cuboctahedra that share corners with eighteen equivalent BaBa6Ce6 cuboctahedra, edges with six equivalent BaBa6Ce6 cuboctahedra, edges with twelve equivalent CeBa6Ce6 cuboctahedra, faces with eight equivalent BaBa6Ce6 cuboctahedra, and faces with twelve equivalent CeBa6Ce6 cuboctahedra. There are two shorter (3.91 Å) and four longer (3.93 Å) Ba–Ba bond lengths. All Ba–Ce bond lengths are 4.01 Å. Ce is bonded to six equivalent Ba and six equivalent Ce atoms to form CeBa6Ce6 cuboctahedra that share corners with eighteen equivalent CeBa6Ce6 cuboctahedra, edges with six equivalent CeBa6Ce6 cuboctahedra, edges with twelve equivalent BaBa6Ce6 cuboctahedra, faces with eight equivalent CeBa6Ce6 cuboctahedra, and faces with twelve equivalent BaBa6Ce6 cuboctahedra. There are two shorter (3.91 Å) and four longer (3.93 Å) Ce–Ce bond lengths.

36 MATERIALS SCIENCE↗
NASA NTRS2006

Pulsed Laser Deposition of High Temperature Protonic Films

Pulsed laser deposition has been used to fabricate nanostructured BaCe(0.85)Y(0.15)O3- sigma) films. Protonic conduction of fabricated BaCe(0.85)Y(0.15)O(3-sigma) films was compared to sintered BaCe(0.85)Y(0.15)O(3-sigma). Sintered samples and laser targets were prepared by sintering BaCe(0.85)Y(0.15)O(3-sigma) powders derived by solid state synthesis. Films 1 to 8 micron thick were deposited by KrF excimer laser on porous Al2O3 substrates. Thin films were fabricated at deposition temperatures of 700 to 950 C at O2 pressures up to 200 mTorr using laser pulse energies of 0.45 - 0.95 J. Fabricated films were characterized by X-ray diffraction, electron microscopy and electrical impedance spectroscopy. Single phase BaCe(0.85)Y(0.15)O(3-sigma) films with a columnar growth morphology are observed with preferred crystal growth along the [100] or [001] direction. Results indicate [100] growth dependence upon laser pulse energy. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 C to 900 C. Electrical conduction behavior was dependent upon film deposition temperature. Maximum conductivity occurs at deposition temperature of 900 oC; the electrical conductivity exceeds the sintered specimen. All other deposited films exhibit a lower electrical conductivity than the sintered specimen. Activation energy for electrical conduction showed dependence upon deposition temperature, it varied

Dynys, Fred W.↗
DOE OSTI2026

Improving protonic ceramic electrochemical cell performance via a dual-phase reaction-sintered bilayer electrolyte

Protonic ceramic electrochemical cells (PCCs) are promising energy conversion devices, but their fabrication remains challenging. In particular, the typical electrolytes for PCCs such as BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3−δ (7111) and BaCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3−δ (4411) suffer from intrinsic barium evaporation issues during high-temperature sintering. This tendency towards barium loss, combined with their highly refractory nature, leads to a tradeoff between sinterability and chemical stability. To address this tradeoff, we propose a bilayer electrolyte combining layers of 4411 and 7111 materials that is designed to enhance sinterability and conductivity through dual-phase reactive sintering. Our findings demonstrate that the bilayer structure exhibits shrinkage behavior closely matched to that of the fuel electrode substrate, with a higher shrinkage compared to a single-layer 4411 electrolyte. Utilizing this bilayer electrolyte structure, our PCCs achieve a peak power density of 637 mW∙cm −2 in fuel-cell mode and a current density of 1060 mA∙cm −2 at 1.3 V in electrolysis mode at 600 °C. Our PCCs demonstrate high Faradaic efficiency of 83% at 1.3 V and 500 °C. Hybrid distribution of relaxation times (DRT) polarization mapping further reveals that the bilayer structure reduces Ohmic and polarization resistance in both fuel-cell and electrolysis modes.

ceramic processing↗
DOE OSTI2023

Materials Design Directions for Solar Thermochemical Water Splitting

The sustainable, economical production of molecular hydrogen is a crucial component of a net zero-greenhouse-gas-emissions future. Solar thermochemical water splitting (STWS) offers a renewable route to hydrogen with the potential to help decarbonize several industries, including transportation, manufacturing, mining, metals processing, and electricity generation, as well as provide sustainable hydrogen as a chemical feedstock. STWS uses high temperatures generated from concentrated sunlight or other sustainable means for high-temperature heat to produce hydrogen and oxygen from steam. For example, in its simplest form of a two-step thermochemical cycle, a redox-active metal oxide is heated to ≈1700-2000 K, driving off molecular oxygen while producing oxygen vacancies in the material. The reduced metal oxide then cools (ideally with the extracted heat recuperated for re-use) and, in a separate step, comes into contact with steam, which reacts with oxygen vacancies to produce molecular hydrogen while recovering the original state of the metal oxide. Despite its promising use of the entire solar spectrum to split water thermochemically, the current estimated cost of hydrogen produced via STWS is ≈4-6× the U.S. Department of Energy (DOE) Hydrogen Shot target value of $1/kg. One contributing approach to bridging this cost gap is the design of new materials with improved thermodynamic properties to enable higher efficiencies. The state-of-the-art (SOA) redox-active metal oxide for STWS is ceria (CeO 2 ), due to its close to optimal, although too high, oxygen vacancy formation enthalpy and large configurational and electronic entropy of reduction. However, ceria requires high operating temperatures and its efficiency is insufficient. Therefore, efforts to increase the efficiency of STWS cycles have focused on further optimizing oxygen vacancy formation enthalpies and augmenting the reduction entropy via substitution or doping and materials discovery schemes. Examples of the latter include the perovskites BaCe 0.25 Mn 0.75 O 3 and (Ca,Ce)(Ti,Mn)O 3 . These efforts and others have revealed intuitive chemical principles for the efficient and systematic design of more effective materials, such as the strong correlation between the enthalpies of crystal bond dissociation and solid-state cation reduction with the enthalpy of oxygen vacancy formation, as well as configurational entropy augmentation via the coexistence of two or more redox-active cation sublattices. The purpose of this chapter is to prepare the reader with an up-to-date account of STWS redox-active materials, both the SOA and promising newcomers, as well as to provide chemically intuitive strategies for improving their cycle efficiencies through materials design – in conjunction with ongoing efforts in reactor engineering and gas separations – to reach the cost points for commercial viability. First, we will introduce the thermodynamics of STWS using a two-step, metal-oxide, thermochemical cycle with economics in mind. We also will compare the pros and cons of processes that do or do not involve phase changes. Second, we will describe the qualities that make ceria the SOA STWS redox-active material, as well as its limitations. Third, we will survey some of the most promising candidates to date in the search for materials to supplant ceria, emphasizing the post-ternary, metal-oxide-perovskite alloys. Lastly, we will enumerate and discuss the following materials design directions for STWS redox-active materials: crystal reduction potentials as a proxy for oxygen vacancy formation enthalpies, engineering the electronic and configurational entropy of reduction via f-shells and simultaneous redox, and vetting materials stability via temperature-dependent phase diagrams and melting-point prediction.

08 HYDROGEN↗
DOE OSTI2025

Heterostructured nano-catalysts with efficient metal-oxide interfaces unlock high-performance direct methanol protonic ceramic fuel cells

Direct methanol protonic ceramic fuel cells (PCFCs) are attractive due to their low cost, convenient storage, and high volumetric energy density, as well as their suitability for transportation. However, the poor coking tolerance of conventional nickel-based anodes leads to their susceptibility to severe carbon deposition and significant deactivation after long-term exposure to hydrocarbons. Herein, we report a nano-catalyst of Ce 0.6 Ni 0.2 Cu 0.2 O 2 with a heterogeneous structure that is spontaneously reduced into a Ce 0.6 Ni 0.2-x Cu 0.2-x O 2-δ (CeNCO) oxide framework interfaced with a nano NiCu alloy (denoted as NC/CeNCO) under operating conditions, as confirmed by analyses of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. A Ni-BaCe 0.7 Y 0.06 Yb 0.06 Zr 0.06 Hf 0.06 Gd 0.06 O 3-δ anode-supported PCFC employing the NC/CeNCO metal-oxide catalyst achieved a peak power density of 1.11 W cm −2 and operational stability of about 100 h at 700 °C when fueled by 35 % CH 3 OH-15 % H 2 O-50 % N 2 . In conclusion, the enhanced performance and coking resistance are attributed to the efficient interfaces of Ni, Cu, and ceria-based oxide in NC/CeNCO for CH 3 OH reforming, as confirmed by analyses of electrochemical performance and Raman spectroscopy with density functional theory calculations, revealing that these interfaces can enhance CH 3 OH activation and promote efficient OH-mediated carbon removal via COH intermediates.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Stable perovskite-fluorite dual-phase composites synthesized by one-pot solid-state reactive sintering for protonic ceramic fuel cells

We report that this work synthesized a series of oxide composites with nominal compositions of BaCe 05 Zr 0.4 Y 0.1 O 3-δ (BCZY)-Ce 0.5 Y 0.5 O 2-δ (YDC) based on the BCZY/YDC molar ratios of 0.5:1, 1:1, 2:1, and 4:1 (BCZY-YDC-0.5–1, BCZY-YDC-1-1, BCZY-YDC-2-1, and BCZY-YDC-4-1) using a one-pot solid state reactive sintering (SSRS) method. The X-ray diffraction (XRD) patterns and refinement proved that the one-pot SSRS at 1450 °C for 12 h could achieve the perovskite-fluorite dual-phase composites (DPCs) with the desired structure compositions. The scanning electron microscopy (SEM) images showed that the two DPCs of BCZY-YDC-1-1 and BCZY-YDC-2-1 formed excellent percolation for perovskite and fluorite phases. The conductivity measurement by electrochemical impedance spectroscopy (EIS) and the transference number measurement by the electromotive force (EMF) test proved that changing the BCZY/YDC molar ratio and operating condition could adjust the DPC's conduction property to make them suitable for electrolytes and electrode scaffolds for protonic ceramic fuel cells (PCFCs). The long-term conductivity testing and the crystal structure analysis after EMF testing under versatile conditions indicated that the DPCs of BCZY-YDC-2-1 and BCZY-YDC-1-1 were durable PCFC component materials. The PCFC button cells with the as-discovered BCZY-YDC-2-1 and BCZY-YDC-1-1 as an electrolyte and an anode scaffold, respectively, and the reported Ba–Ce–Fe–Co–O perovskite-perovskite composite as a cathode showed promising performance under H 2 /air gradient.

08 HYDROGEN↗