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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electrochemical Synthesis of Zeolite Coatings with Controlled Crystal Polymorphism and Self-Regulating Growth

Zeolite coatings are studied as molecular sieves for membrane separation, membrane reactors, and chemical sensor applications. They are also studied as anticorrosive films for metals and alloys, antimicrobial and hydrophobic films for heating, ventilation, and air conditioning, and dielectrics for semiconductor applications. Zeolite coatings are synthesized by hydrothermal, ionothermal, and dry-gel conversion approaches, which require high process temperatures and lengthy times (ranging from hours to days). Here, we report the first zeolite coatings synthesized via electrochemical deposition on a cathodic electrode, with controlled crystal polymorphism achieved within subhourly duration. We demonstrate this approach by developing sodium zeolite (e.g., sodalite (SOD), NaA (LTA), and Linde Type N (LTN)) coatings on a titanium electrode and extending the synthesis method to porous stainless steel. The coating morphology and crystallinity depend on the temperature, time, and applied current. The coating thickness is independent of the applied current, showing the presence of a self-regulating mechanism to ensure a uniform coating thickness across the metal surface. The electrochemical zeolite growth mechanism was elucidated with high-resolution transmission electron microscopy, and applications of the resultant zeolite coatings for oil/water separation and ethanol/water pervaporation were exploited. Electrochemical synthesis represents a novel, simple, fast, and environmentally friendly approach to preparing zeolite coatings. It can potentially be generalized for developing zeolite materials with diverse framework structures, morphologies, and orientations for substrates with complicated geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Efficient indium-tin-oxide free inverted organic solar cells based on aluminum-doped zinc oxide cathode and low-temperature aqueous solution processed zinc oxide electron extraction layer

Indium-tin-oxide (ITO) free inverted organic solar cells (IOSCs) based on aluminum-doped zinc oxide (AZO) cathode, low-temperature aqueous solution processed zinc oxide (ZnO) electron extraction layer, and poly(3-hexylthiophene-2, 5-diyl):[6, 6]-phenyl C{sub 61} butyric acid methyl ester blend were realized in this work. The resulted IOSC with ZnO annealed at 150 °C shows the superior power conversion efficiency (PCE) of 3.01%, if decreasing the ZnO annealing temperature to 100 °C, the obtained IOSC also shows a PCE of 2.76%, and no light soaking issue is observed. It is found that this ZnO film not only acts as an effective buffer layer but also slightly improves the optical transmittance of AZO substrates. Further, despite the relatively inferior air-stability, these un-encapsulated AZO/ZnO IOSCs show comparable PCEs to the referenced ITO/ZnO IOSCs, which demonstrates that the AZO cathode is a potential alternative to ITO in IOSCs. Meanwhile, this simple ZnO process is compatible with large area deposition and plastic substrates, and is promising to be widely used in IOSCs and other relative fields.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Development & Validation of Low-Cost, Highly-Durable, Spinel-Based Materials for SOFC Cathode-Side Contact (Final Report)

A cathode-side contact layer is required to provide and maintain stable electrical conduction paths between the interconnect and cathode in a solid oxide fuel cell (SOFC) stack assembly and thus minimize the ohmic resistance and stack power loss. Current cathode-interconnect contact materials are based on noble metals, electrically-conductive perovskites, their composite materials, etc. These materials are either too expensive or do not possess the overall balanced performance required for the cathode-side contact application. To achieve the DOE SOFC system cost and performance stability goals, a new generation of low-cost, high-performance contact materials needs to be developed. In this project, spinel-based materials thermally converted from the Fe-Ni and Co-Mn based alloy precursors were developed and validated for the cathode-side contact application. The precursor alloy compositions were optimized via a combination of composition screening in the (Ni,Fe) 3 O 4 and (Mn,Co) 3 O 4 spinel system, alloy design using physical metallurgy principles, and cost considerations. The alloy powders with the desired composition and particle size were manufactured via gas atomization. The optimal process parameters for thermal conversion of these alloy precursor layers to a spinel-based layer were identified, i.e., 900°C x 2h in air, which is close to the initial stack firing condition. The area-specific resistances (ASRs) of the interconnect/contact/cathode test assemblies with the developed contact layer were determined for various durations (up to 5000 h) under simulated cathodic operation conditions. Some of the alloy-derived spinel contacts exhibited the lowest ASR and ASR degradation rate. The in-stack performance of the most promising alloy-derived contact layer is currently being evaluated via stack testing. To reduce the stack cost, the Co-Mn based alloy powders were utilized as the precursor for synthesis of dense spinel-based interconnect coating. By optimizing both the initial powder size/distribution and the alloy powder composition, a dense (Mn,Co) 3 O 4 -based spinel coating was achieved. Furthermore, co-sintering of the coating/contact dual-layer structure under the initial stack firing condition was realized by utilizing the tailored Co-Mn alloy precursors. Cost analysis of the developed technology indicated a total stack cost reduction of around 10.6% with the implementation of co-sintering of the interconnect coating and the contact layer during initial stack firing. Since low-cost processes such as screen printing is utilized in the precursor application and no reduction heat treatment is needed for the coating formation, the developed technology can be readily implemented at the industrial partner’s manufacturing facilities with no additional capital investment needed.

08 HYDROGEN↗
DOE OSTI2022

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2016

How to sustainably feed a microbe: Strategies for biological production of carbon-based commodities with renewable electricity

As interest and application of renewable energy grows, strategies are needed to align the asynchronous supply and demand. Microbial metabolisms are a potentially sustainable mechanism for transforming renewable electrical energy into biocommodities that are easily stored and transported. Acetogens and methanogens can reduce carbon dioxide to organic products including methane, acetic acid, and ethanol. The library of biocommodities is expanded when engineered metabolisms of acetogens are included. Typically, electrochemical systems are employed to integrate renewable energy sources with biological systems for production of carbon-based commodities. Within these systems, there are three prevailing mechanisms for delivering electrons to microorganisms for the conversion of carbon dioxide to reduce organic compounds: (1) electrons can be delivered to microorganisms via H 2 produced separately in a electrolyzer, (2) H 2 produced at a cathode can convey electrons to microorganisms supported on the cathode surface, and (3) a cathode can directly feed electrons to microorganisms. Each of these strategies has advantages and disadvantages that must be considered in designing full-scale processes. Furthermore, this review considers the evolving understanding of each of these approaches and the state of design for advancing these strategies toward viability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2018

Statically and Dynamically Stable Lithium-sulfur Batteries

The commercialization of lithium-sulfur (Li-S) batteries is hampered by several intrinsic materials challenges: low electronic and ionic conductivity of the active material, severe polysulfide migration from the cathode to the anode, and instability of the Li-metal anode. The poor conductivity limits the electrochemical utilization of the active material and often necessitates a high content of electrochemically inactive, conductive carbon or functional polymers in the cathode region, which lowers the practical energy density. The polysulfide migration causes static and dynamic instabilities with high capacity fade, poisoning of the Li-metal surface, and poor cycling efficiency, hindering the practical viability of Li-S batteries. Recently, it is becoming obvious that the development of practically viable high-energy-density Li-S batteries is determined largely by attaining the necessary cell-design parameters. The essential extrinsic parameters include a sulfur loading of at least 5 mg cm-2, a sulfur content of over 65 wt.%, and a low electrolyte/sulfur (E/S) ratio of less than 11 milliliter per gram. To overcome the above challenges, our group has demonstrated in this project that innovations in polysulfide-filter-coated separators and advanced electrode substrates greatly enhance the electrochemical utilization and efficiency with reasonably high sulfur loadings and low E/S ratios in the cells. This is because Li-S batteries involve conversion reactions unlike the insertion-reaction electrodes in commercial Li-ion batteries, so cell components/designs directly borrowed from Li-ion batteries may need new architectures or chemical/physical characteristics to be adapted to sulfur cathodes. Our cell-component design provides the fabricated Li-S cells with enhanced electrochemical performance: high utilization of the active material, extended cycle life, and good storage properties. More importantly, these custom cell configurations allow the cells to employ the easily prepared sulfur cathodes with a high sulfur loading (up to 60 mg cm-2) and a high sulfur content (80 wt.%) with a low E/S ratio of as low as 4.0 milliliter per gram. Our progress illustrates that the approaches presented and developed in this project offer practically viable solutions for the Li-S technology development.

25 ENERGY STORAGE↗
DOE OSTI2017

Polarization loss correction derived from hydrogen local-resistance measurement in low Pt-loaded polymer-electrolyte fuel cells

The reduction of platinum-loading on the cathode side of polymer-electrolyte fuel cells leads to a poorly understood increase in mass-transport resistance (MTR) at high current densities. This local resistance was measured using a facile hydrogen-pump technique with dilute active gases for membrane-electrode assemblies with catalyst layers of varying platinum-loading (0.03-0.40 mgPt/cm²). Furthermore, polarization curves in H 2 /air were measured and corrected for the overpotential caused by the increased MTR for low loadings on the air side due to the reduced concentration of reactant gas at the catalyst surface. The difference in performance after correction for all resistances including the MTR is minor, suggesting its origin to be diffusive in nature, and proving the meaningfulness of the facile hydrogen-pump technique for the characterization of the cathode catalyst layer under defined operation conditions.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Core-Shell Heterostructures as Functional Materials for Solid Oxide Fuel Cell (SOFC) Electrodes

The principal objective of this project was to synthesize core-shell heterostructures for solid oxide fuel cell cathodes using a molten salt solvent. In doing so, the main goals were split into a) to elucidate and understand the influence of molten salt chemistries to expeditiously synthesize perovskite type oxides for solid oxide fuel cells, b) provide a chemical framework for future molten salt syntheses of energy relevant ceramic materials, c) demonstrate and investigate the required parameters for the optimal core-shell synthesis and yield of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) – La 0.8 Sr 0.2 MnO 3 (shell), and d) demonstrate improved cathode performance of core-shell LSCF-LSM compared to an LSCF cathode on symmetric cells. The results clearly show that a) the influence of the molten salt cation outweighs the anion in regards to product stoichiometry, b) molten salts should be tailored to balance cationic and anionic acidity for high product yield, c) high yield of core-shell nanoparticles can be achieved by optimal mass ratio between core to shell, dwell time in the salt, size ratio between core to shell, and mass ratio between overall powder to salt, and d) the core-shell LSCF-LSM cathodes have lower polarization resistances than LSCF at higher temperatures. More work is required to optimize core-shell cathode performance at lower temperatures. However, this work thus provided justification for using the molten salt synthesis for SOFC cathodes and provided insights into future material modifications for improved performance.

08 HYDROGEN↗
DOE OSTI2015

Air stable organic-inorganic nanoparticles hybrid solar cells

A solar cell includes a low work function cathode, an active layer of an organic-inorganic nanoparticle composite, a ZnO nanoparticle layer situated between and physically contacting the cathode and active layers; and a transparent high work function anode that is a bilayer electrode. The inclusion of the ZnO nanoparticle layer results in a solar cell displaying a conversion efficiency increase and reduces the device degradation rate. Embodiments of the invention are directed to novel ZnO nanoparticles that are advantageous for use as the ZnO nanoparticle layers of the novel solar cells and a method to prepare the ZnO nanoparticles.

14 SOLAR ENERGY↗
DOE OSTI2014

Design, conditioning, and performance of a high voltage, high brightness dc photoelectron gun with variable gap

A new high voltage photoemission gun has been constructed at Cornell University which features a segmented insulator and a movable anode, allowing the cathode-anode gap to be adjusted. In this work, we describe the gun's overall mechanical and high voltage design, the surface preparation of components, as well as the clean construction methods. We present high voltage conditioning data using a 50 mm cathode-anode gap, in which the conditioning voltage exceeds 500 kV, as well as at smaller gaps. Finally, we present simulated emittance results obtained from a genetic optimization scheme using voltage values based on the conditioning data. These results indicate that for charges up to 100 pC, a 30 mm gap at 400 kV has equal or smaller 100% emittance than a 50 mm gap at 450 kV, and also a smaller core emittance, when placed as the source for the Cornell energy recovery linac photoinjector with bunch length constrained to be <3 ps rms. For 100 pC up to 0.5 nC charges, the 50 mm gap has larger core emittance than the 30 mm gap, but conversely smaller 100% emittance.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2016

Optimizing AlF{sub 3} atomic layer deposition using trimethylaluminum and TaF{sub 5}: Application to high voltage Li-ion battery cathodes

Atomic layer deposition (ALD) of conformal AlF{sub 3} coatings onto both flat silicon substrates and high-voltage LiNi{sub 0.5}Mn{sub 0.3}Co{sub 0.2}O{sub 2} (NMC) Li-ion battery cathode powders was investigated using a Al(CH{sub 3}){sub 3}/TaF{sub 5} precursor combination. This optimized approach employs easily handled ALD precursors, while also obviating the use of highly toxic HF(g). In studies conducted on planar Si wafers, the film's growth mode was dictated by a competition between the desorption and decomposition of Ta reaction byproducts. At T ≥ 200 °C, a rapid decomposition of the Ta reaction byproducts to TaC led to continuous deposition and high concentrations of TaC in the films. A self-limited ALD growth mode was found to occur when the deposition temperature was reduced to 125 °C, and the TaF{sub 5} exposures were followed by an extended purge. The lower temperature process suppressed conversion of TaF{sub x}(CH{sub 3}){sub 5−x} to nonvolatile TaC, and the long purges enabled nearly complete TaF{sub x}(CH{sub 3}){sub 5−x} desorption, leaving behind the AlF{sub 3} thin films. NMC cathode powders were coated using these optimized conditions, and coin cells employing these coated cathode particles exhibited significant improvements in charge capacity fade at high discharge rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Face-centered tetragonal (FCT) Fe and Co alloys of Pt as catalysts for the oxygen reduction reaction (ORR): A DFT study

Proton exchange membrane fuel cells (PEMFCs) are promising candidates for alternate energy conversion devices owing to their various advantages including high efficiency, reliability, and environmental friendliness. The performance of PEMFCs is fundamentally limited by the sluggish kinetics of the oxygen reduction reaction (ORR) at the cathode. Various studies have addressed myriads of Pt-based alloys as potential catalysts for ORR. However, most of these studies only focus on the cubic-structured Pt-based alloys which require further improvements especially in terms of stability and required loading. We perform first-principle density functional theory calculations to explore Fe and Co alloys of Pt in a different face centered tetragonal (L1 0 ) geometry as potential catalysts for ORR. The work focuses on understanding the reaction mechanism of ORR by both dissociative and associative mechanisms on L1 0 –FePt/Pt(111) and L1 0 –CoPt/Pt(111) surfaces. The binding pattern of each reaction intermediate is studied along with the complete reaction free energy landscape as a function of Pt overlayers. The L1 0 –FePt/Pt(111) and L1 0 –CoPt/Pt(111) surfaces show higher calculated surface activity for ORR as compared to the native fcc Pt(111) surface. The decrease in the required overpotential (η) for the alloys with respect to the unstrained Pt(111) surface is found to be in the range (0.04 V–0.25 V) assuming the dissociative mechanism and (0.02 V–0.10 V) assuming the associative mechanism, where the variation depends on the thickness of Pt overlayers. We further correlate the binding behavior of the reaction intermediates to the applied biaxial strain on the Pt(111) surface with the help of a mechanical eigenforce model. The eigenforce model gives a (semi-) quantitative prediction of the binding energies of the ORR intermediates under applied biaxial strain. The numerical values of the limiting potential (U L ) obtained from the eigenforce model are found to be very close to ones obtained from electronic structure calculations (less than 0.1 V difference). Finally, the eigenforce model is further used to predict the ideal equi-biaxial strain range required on Pt(111) surfaces for optimum ORR activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Self-supported MoO 2 /MoS 2 nano-sheets embedded in a carbon cloth as a binder-free substrate for high-energy lithium–sulfur batteries

As one of the most prospective candidates for next-generation rechargeable batteries, lithium-sulfur (Li-S) batteries currently still encounter great challenges associated with the low conductivity, severe shuttle effects, and sluggish redox kinetics. Herein, a self-supported sulfur host is fabricated by an in-situ growth of MoO 2 /MoS 2 nano-sheets on a carbon cloth (CC). First, carbon cloth serves as a good template for the morphology-controlled synthesis of nanostructured materials, which not only alleviates the agglomeration of MoO2/MoS2, but also enhances the flexibility and mechanical strengthen of the hybrid architecture as a free-standing host. Second, the polysulfide-trapping ability can be greatly enhanced by both physical and chemical adsorption from the MoO 2 /MoS 2 -anchored carbon cloth. Moreover, the partially sulfurized MoO 2 /MoS 2 nano-sheets integrate the benefits of conductive MoO 2 and sulfiphilic MoS 2 , thus facilitating fast charge transfer and redox kinetics of polysulfide conversion. As a result, these attributes enable the host to hold a high sulfur loading (up to 7.6 mg cm -2 ), which exceeds most of the reported carbon cloth-related cathode work in the literature. Furthermore, the Li-S cells can achieve a high peak capacity of 1350 mA h g -1 , excellent rate capability (C/20 - 2C rate), impressive areal capacity (up to 6.3 mA h cm -2 ), and a high capacity retention of 85% after 100 cycles.

25 ENERGY STORAGE↗
DOE OSTI2016

Thermodynamics of a Dual Stage Sodium Thermo-Electro-Chemical Converter

The need for reliable and distributable energy is evident, but one prominent obstacle is the lack of an efficient direct heat-to-electricity converter. The sodium thermo-electro-chemical converter (Na-TECC) is a highly efficient thermally regenerative electrochemical system (TRES) that can fill this void. This electrochemical technology uses an ion-selective solid-electrolyte called beta-alumina that is highly conductive to sodium cations. The Na-TECC generates electric power by allowing high pressure sodium cations to expand isothermally through the solid-electrolyte. Theoretically, a device interacting with thermal reservoirs at 1150 K and 550 K should operate above 45% efficiency, but actual devices have not surpassed efficiencies of 20%. The maximum potential voltage in these previous devices was substantially reduced by the kinetic limitations of the charge transfer in the cathode (referred to as the overpotential) and by Joule heating losses due to the solid-electrolyte resistance, electrode resistance, and current collector resistance. To overcome this discrepancy, a dual stage conversion process is being proposed. Rather than using one isothermal expansion step, the dual cycle will employ two separate electrolytes to allow two separate expansion steps: one at the high temperature, and another at an intermediate temperature. This new cycle is thermodynamically favorable as it allows for regeneration from the isobaric cooling of the first expansion step, and reheat to complete the expansion in the second step. This allows the engine to reach a lower condenser temperature than its single stage counterpart for a given heat input, resulting in an increased overall efficiency. The temperature drop across each electrolyte in the dual stage device (e.g., ~ 400 K) is smaller than the temperature drop across a comparable single stage device (e.g., ~ 800 K). This makes the device amenable to better thermal management and allows for less heat loss. Also, the intermediate stage will mitigate the thermal shock across the very thin (< 1 mm) solid electrolyte, reduce crack propagation, limit the percolation of the molten dendrites, and ultimately increase the lifetime of the device. A dual stage concept for the Na-TECC has never been demonstrated in literature, so it is necessary to properly re-define the thermodynamic parameters such as heat loss, maximum power, and optimal current density. Certain drawbacks from a dual stage concept will also be addressed, such as the need for larger electrochemical area and the increased pressure losses. It will be demonstrated that the dual stage device must have lower thermal losses than a single stage device if it is to have a higher efficiency. The improved operation of the Na-TECC can have a transformational effect on small combined heat and power (CHP) systems at the 1-5 kW range.

14 SOLAR ENERGY↗
DOE OSTI2019

Direct thermal visualization of micro-scale hydrogen evolution reactions in proton exchange membrane electrolyzer cells

The heat generated from electrochemical reactions has been considered one of the most significant issues in terms of the reliability of energy conversion devices. So far, no systematic study on the relation between heat generation and electrochemical reaction exists, especially in the form of experiments. In this study, changes of the temperature distribution and hydrogen evolution reaction (HER) on the catalyst coated membrane (CCM) in proton exchange membrane electrolyzer cells (PEMECs) are in-situ visualized with the help of a novel PEMEC design, thermal spectroscopy and high-speed visualization system. At the channel-scale, the temperature increases rapidly for most of the active areas, and finally reaches the equilibrium state at 27 °C. The temperature distribution is non-uniform throughout the process. In addition, a series of pore-scale analyses are provided to clarify the relation between the temperature distribution and electrochemical reaction area. More interestingly, the rapid heat generation areas are found to be in a good agreement with the electrochemical reaction areas, which confirms that the heat is released during the reaction processes. Finally, the temperature evolution phenomena on the LGDL surface have also been recorded. These findings could help better understand the correlation between the cathode side electrochemical reaction and heat generation.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

Selective CO 2 Reduction on 2D Mesoporous Bi Nanosheets

The conversion of CO 2 to value-added products using electrical or solar energy represents an attractive means for the capture and utilization of atmospheric CO 2 . Formate is a popular product from CO 2 reduction, but its reaction selectivity is usually unsatisfactory. Tin-based materials have attracted the most attention for formate production at present. Unfortunately, most of them only exhibit moderate selectivity in a narrow and highly cathodic potential window. In this study, it is demonstrated that traditionally under-explored bismuth has a much greater potential for formate production than tin or other materials. Mesoporous bismuth nanosheets are prepared here by the cathodic transformation of atomic-thick bismuth oxycarbonate nanosheets. They enable the selective CO 2 reduction to formate with large current density, excellent Faradaic efficiency (approximate to 100%) over a broad potential window and great operation stability. Moreover, Bi nanosheets are integrated with an oxygen evolution reaction electrocatalyst in full cells, and achieve efficient and robust solar conversion of CO 2 /H 2 O to formate/O 2 .

36 MATERIALS SCIENCE↗