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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

High-Spatial-Resolution Quantitative Chemomechanical Mapping of Organic Composite Cathodes for Sulfide-Based Solid-State Batteries

Understanding the chemo-mechanical behaviors of electrodes, particularly at the electrode/electrolyte interfaces, is critical for improving the performance of all-solid-state batteries. However, due to the instability of electrolyte materials under ambient conditions, such characterizations are challenging, particularly for sulfide-based all-solid-state batteries. Herein, by combining time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) and in-SEM nanoindentation measurements, a systematic quantitative investigation of the chemo-mechanical behaviors of pyrene-4,5,9,10-tetraone (PTO) /Li 6 PS 5 Cl composite cathodes is carried out. Chemical and quantitative mechanical information of the composite cathode were collected with high spatial resolution after developing and implementing an air-free characterization protocol. By directly connecting the Young’s modulus and hardness with the Li distribution in the composite cathode, a comprehensive chemo-mechanical mapping of the PTO/ Li 6 PS 5 Cl composite cathode has been established. Furthermore, this work improves our knowledge of the critical chemo-mechanical phenomena that occur at the cathode/electrolyte interfaces in all-solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Surface plasmon driven near- and midinfrared photoconductivity in ligand-free ITO nanocrystal films

Semiconductor nanocrystals (NCs) offer exciting opportunities to deploy infrared optoelectronic technology in a variety of applications that are off-limits to conventional single-crystalline materials. However, the performance and stability of state-of-the-art NC-based devices strongly depend on the details of the NC surface and its passivating ligands. Here, the authors use indium tin oxide NC films stripped of organic ligands and conformally coated with Al 2 O 3 to show that absorption enabled by infrared localized surface plasmon resonances permit infrared photoconduction. For Au electrodes, these metallic NC films exhibit stable photoconductive performance over months in ambient and under electrical stress.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Robust Interfacial Effect in Multi-interface Environment through Hybrid Reconstruction Chemistry for Enhanced Energy Storage

Electrochemical-oxidation-driven reconstruction has emerged as an efficient approach for developing advanced materials, but the reconstructed microstructure still faces challenges including inferior conductivity, unsatisfying intrinsic activity, and active-species dissolution. In this report we present hybrid reconstruction chemistry that synergistically couples electrochemical oxidation with electrochemical polymerization (EOEP) to overcome these constraints. During the EOEP process, the metal hydroxides undergo rapid reconstruction and dynamically couple with polypyrrole (PPy), resulting in an interface-enriched microenvironment. We observe that the interaction between PPy and the reconstructed metal center (i.e., Mn > Ni, Co) is strongly correlated. Theoretical calculation results demonstrate that the strong interaction between Mn sites and PPy breaks the intrinsic limitation of MnO 2 , rendering MnO 2 with a metallic property for fast charge transfer and enhancing the ion-adsorption dynamics. Operando Raman measurement confirms the promise of EOEP-treated Mn(OH) 2 (E-MO/PPy) to stably work under a 1.2 V potential window. The tailored E-MO/PPy exhibits a high capacitance of 296 F g –1 at a large current density of 100 A g –1 . Here our strategy presents breakthroughs in upgrading the electrochemical reconstruction technique, which enables both activity and kinetics engineering of electrode materials for better performance in energy-related fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Solution-Deposited and Patternable Conductive Polymer Thin-Film Electrodes for Microbial Bioelectronics

Microbial bioelectronic devices integrate naturally occurring or synthetically engineered electroactive microbes with microelectronics. These devices have a broad range of potential applications, but engineering the biotic–abiotic interface for biocompatibility, adhesion, electron transfer, and maximum surface area remains a challenge. Prior approaches to interface modification lack simple processability, the ability to pattern the materials, and/or a significant enhancement in currents. We report a novel conductive polymer coating that significantly enhances current densities relative to unmodified electrodes in microbial bioelectronics is reported. The coating is based on a blend of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) crosslinked with poly(2-hydroxyethylacrylate) (PHEA) along with a thin polydopamine (PDA) layer for adhesion to an underlying indium tin oxide (ITO) electrode. When used as an interface layer with the current-producing bacterium Shewanella oneidensis MR-1, this material produces a 178-fold increase in the current density compared to unmodified electrodes, a current gain that is higher than previously reported thin-film 2D coatings and 3D conductive polymer coatings. The chemistry, morphology, and electronic properties of the coatings are characterized and the implementation of these coated electrodes for use in microbial fuel cells, multiplexed bioelectronic devices, and organic electrochemical transistor based microbial sensors are demonstrated. It is envisioned that this simple coating will advance the development of microbial bioelectronic devices.

patterned bioelectronics↗
DOE OSTI2023

Modulating the Mixing Gibbs Free Energy to Enhance Solid–Liquid Phase Separation for High–Performance Organic Solar Cells

Organic solar cells (OSC) feature a hierarchical structure with the electron donor/acceptor layer sandwiched by anode and cathode, which raises the importance of controlling the molecular crystal orientation, domain size, and vertical distribution to facilitate the charge collection at electrodes. However, the similar conjugated backbone of donor/acceptor material and fast film–formation kinetics have led to spinodal–decomposition–orientated phase separation that result in the film presenting an intimately mixed morphology and random molecular orientation. To solve the issue, the mixing Gibbs free energy–triggered solid–liquid phase separation during the film formation process is enhanced by solidifying one component and solvating the other based on a liquid additive. Following the liquid evaporation process, a favorable vertical distribution is obtained. Meanwhile, the prolonged solvation process enlarges the domain size and assists the molecules to diffuse and orient properly, enabling better exciton/charge dynamics during the power conversion processes. As a result, the fabricated devices exhibit a fill factor over 80% and an efficiency of 18.72%, which is one of the top efficiencies for binary OSCs. In conclusion, insights and a methodology is provided here to manipulate the organic donor/acceptor phase separation in terms of mixing Gibbs free energy.

14 SOLAR ENERGY↗
DOE OSTI2020

EFRC Accomplishments 2014-2020: NorthEast Center for Chemical Energy Storage (NECCES)

The mission of NECCES is to develop an understanding of how key electrode reactions occur in cathode materials for Li based batteries, and how they can be controlled to improve electrochemical performance, from the atomistic level to the macroscopic level through the life-time of the operating battery. This mission will allow the determination of the ultimate limits of intercalation reactions for chemical energy storage. The approach and specific research goals of NECCES are to: 1. Attain reversible multi-electron transfer in a cathode material using lithium, using the model compound ε -VOPO 4 ; 2. Close the gap between the theoretical and practical energy density for intercalation compounds, using the model compound LiNi 0.85 Co 0 .10Al 0.05 O 2 ; 3. Understand the transition from cation redox to anion redox electrochemistry; 4. Understand performance limiting transport in positive electrode structures from the local through the meso to the macroscale.

25 ENERGY STORAGE↗
NASA NTRS1970

Electrodeposited inorganic separators for alkaline batteries

Coating electrodes of silver-cadmium cells with thermostable electrodeposits of calcium hydroxide or magnesium hydroxide reduces silver migration and increases cell life. Absence of organic matter enables assembled cells to be sterilized without oxidation of the material of the separators.

Carson, W. N., Jr.↗
DOE OSTI2023

Self-Organization and Nitrogen Incorporation in Diamond-Like Carbon Microstructures Synthesized by Nonthermal Plasma

Nonthermal plasma activation of light alkanes is an encouraging decarbonization strategy to produce chemicals or fuels from abundant and/or flared carbon sources. However, prolific carbon growth on both the catalyst and electrode has limited its practicality, requiring additional knowledge of the carbon structure and growth mechanism before breakthroughs are realized. Furthermore, visual evidence is provided for nonuniform diamond-like carbon (DLC) microstructures that materialize in a coaxial dielectric barrier discharge (DBD) reactor flowing ethane and He at 278 K. Through a connection to known behaviors of DBD microdischarge patterns, the microstructure spacing was controlled by altering the applied voltage (ΔV) of the plasma or the burning voltage (U b ). Additionally, carbon valorization through nitrogen incorporation from N 2 was explored as an orthogonal solution to carbon mitigation, with N/C values >0.25 achieved and both sp 2 and sp 3 C–N bonding observed in the microstructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

System and method for organic electronic device patterning

A method for fabricating an organic electronic device comprises providing a plurality of photoresist structures on a substrate, the substrate having a first electrode layer, the photoresist structures having a bottom surface attached to the substrate and a top surface opposite the bottom surface, the top surface having a dimension greater than a dimension of the bottom surface, positioning a mask over the structures, the mask having a plurality of openings, and depositing an emissive material over the substrate through at least one of the plurality of openings to form at least one emissive element. An organic electronic device and a method of fabricating an organic electronic component are also described.

Forrest, Stephen R.↗
DOE OSTI2023

Degradation in Ni-Rich LiNi 1– x – y Mn x Co y O 2 /Graphite Batteries: Impact of Charge Voltage and Ni Content

Ni-rich LiNi 1– x–y Mn x CoyO 2 (NMC) materials are attractive as cathodes for Li-ion batteries due to their high energy density and low Co content. However, these materials may display poor electrochemical reversibility relating to structural and interfacial instabilities. The influence of Ni content and level of delithiation during charge on degradation mechanisms and relevance to electrochemical cycling behavior are probed for LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode materials in a full cell configuration under two upper voltage limits (4.1 and 4.3 V). The combined use of dQ/dV analysis of electrochemical voltage profiles, operando XRD, and postcycling scanning electron microscopy (SEM) measurements indicates that a major contributor to capacity fade is the large anisotropic volume change from an H2 $\leftrightarrows$ H3 phase transition and associated mechanical degradation particularly for NMC811. Notably, transition metal dissolution and deposition on the negative electrode are found to correlate with the structural changes occurring in the cathode under high voltage charge. X-ray photoelectron spectroscopy (XPS) analyses of the cycled cathodes reveal a more organic-rich cathode–electrolyte interphase (CEI) when cycling to 4.3 V with lower relative amounts of LiF. Surface reconstruction is not a significant factor under these cycling conditions as determined by soft X-ray absorption spectroscopy (sXAS) analysis. The results emphasize the opportunity to match the electrochemical test parameters with the specific NMC active material to mitigate degradation and extend cycle life.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Rheological and microstructural characterization of aqueous suspensions of carbon black and reduced graphene oxide

Carbon black is often used as a conductivity enhancer in battery electrodes. Reduced graphene oxide is another conducting material, with a high aspect ratio sheet-like morphology, and offers the possibility of generating a conducting network at loadings that are small compared to carbon black. Suspensions of conducting carbon, active materials and binders are typically coated on current collectors during the formation of electrodes. The rheology of these suspensions is an important indicator of the connectivity of particles in the suspension and impacts the electrical conductivity as well as the thickness of the coated layer. In this work, the rheology and microstructures of aqueous suspensions of para-aminobenzoic acid terminated carbon black (CB) with and without reduced graphene oxide (RGO) were investigated. The CB loading varied between 0.05 wt.% -10 wt.%, while the samples containing RGO had an RGO loading of 0.05 wt.%. The pH of the suspension was varied from 7.5 to 3. The carboxyl groups on the CB surface are deprotonated at pH 7.5, making the particles hydrophilic. Protonation of the carboxylate groups at pH 3 makes the particles partially hydrophobic. Suspensions of CB showed Newtonian behavior at all loadings for pH 7.5, and at loadings below 1.5 wt.% for pH 3. They are shear thinning at loadings between 1.5–10 wt.%. Interestingly, the low shear viscosity is non-monotonic with CB loading, rising up to a CB loading of 7.5 wt.%, and then dropping at 10 wt.%. Cryogenic scanning electron microscopy (SEM) showed CB particles forming aggregates at pH 3 for CB loadings greater than 1.5 wt.%. At pH 3, addition of 0.05 wt.% RGO resulted in a viscosity increase for suspensions containing 0.5 wt.% CB, as the RGO formed connections with CB particles that enhanced network formation. Adding RGO had little effect on suspensions that had 1.5 wt.% CB. The combination of SEM imaging and suspension rheology provides insight into the particle connectivity for the carbon-based materials studied here. These insights will be useful in determining coating conditions for slurries used in rechargeable battery electrodes.

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

Electrochemical Synthesis and Investigation of Stoichiometric, Phase-Pure CoSb 2 O 6 and MnSb 2 O 6 Electrodes for the Oxygen Evolution Reaction in Acidic Media

The electrochemical oxidation of water to oxygen gas is the primary counter reaction to the formation of hydrogen gas via water splitting. In acidic media, the only well-established and active oxygen evolution catalysts are expensive noble metal oxides such as IrO x and RuO x , necessitating the development of practical oxygen evolution catalysts that are stable in acidic media. In this study, we prepared stoichiometric, phase-pure CoSb 2 O 6 and MnSb 2 O 6 electrodes using electrochemical synthesis and investigated their ability to oxidize water in 0.5 M H 2 SO 4 (pH 0.3). In addition, their stabilities during the oxygen evolution reaction (OER) were carefully examined by comparing their morphologies, crystallinities, compositions, and surface compositions before and after the OER. The chlorine evolution reaction on CoSb 2 O 6 and MnSb 2 O 6 in acidic media was also examined so that their performances can be compared with previously reported non-stoichiometric CoSb 2 O 6 and MnSb 2 O 6 electrodes. The electrochemical properties and stabilities of stoichiometric, phase-pure CoSb 2 O 6 and MnSb 2 O 6 reported in this study can provide useful insights into the development and understanding of acid-stable, non-noble metal oxide-based OER catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Highly Efficient Urea Oxidation via Nesting Nano-Nickel Oxide in Eggshell Membrane-Derived Carbon

Here, we reported a strategy of using an eggshell membrane to produce hierarchically porous carbon as a low-cost substrate for synthesizing a nano-nickel oxide catalyst (C@NiO), which can effectively turn biowaste—urea—into energy through an electrochemical approach. Here, the interwoven carbon networks within NiO led to highly efficient urea oxidation due to the strong synergistic effect. The as-prepared electrode only needed 1.36 V versus reversible hydrogen electrode to realize a high efficiency of 10 mA cm –2 in 1.0 M KOH with 0.33 M urea and delivered an even higher current density of 25 mA cm –2 at 1.46 V, which is smaller than that of the porous carbon and commercial Pt/C catalyst. Benefiting from theoretical calculations, Ni(III) active species and the porous carbon further enabled the electrocatalyst to effectively inhibit the “CO 2 poisoning” of electrocatalysts, as well as ensuring its superior performance for urea oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1987

Polyphase alloys as rechargeable electrodes in advanced battery systems

The rechargeability of electrochemical cells is often limited by negative electrode problems. These may include loss of capacity, increased impedance, macroscopic shape change, dendrite growth, or a tendency for filamentary or whisker growth. In principle, these problems can be reduced or eliminated by the use of alloys that undergo either displacement or insertion reactions at reactant species activities less than unity, rather than pure elements. The fundamental reasons for some of these problems with elemental electrodes, as well as the basic principles involved in the different behavior of alloys, are briefly discussed. More information is now available concerning the thermodynamic and kinetic properties of a number of alloys of potential interest for use as electrodes in elevated temperature lithium battery systems. Recent results have extended these results down to ambient temperatures, indicating that some such materials may be of interest for use with new low temperature molten salt electrolytes, or with organic solvent electrolytes. The all solid mixed conductor matrix concept is also reviewed.

Huggins, Robert A.↗
DOE OSTI2021

Cascade CO 2 electroreduction enables efficient carbonate-free production of ethylene

CO 2 electroreduction provides a route to convert waste emissions into chemicals such as ethylene (C 2 H 4 ). However, the direct transformation of CO 2 -to-C 2 H 4 suffers from CO 2 loss to carbonate, consuming up to 72% of energy input. A cascade approach—coupling a solid-oxide CO 2 -to-CO electrochemical cell (SOEC) with a CO-to-C 2 H 4 membrane electrode assembly (MEA)—would eliminate CO 2 loss to carbonate. However, this approach requires a CO-to-C 2 H 4 MEA with energy efficiency well beyond demonstrations to date. Focusing on the MEA, in this study we find that an N-tolyl substituted tetrahydro-bipyridine film improves the stabilization of key reaction intermediates, while an SSC ionomer enhances CO transport to the Cu surface, enabling a C 2 H 4 faradaic efficiency of 65% at 150 mA cm –2 for 110 h. Demonstrating a cascade SOEC-MEA approach, we achieve CO 2 -to-C 2 H 4 with a ~48% reduction in energy intensity compared with the direct route. We further reduce the energy intensity by coupling CO electroreduction (CORR) with glucose electrooxidation.

10 SYNTHETIC FUELS↗
DOE OSTI2020

Enabling electrochemical N 2 reduction to NH 3 in the low overpotential region using non-noble metal Bi electrodes via surface composition modification

The electrochemical N 2 reduction reaction (ENRR) that can produce NH 3 using water as the hydrogen source at ambient temperature and pressure can be an exciting alternative to the Haber–Bosch process. The major challenge for electrochemical NH 3 production is the competing hydrogen evolution reaction (HER), which seriously limits the faradaic efficiency (FE) for NH 3 production. To date, noble metal electrocatalysts that are inactive for the HER have mainly been investigated for the ENRR. Studies reporting a FE greater than 10% for NH 3 production using non-noble metal catalysts in the low overpotential region (E ≤ 0.2 V vs. RHE) are very rare. This study reports effective electrochemical surface modification strategies that drastically increase the ENRR activity of a non-noble Bi electrode in the low overpotential region and achieve a FE for NH 3 production as high as 13.2% at -0.2 V vs. RHE in pH 7.5 phosphate buffer. Finally, the effect of each of the surface modifications on the activity for the ENRR and the electrode stability during the ENRR were systematically elucidated, which may be used to develop general strategies to enhance the ENRR activities of other non-noble metal electrodes in the low overpotential region.

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

4D Printing of Stretchable Supercapacitors via Hybrid Composite Materials

Stretchable supercapacitors (SCs) have attracted significant attention in developing power-independent stretchable electronic systems due to their intrinsic energy storage function and unique mechanical properties. Most current SCs are generally limited by their low stretchability, complicated fabrication process, and insufficient performance and robustness. This study presents a facile method to fabricate arbitrary-shaped stretchable electrodes via 4D printing of conductive composite from reduced graphene oxide, carbon nanotube, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. The electrode patterns of an arbitrary shape can be deposited onto prestretched substrates by aerosol-jet printing, then self-organized origami (ridge) patterns are generated after releasing the substrates from holding stretchers due to the mismatched strains. The stretchable electrodes demonstrate superior mechanical robustness and stretchability without sacrificing its outstanding electrochemical performance. The symmetric SC prototype possesses a gravimetric capacitance of ≈21.7 F g -1 at a current density of 0.5 A g -1 and a capacitance retention of ≈85.8% from 0.5 to 5 A g -1 . A SC array with arbitrary-shaped electrodes is also fabricated and connected in series to power light-emitting diode patterns for large-scale applications. Finally, the proposed method paves avenues for scalable manufacturing of future energy-storage devices with controlled extensibility and high electrochemical performance.

36 MATERIALS SCIENCE↗
NASA NTRS1983

Advanced inorganic separators for alkaline batteries and method of making the same

A flexible, porous battery separator includes a coating applied to a porous, flexible substrate. The coating comprises: (1) a thermoplastic rubber-based resin which is insoluble and unreactive in the alkaline electrolyte, (2) a polar organic plasticizer which is reactive with the alkaline electrolyte to produce a reaction product which contains a hydroxyl group and/or a carboxylic acid group, and (3) a mixture of polar particulate filler materials which are unreactive with the electrode. The mixture comprises at least one first filler material having a surface area of greater than 25 sq meters/gram, at last one second filler material having a surface area of 10 to 25 sq meters/gram. The volume of the mixture of filler materials is less than 45% of the total volume of the fillers and the binder. The filler surface area per gram of binder is about 20 to 60 sq meters/gram, and the amount of plasticizer is sufficient to coat each filler particle.

Sheibley, D. W.↗