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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 307 records · Page 17

Baselining Activity and Stability of ORR Catalysts and Electrodes for Proton Exchange Membrane Fuel Cells for Heavy-Duty Applications

Activity and stability of electrodes with Pt and PtCo alloy catalysts supported on high surface area carbon, hereafter to as a-Pt/C and d-PtCo/C, were evaluated for heavy-duty applications. Both catalysts had nearly identical Pt loading (50-wt% Pt on carbon and 0.25 mg Pt cm −2 ) and had undergone thermal treatment to stabilize them by growing the average particle size to 4–5 nm. Both were subjected to 90,000 (90 k) standard accelerated stress tests (AST) cycles consisting of 0.6–0.95 V square wave potentials, 3-s hold at upper and lower potential limits in H 2 /N 2 at 1.5 atm, 80 °C and 100% RH. Test protocols were developed to monitor the performance losses and characterize them in terms of activity for the oxygen reduction reaction (ORR), oxygen transport in the electrode and proton transport in the membrane and cathode catalyst layer. Despite the nearly double initial ORR activity, the PtCo/C electrode degraded faster due to the leaching of Co from the catalyst that had started even before the imposition of the AST potential cycles. Commensurate with Co leaching, Co poisoning of ionomer is responsible for the inferior performance of d-PtCo/C electrode at high current densities both before and after AST.

30 DIRECT ENERGY CONVERSION↗

LiCoO 2 -Based Fiber Cathodes for Electrospun Full Cell Li-ion Batteries

Here, particle/polymer electrospinning was used to prepare fiber mat cathodes containing LiCoO 2 nanoparticles, carbon powder, and poly(vinylidene fluoride) for Li-ion batteries. The fibers had a high LiCoO 2 particle content (70 wt%) which allowed for a high gravimetric capacity of 90 mAh g -1 (corresponding to 128 mAh g$-1\atop{LiCoO2}$) at 0.1C (1C = 274 mAh g$-1\atop{LiCoO2}$). Cathode performance was stable in a half cell with 78% capacity retention over 200 cycles at 0.5C. Unlike previous work on electrospun LiCoO 2 nanofibers prepared using sol-gel chemistry and high temperature processing, the particle/polymer fiber mat cathodes reported here were made thick with a high fiber volume fraction for high areal and volumetric capacities at fast charge/discharge rates (e.g., 0.81 mAh cm -2 and 62 mAh cm -3 at 2C) which were much greater than that of a slurry cast cathode of the same composition (0.004 mAh cm -2 and 0.30 mAh cm -3 at 2C). Full cells containing a LiCoO 2 /C/PVDF fiber mat cathode and C/PVDF fiber mat anode were also prepared and characterized. These electrospun batteries exhibited a high energy density of 144 Wh kg -1 at 0.1C and an areal capacity of 1.03 mAh cm -2 at 1C. The excellent performance of the electrospun particle/polymer cathodes and anodes is attributed to electrolyte penetration throughout the 3D fiber electrode mats, a large electrode/electrolyte interfacial area, and short Li + transport pathways between the electrolyte and active material nanoparticles in the radial fiber direction.

30 DIRECT ENERGY CONVERSION↗

Printed biofuel cells

Methods, systems, and devices are disclosed for implementing a biofuel cell device for extracting energy from a biofuel. In one aspect, a biofuel cell device includes a substrate, an anode including a catalyst to facilitate the conversion of a fuel in a biological fluid in an oxidative process that releases electrons captured at the anode, thereby extracting energy from the fuel substance, a cathode configured on the substrate adjacent to the anode and separated from the anode by a spacing region, and a load electrically coupled to the anode and cathode via electrical interconnects to obtain the extracted energy as electrical energy.

09 BIOMASS FUELS↗

Effect of Pressure and Temperature on Carbon Dioxide Reduction at a Plasmonically Active Silver Cathode

Here, carbon dioxide reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. Carbon dioxide partial pressures (P Co 2 ) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at -0.7, -0.9, and -1.1 V RHE . At a given applied overpotential the total current density increased with increasing P Co 2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P Co 2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2 ) evolution reaction decreased with increasing P Co 2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P Co 2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32°C at -0.7, -0.9, and -1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Long-Term Cr Poisoning Effect on LSCF-GDC Composite Cathodes Sintered at Different Temperatures

Here, the impact of sintering temperature on Cr-poisoning of solid oxide fuel cell (SOFC) cathodes was systematically studied. La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3-δ - Ce 0.9 Gd 0.1 O 2-δ symmetric cells were aged at 750°C in synthetic air with the presence of Crofer 22 APU, a common high temperature interconnect, over 200 hours and electrochemical impedance spectroscopy (EIS) was used to determine the degradation process. Both the ohmic resistance (R Ω ) and polarization resistance (R P ) of LSCF-GDC cells, extracted from EIS spectra, for different sintering temperatures increase as a function of aging time. Furthermore, the Cr-related degradation rate increases with decreased cathode sintering temperature. The polarization resistance of cathode sintered at lower temperature (950°C) increases dramatically while aging with the presence of Cr and also significantly decreases the oxygen partial pressure dependence after aging. The degradation rate shows a positive correlation to the concentration of Cr. The results indicate that decreased sintering temperature increases the total surface area, leading to more available sites for Sr-Cr-O nucleation and thus greater Cr degradation.

30 DIRECT ENERGY CONVERSION↗

Conductive spinels derived from Co–Mn based alloy precursor for SOFC cathode-side contact application

The utilization of gas-atomized Co–Mn based alloy precursor is a promising approach to lowering the sintering temperature of the spinel contact layer and enhancing its performance. In this work, simulated interconnect/contact/cathode cells are employed to investigate the effects of different metallic precursors (i.e., three Co–Mn based alloy powders and a mixture of Co + MnO 2 powders) on the microstructure and performance of the reactively-sintered MnCo 2 O 4 -based contact layer. While excellent overall electrical performance is observed for all the cells with the four contact precursors during 1000-h testing at 800 °C in air, the cell with the Ce-doped alloy contact precursor shows the lowest cell area specific resistance (ASR) and ASR degradation rate. Cross-sectional observation of the tested cells is conducted to assess the compatibility of the contact layer with adjacent components as well as its effectiveness in reducing the Cr 2 O 3 scale growth and blocking Cr migration from the interconnect to the cathode.

08 HYDROGEN↗

Controlling Interlayer Disorder Toward Reversible Phase Transition in a Layered Sodium Manganese Oxide Cathode

Sodium manganese oxides are promising Na-ion battery cathodes but they suffer from irreversible phase transitions during electrochemical reactions. Most strategies to date have aimed to suppress the phase transitions by stabilizing their layered structures through limiting the content of extractable Na + . Here, we conversely increase atomic disorder in the Na-birnessite, a layered sodium manganese oxide, and thereby modulate its phase transition behavior toward improved electrochemical reversibility. Our study reveals that Mn vacancies and Mn migrated into the interlayer affect interlayer local environment of Na + and water molecules consequently enhancing Na + mobility. We observe better capacity retention for disordered “D-Na-birnessite”, which undergoes a reversible phase transition from the birnessite-type structure to an O′3-type α-Na x MnO 2 -like structure through another intermediate metastable birnessite-type phase. In conclusion, this research highlights the positive effects of atomic disorder to regulate phase transition routes for achieving superior electrochemical reversibility, finally paving the way to overcoming the limits of layered oxide cathodes.

Kang, Seongkoo [Korea Univ., Seoul, (Korea, Republ↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗

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↗