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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 OSTI2022

Ion Transport in Batteries with Polymer Electrolytes

We discuss polymer electrolytes for use in rechargeable lithium batteries. Polymer electrolytes have the potential to enable batteries with lithium metal anodes. These batteries have significantly higher theoretical energy densities than current lithium-ion batteries. We consider binary mixtures of polymers and salts. We also cover more complex systems such as polymer electrolytes swollen with a solvent (gel polymer electrolytes) and microphase separated polymer electrolytes. By covalently attaching the anions to the chains in a polymer solid, one obtains a single-ion conductor. We mainly focus on experiments wherein the polymer electrolyte is placed between two lithium metal electrodes. These experiments enable the determination of three transport parameters, ionic conductivity, salt diffusion coefficient, and transference number, and the thermodynamic factor. The properties of dry polymer electrolytes are contrasted with those of gel polymer electrolytes. The gel systems exhibit higher conductivity while the dry systems exhibit superior mechanical properties. We discuss interfacial impedance when lithium metal is contacted with polymer electrolytes and the importance of coulombic efficiency.

Yu, Xiaopeng↗
NASA NTRS1993

Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

Du, Ping↗
DOE OSTI2022

Anion chemical composition of poly(ethylene oxide)-based sulfonylimide and sulfonate lithium ionomers controls ion aggregation and conduction

Maximizing ion conduction in single-ion-conducting ionomers is essential for their application in energy-related technologies such as Li-ion batteries. Understanding the anion chemical composition impacts on ion conduction offers new perspectives to maximize ion transport, since the current approach of lowering T g has apparently reached a limit (lowest T g ~ 190 K, highest conductivity ~10 -5 –10 -4 S cm -1 ). Here, a series of random ionomers are synthesized by copolymerizing poly(ethylene glycol)methacrylate with either sulfonylimide lithium methacrylate (MTLi) or sulfonate lithium methacrylate (MSLi) using reversible addition–fragmentation chain transfer (RAFT) polymerization. Li-Ion conduction and self-diffusion coefficients (DLi+) of the ionomers are characterized with dielectric relaxation spectroscopy (DRS) and pulsed-field-gradient (PFG) NMR diffusometry, respectively. Increasing ion content decreases the Li-ion conductivity and D Li+ , as expected from the increased T g . Moreover, a considerably lower ionic conductivity and D Li+ are observed for MSLi compared to MTLi at constant ion content and T g /T. As revealed from X-ray scattering, strong ion aggregation in MSLi results in much lower conductivity and DLi+ compared with less aggregated MTLi based on the more delocalized sulfonylimide anion. These results emphasize the detrimental and molecularly specific role of ion aggregation in Li-ion conductivity, and highlight the necessity for minimizing ion aggregation via the rational choice of anion chemical composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Solid-State, Single-Ion Conducting, Polymer Blend Electrolytes with Enhanced Li + Conduction, Electrochemical Stability, and Limiting Current Density

The development of solid-state polymer electrolytes with high lithium conductivity is crucial to improve lithium-ion battery performance and ameliorate the safety challenges associated with current solvent-based electrolytes. Unfortunately, sluggish polymer segmental dynamics are known to constrain conductivity enhancements in solid-state polymer electrolyte systems, limiting overall performance. In this work, a glassy single-ion-conducting polymer, poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] (PLiMTFSI), was blended with a flexible polymer, poly(oligo-oxyethylene methyl ether methacrylate) (POEM), and the impact of PLiMTFSI molecular weight and ion concentration on the thermal and ion-conducting behavior of blend electrolytes was investigated. High ionic conductivities approaching 1 × 10 -2 S/cm at 150 °C were realized in this polymer blend electrolyte system as a result of decoupling Li + transport from polymer segmental dynamics. The decoupled ion transport was attributed to the packing frustration of the glassy PLiMTFSI – sufficient percolating free volume was generated to produce effective ion diffusion pathways. This decoupling was tunable as the ion transport could be altered from being closely coupled to the polymer segmental dynamics (Vogel–Tammann–Fulcher-like) to hopping (Arrhenius-like) by increasing the PLiMTFSI molecular weight and ion concentration. Moreover, the immobilized TFSI anion resulted in high Li + selectivity (Li + transference number = 0.9), high electrochemical stability (up to 4.7 V against Li + / Li), and limiting current density of 1.8 mA/cm 2 (electrolyte thickness = 0.05 cm). These features suggest that this single-ion-conducting, polymer blend electrolyte might be a promising alternative to a benchmark system – salt-doped polyethylene oxide. Moreover, the above characteristics can support the battery operation at higher voltages using energy-dense Li metal anodes, with faster charging rates and enhanced energy/power densities. Altogether, the results suggest that polymer chain packing frustration can be exploited to overcome the constraints of slow polymer segmental relaxations to achieve rapid and highly selective ion transport and enhanced performance in solid-state polymer electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Beyond Simple Dilution: Superior Conductivities from Cosolvation of Acetonitrile/LiTFSI Concentrated Solution with Acetone

Concentrated solutions of Li salts in acetonitrile are promising alternative electrolytes for the next generation of Li batteries as they may exhibit superior electrochemical properties. However, the reduced mobility of the chemical species is a barrier yet to be overcome, and for this, we explore the utilization of acetone as a cosolvent. Although acetone is a polar compound, we find that its addition to the LiTFSI/acetonitrile solution does not follow the trends expected for a simple dilution process. At a low concentration, acetone subtly shifts acetonitrile from the first to extended solvation sheaths of the ions. Still, most of the original structure of the solution is preserved, and mobile high-concentration clusters are formed in the solution. At higher concentrations, the cosolvation promotes cation–anion interactions but with a different nature from those in the original solution and still allows for a further increase in conductivity. Additionally, the non-coordinating fraction of acetonitrile acquires features resembling the pure solvent, which is a possible additional facilitating factor for ionic diffusion.

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

Nanostructured ZnO-Based Electrochemical Sensor with Anionic Surfactant for the Electroanalysis of Trimethoprim

In this research, detection of trimethoprim (TMP) was carried out using a nanostructured zinc oxide nanoparticle-modified carbon paste electrode (ZnO/CPE) with an anionic surfactant and sodium dodecyl sulphate (SDS) with the help of voltametric techniques. The electrochemical nature of TMP was studied in 0.2 M pH 3.0 phosphate-buffer solution (PBS). The developed electrode displayed the highest peak current compared to nascent CPE. Effects of variation in different parameters, such as pH, immersion time, scan rate, and concentration, were investigated. The electrode process of TMP was irreversible and diffusion controlled with two electrons transferred. The effective concentration range (8.0 × 10 -7 M–1.0 × 10 -5 M) of TMP was obtained by varying the concentration with a lower limit of detection obtained to be 2.58 × 10 -8 M. In addition, this approach was effectively employed in the detection of TMP in pharmaceutical dosages and samples of urine with the excellent recovery data, suggesting the potency of the developed electrode in clinical and pharmaceutical sample analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Tailoring Ion Transport in Li 3‐3y Ho 1+y Cl 6‐x Br x via Transition‐Metal Free Structural Planes and Charge Carrier Distribution

Abstract Localized atomistic disorder in halide‐based solid electrolytes (SEs) can be leveraged to boost Li + mobility. In this study, Li + transport in structurally modified Li 3 HoCl 6 , via Br − introduction and Li + deficiency, is explored. The optimized Li 3‐3 y Ho 1+ y Cl 6‐ x Br x achieves an ionic conductivity of 3.8 mS cm −1 at 25 °C, the highest reported for holmium halide materials. 6,7 Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li + motional rate neighboring 116 MHz. X‐ray diffraction analyses reveal mixed‐anion‐induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho‐free planes with favorable energetics for Li + migration. Bond valence site energy analysis highlights preferred Li + transport pathways, particularly in structural planes devoid of Ho 3+ blocking effects. Molecular dynamics simulations corroborate enhanced Li + diffusion with Br − introduction into Li 3 HoCl 6 . Li‐Ho electrostatic repulsions in the (001) plane presumably drive Li + diffusion into the Ho‐free (002) layer, enabling rapid intraplanar Li + motion and exchange between the 2d and 4h sites. Li 3‐3 y Ho 1+ y Cl 6‐ x Br x also demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high‐performance fast ion conductors for all‐solid‐state batteries.

Chemistry↗
NASA NTRS1980

Advances in membrane technology for the NASA redox energy storage system

Anion exchange membranes used in the system serve as a charge transferring medium as well as a reactant separator and are the key enabling component in this storage technology. Each membrane formulation undergoes a series of screening tests for area-resistivity, static (non-flow) diffusion rate determination, and performance in Redox systems. The CDIL series of membranes has, by virtue of its chemical stability and high ion exchange capacity, demonstrated superior properties in the redox environment. Additional resistivity results at several acid and iron solution concentrations, iron diffusion rates, and time dependent iron fouling of the various membrane formulations are presented in comparison to past standard formulations.

Ling, J. S.↗
DOE OSTI2021

Buffered Coordination Modulation as a Means of Controlling Crystal Morphology and Molecular Diffusion in an Anisotropic Metal-Organic Framework

We know significant advances have been made in the synthesis of chemically selective environments within metal-organic frameworks, yet materials development and industrial implementation have been hindered by the inability to predictively control crystallite size and shape. One common strategy to control crystal growth is the inclusion of coordination modulators, which are molecular species designed to compete with the linker for metal coordination during synthesis. However, these modulators can simultaneously alter the pH of the reaction solution, an effect that can also significantly influence crystal morphology. Herein, noncoordinating buffers are used to independently control reaction pH during metal-organic framework synthesis, enabling direct interrogation of the role of the coordinating species on crystal growth. We demonstrate the efficacy of this strategy in the synthesis of low-dispersity single-crystals of the framework Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) in a pH 7-buffered solution using cobalt(II) acetate as the metal source. Density functional theory calculations reveal that acetate competitively binds to Co during crystallization, and by using a series of cobalt(II) salts with carboxylate anions of varying coordination strength, it is possible to control crystal growth along the c -direction. Finally, we use zero length column chromatography to show that crystal morphology has a direct impact on guest diffusional path length for the industrially important hydrocarbon m -xylene. Together, these results provide molecular-level insight into the use of modulators in governing crystallite morphology and a powerful strategy for the control of molecular diffusion rates within metal-organic frameworks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Anion and Cation Migration at 2D/3D Halide Perovskite Interfaces

Here, this study explores the ionic dynamics in 2D/3Dperovskite solar cells, which are known for their improved efficiency and stability. The focus is on the impact of halide choice in 3D perovskites treated with phenethylammonium halide salts (PEAX, X = Br and I). Our findings reveal that light and heat drive ionic migration in these structures, with PEA + species diffusing into the 3D film in PEABr-treated samples. Mixed-halide 3D perovskites show halide interdiffusion, with bromine migrating to the surface and iodine diffusing into the film. Cathodoluminescence microscopy reveals localized 2Dphases on the 3D perovskite, which become more evenly distributed after thermal treatment. Both PEAX salts enhance the performance of photovoltaic devices. This improvement is attributed to the passivation capabilities of the salts themselves and their respective Ruddlesden–Popper (RP) phases. Annealed PEAI-treated devices show a better balance between efficiency and statistical distribution of photovoltaic parameters.

25 ENERGY STORAGE↗
DOE OSTI2020

Time-resolved in situ visualization of the structural response of zeolites during catalysis

Zeolites form an important class of materials that are widely used in various fields. Their unique properties come primarily from their size, shape, and connectivity of their sub-nm crystalline voids, the Si/Al ratio of the anionic framework, and the number and the nature of charge-balancing cations.The inhomogeneous distribution of the Si/Al ratio within crystals, and hence the cation density, the presence of organic residues, and their inhomogeneous distribution within crystals sensitively affect their performances because these factors influencethe intra-crystalline diffusion rates of the reactants and products. However, the information regarding these inhomogeneities in zeolite crystals cannot be obtained by conventional analytical tools because they only provide information regardingthe average properties of zeolite crystals. Here we employin situX-ray free electron laser-based time-resolved coherent X-ray diffraction imaging to investigate the internal deformations originating from the inhomogeneous Cu ion distributions in Cu-exchanged ZSM-5 zeolite crystals during the deoxygenation of nitrogen oxides with propene. We show that the interactions between the reactants and the active sites lead to an unusual strain distribution,which is confirmed by density functional theory simulations. Moreover, this elucidates the factors responsible for distinct active regions,which are essential to maximizing some applications with enhanced performances. These observations provide insights into the role of structural inhomogeneity in zeolites during a catalytic processand will assist the future design of zeolites for their applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Fabrication and Characterization of Cross-Linked Phenyl-Acrylate-Based Ion Exchange Membranes and Performance in a Direct Urea Fuel Cell

Ion exchange membranes (IEMs) are crucial for direct fuel cells, including direct methanol and direct urea fuel cells (DUFCs). While commercially available IEMs (e.g., FAA-3-50) show decent power density in direct fuel cells, they experience considerable methanol or urea crossover, reducing device performance and motivating design of IEMs that suppress fuel crossover. Here, we prepare cross-linked IEMs with high mechanical toughness utilizing a cross-linker (methylenebis(acrylamide)), hydrophobic monomer (phenyl acrylate (PA) or phenyl methacrylate (PMA)), and charged monomer (2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) for cation exchange or methacroylcholine chloride (MACC) for anion exchange). To validate these membranes in a fuel cell application, we perform DUFC experiments utilizing a PA/MACC AEM and observe good power density compared to FAA-3-50. Furthermore, to understand the role of urea crossover in DUFC performance, permeabilities of both membranes to urea are measured by diffusion cells with in situ ATR-FTIR spectroscopy, where our PA/MACC exhibited lower urea permeability than FAA-3-50.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Polarization of Valence Orbitals by the Intramolecular Electric Field from a Diffuse Dipole-Bound Electron

The diffuse electron in a dipole-bound state is spatially well-separated from the valence electrons and is known to have negligible effects on the dipole-bound state’s molecular structure. Here, we show a dipole-bound state is observed in deprotonated 4-(2-phenylethynyl)-phenoxide anions, 348 cm -1 below the anion’s detachment threshold. The photodetachment of the dipole-bound electron is observed to accompany a simultaneous shake-up process in valence orbitals in this aromatic molecular anion. This shake-up process is due to configuration mixing as a result of valence orbital polarization by the intramolecular electric field of the dipole-bound electron. Furthermore, this observation suggests that dipole-bound anions can serve as a new platform to probe how oriented electric fields influence the valence electronic structure of polyatomic molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Novel use of positively charged nylon transfer membranes for trapping indoleacetic acid or other small anions during efflux from plant tissues

Positively charged nylon blotting membranes were used as an anion binding medium to trap [14C]indoleactic acid (IAA) as it exited cells at the basal ends of Coleus blumei L. stem and Zea mays L. coleoptile segments. Autoradiography was used to visualize where the [14C] that moved out of the cut ends was localized on the nylon membrane. Diffusion of [14C]IAA from the initial point of contact with the nylon membrane was minimal. Comparison of the autoradiograms with anatomical tissue prints of the cut ends of the segments was used to determine what tissues participate in IAA movement. The results of these initial studies were consistent with other reports suggesting that [14C]IAA movement was primarily associated with vascular tissues in both C. blumei stems and corn coleoptiles, but the resolution was not sufficient to identify which vascular tissues were involved in IAA transport. With further refinements, this technique could also be used for studying the movement of other small charged molecules through plant tissues.

NASA Discipline Plant Biology↗
DOE OSTI2022

Identification and quantification of multinuclear Cu active sites derived from monomeric Cu moieties for dry NO oxidation over Cu-SSZ-13

The identification and quantification of multinuclear Cu-oxo cations in Cu-zeolites is a challenge amidst the dynamic nature of Cu ions in Cu-zeolites. Herein, we synthesized Cu-SSZ-13 zeolites containing varying densities of monomeric Cu cations (Z 2 Cu and ZCuOH, where Z represents an anionic site on the zeolite framework). The number of Cu-oxo cations, quantified using carbon monoxide temperature programmed reduction (CO-TPR), quadratically increased with increasing ZCuOH density, evidencing that proximal ZCuOH sites are precursors to Cu-oxo dimers. We also find that dehydrated proximal ZCuOH with overlapping diffusion radii of at most 0.5 nm can form Cu-oxo dimers. CO-TPR also revealed the presence of three distinct pools (i.e types) of Cu-oxo dimers; these pools catalyze dry NO oxidation at different turnover rates, with the fastest pool 2 to 30 times faster than the slowest pool. Finally, from reaction kinetics and rate law analysis, we also proposed a cohesive dry NO oxidation mechanism and demonstrated that nitrates detected by in situ FTIR are a spectator species.

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

Direct observation of the local microenvironment in inhomogeneous CO 2 reduction gas diffusion electrodes via versatile pOH imaging

In this study, we report how the micrometer-scale morphology of a carbon dioxide reduction (CO 2 R) gas diffusion electrode (GDE) affects the mass transport properties and with it, the local CO 2 R performance. We developed a technique to probe the microenvironment in a CO 2 R GDE via local pOH imaging with time- and three-dimensional spatial, micrometer-scale resolution. The local activity of hydroxide anions (OH - ), represented by the pOH value, around a GDE in contact with an aqueous electrolyte is a crucial parameter that governs the catalytic activity and CO 2 R selectivity. Here, we use fluorescence confocal laser scanning microscopy (CLSM) to create maps of the local pOH around a copper GDE by combining two ratiometric fluorescent dyes, one of which is demonstrated as a pOH sensor for the first time in this work. We observe that the local pOH decreases when current is applied due to the creation of OH - as a byproduct of CO 2 R. Interestingly, the pOH is lower inside microtrenches compared to the electrode surface and decreases further as trenches become more narrow due to enhanced trapping of OH - . We support our experimental results with multiphysics simulations that correlate exceptionally well with measurements. These simulations additionally suggest that the decreased pOH inside microcavities in the surface of a CO 2 R GDE leads to locally enhanced selectivity towards multicarbon (C 2+ ) products. This study suggests that narrow microstructures on the length scale of 5 μm in a GDE surface serve as local CO 2 R hotspots, and thus highlights the importance of a GDE's micromorphology on the CO 2 R performance.

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

Water limiting current measurements in anion exchange membrane fuel cells (AEMFCs); part 1: Water limiting current method development

We report water management is critical in optimizing anion exchange membrane fuel cell (AEMFCs) performance and durability. The role of membranes on determining cell water balance in AEMFCs has received limited study. A more thorough understanding of membrane water transport parameters is necessary for thorough cell optimization. In this study, a novel method for probing limiting current based on water flux across an AEMFC is presented for the first time. The water limiting current has been investigated as a function of relative humidity of anode and cathode streams, cathode backpressure and cell operating temperature. From these studies, it is clearly shown that water diffusion through the membrane from the anode is the most critical mechanism for achieving high current density performance and durability. The developed method can act as a novel screening technique that focuses on the impacts of water transport parameters and helps identify promising membrane materials based on their water transport properties. A critical but underappreciated facet of AEMFC performance and durability.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Editors’ Choice—Review—Designing Defects and Diffusion through Substitutions in Metal Halide Solid Electrolytes

Ternary metal halides A 3 MX 6 , ( A = Li + , Na + ; M = trivalent metal; X = halide) are a promising family of solid electrolytes for potential applications in all-solid-state batteries. Recent research efforts have demonstrated that chemical substitution at all three sites is an effective strategy to controlling battery-relevant material properties. The A 3 MX 6 family exhibits a wide breadth of structure and anion sublattice types, making it worthwhile to comprehend how chemical substitutions manifest desirable functional properties including ion transport, electrochemical stability, and environmental tolerance. Yet, a cohesive understanding of the materials design principles for these substitutions have not yet been developed. Here, we bring together prior literature focused on chemical substitutions in the A 3 MX 6 ternary metal halide solid electrolytes. Using materials chemistry perspectives and principles, we aim to provide insights into the relationships between crystal structure, choice of substituting ions and the extent of substitutions, ionic conductivity, and electrochemical stability. We further present targeted approaches to future substitution studies to enable transformative advances in A 3 MX 6 solid electrolytes and all-solid-state batteries.

25 ENERGY STORAGE↗