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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Characterization of ι-carrageenan and its derivative based green polymer electrolytes

The new types of green polymer electrolytes based on ι-carrageenan derivative have been prepared. ι-carrageenan act as precursor was reacted with monochloroacetic acid to produce carboxymethyl ι-carrageenan. The powders were characterized by Attenuated Total Reflection Fourier Transform infrared (ATR-FTIR) spectroscopy and {sup 1}H nuclear magnetic resonance (NMR) to confirm the substitution of targeted functional group in ι-carrageenan. The green polymer electrolyte based on ι-carrageenan and carboxymethyl ι-carrageenan was prepared by solution-casting technique. The films were characterized by electrochemical impedance spectroscopy to determine the ionic conductivity. The ionic conductivity ι-carrageenan film were higher than carboxymethyl ι-carrageenan which 4.87 ×10{sup −6} S cm{sup −1} and 2.19 ×10{sup −8} S cm{sup −1}, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Roadmap for Sustainable Mixed Ionic–Electronic Conducting Membranes

Mixed ionic-electronic conducting (MIEC) membranes have gained growing interest recently for various promising environmental and energy applications, such as H 2 and O 2 production, CO 2 reduction, O 2 and H 2 separation, CO 2 separation, membrane reactors for production of chemicals, cathode development for solid oxide fuel cells, solar-driven evaporation and energy-saving regeneration as well as electrolyzer cells for power-to-X technologies. The purpose of this roadmap, written by international specialists in their fields, is to present a snapshot of the state-of-the-art, and provide opinions on the future challenges and opportunities in this complex multidisciplinary research field. As the fundamentals of using MIEC membranes for various applications become increasingly challenging tasks, particularly in view of the growing interdisciplinary nature of this field, a better understanding of the underlying physical and chemical processes is also crucial to enable the career advancement of the next generation of researchers. As an integrated and combined article, it is hoped that this roadmap, covering all these aspects, will be informative to support further progress in academics as well as in the industry-oriented research toward commercialization of MIEC membranes for different applications.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Green polymer electrolytes based on chitosan and 1-butyl-3-methylimidazolium acetate

Green polymer electrolytes based on chitosan as the polymer matrix and ionic liquid 1-butyl-3-methylimidazolium acetate [Bmim][OAc] as charge carriers were prepared by solution casting technique. Complexes with various amount of ionic liquid loading were investigated as possible ionic conducting polymers. The ionic conductivity was found to increase with increasing weight percent of ionic liquid. The highest ionic conductivity of the charged chitosan-[Bmim][OAc] was 2.44 × 10{sup −3} S cm{sup −1} at 90 wt.% of [Bmim][OAc] content at ambient temperature. Attenuated Total Reflection Fourier Transform infrared (ATR-FTIR) spectroscopy has proven the interaction between chitosan and [Bmim][OAc]. X-ray Diffraction (XRD) has shown that the amorphosity of the complexes increase as the amount of [Bmim][OAc] increase.

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

Impact of Oxygen Non-Stoichiometry on Near-Ambient Temperature Ionic Mobility in Polaronic Mixed-Ionic-Electronic Conducting Thin Films

Enhanced ionic mobility in mixed ionic and electronic conducting solids contributes to improved performance of memristive memory, energy storage and conversion, and catalytic devices. Ionic mobility can be significantly depressed at reduced temperatures, for example, due to defect association and therefore needs to be monitored. Measurements of ionic transport in mixed conductors, however, proves to be difficult due to dominant electronic conductivity. This study examines the impact of different levels of quenched-in oxygen deficiency on the oxygen vacancy mobility near room temperature as measured by a novel dynamic current-voltage analysis. A Pr 0.1 Ce 0.9 O 2-δ film was grown by pulsed laser deposition and subsequently annealed, from 400-600° C, in various oxygen partial pressures to modify its oxygen vacancy concentration while minimizing microstructural growth and cation segregation. To monitor changes in film non-stoichiometry, we leverage the existence of an optical absorption center, related to the oxidation state of Pr ions in Pr0.1Ce0.9O2-δ. The oxygen vacancy migration enthalpy was found to exhibit a small increase from 0.73± 0.04 to 0.79 ± 0.02 eV with increasing oxygen deficiency, while the pre-factor was found to increase by a factor of 135. Here, a nearly 13-fold increase in ionic mobility at 60 °C for increases in oxygen non-stoichiometry from 0.032 ± 0.001 to 0.042± 0.001 was thereby detected. Raman spectroscopy was employed to rule out changes in strain as the primary cause for the significant change in mobility. Several factors potentially contributing to the large pre-factor changes are examined and discussed. Insights into how ionic defect concentration can markedly impact ionic mobility should help in elucidating the origins of variations seen in nanoionic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Proton Conducting Sulfonated Poly(Ionic Liquid) Block Copolymers

Herein, we report the synthesis of proton-conducting sulfonated poly(ionic liquid) block copolymers (S-PILBCPs) containing one block with sulfonic acid (sulfonated styrene, SS) and the other with an IL moiety (vinylbenzylmethylimidazolium bis(trifluoromethylsulfonyl)imide, VBMIm-TFSI) using reversible addition–fragmentation chain-transfer (RAFT) polymerization and post-polymerization modifications (i.e., functionalization, anion exchange reactions, and sulfonation). The S-PILBCPs uniquely conjoin the SS block with mobile protons (H + ) and the PIL block with mobile anions (TFSI – ), where multiple highly desired properties, including high proton conductivity (from the SS block), and high IL-philicity and oxygen solubility (from the PIL block) can exist compartmentally within a microphase separated morphology (evidenced by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS)). High ion conductivity of 79.7 mS/cm at a PIL block composition of 21.6 mol % was observed at 80 °C and 90% relative humidity (RH) (comparable to the benchmark Nafion ionomer). This work successfully demonstrates the design of S-PILBCPs as a new material platform and showcases its promise as an ionomer for proton exchange membrane fuel cells (PEMFCs) as they simultaneously and compartmentally combine proton conductivity and oxygen solubility. Furthermore, these benefits have recently been leveraged to achieve substantial improvement in oxygen reduction reaction (ORR) activity and subsequently fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Unraveling the physics of nanofluidic phenomena at the single-molecule level

Despite groundbreaking potential in a broad application space, several nanofluidic phenomena remain poorly understood. Toward advancing the understanding of fluid behavior under nanoscale confinement, we developed a novel, ideal platform for fundamental molecular transport studies, in which the fluidic channel is a single carbon nanotube (CNT). CNTs offer the advantage of simple chemistry and structure, which can be synthetically tuned with nanometer precision and accurately modeled. With combined experimental and computational approaches, we demonstrated that CNT pores with 1-5 nm diameters conduct giant ionic currents that follow an unusual sublinear electrolyte concentration dependence. The large magnitude of the ionic conductance appears to originate from a strong electro-osmotic flow in smooth CNT pores. First-principle simulations suggest that electro-osmotic flow arises from localized negative polarization charges on carbon atoms near a potassium (K + ) ion and from the strong cation-graphitic wall interactions, which drive K + ions much closer to the wall than chlorides (Cl - ). Single-molecule translocation studies reveal that charged molecules may be distinguished from neutral species on the basis of the sign of the transient current change during their passage through the nanopore. Together with shedding light on a few controversial questions in the CNT nanofluidics area, these results may benefit LLNL’s Security Mission by providing the foundation for the development of advanced single-molecule detection system for bio/chem/explosive analytes. In addition, these experimental and computational platforms can be applied to advance fundamental knowledge in other fields, from energy storage and membrane separation to superfluid physics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Argyrodite-type advanced lithium conductors and transport mechanisms beyond paddle-wheel effect

Abstract Development of next-generation solid-state Li-ion batteries requires not only electrolytes with high room-temperature (RT) ionic conductivities but also a fundamental understanding of the ionic transport in solids. In spite of considerable work, only a few lithium conductors are known with the highest RT ionic conductivities ~ 0.01 S/cm and the lowest activation energies ~0.2 eV. New design strategy and novel ionic conduction mechanism are needed to expand the pool of high-performance lithium conductors as well as achieve even higher RT ionic conductivities. Here, we theoretically show that lithium conductors with RT ionic conductivity over 0.1 S/cm and low activation energies ~ 0.1 eV can be achieved by incorporating cluster-dynamics into an argyrodite structure. The extraordinary superionic metrics are supported by conduction mechanism characterized as a relay between local and long-range ionic diffusions, as well as correlational dynamics beyond the paddle-wheel effect.

25 ENERGY STORAGE↗
DOE OSTI2016

YSZ thin films with minimized grain boundary resistivity

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e.g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here in this paper, we report that the ionic conductivity of yttria stabilized zirconia thin films with nano-columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500 °C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film–substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg 2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Stabilization of garnet/Li interphase by diluting the electronic conductor

The high interfacial resistance and lithium (Li) dendrite growth are two major challenges for solid-state Li batteries (SSLBs). The lack of understanding on the correlations between electronic conductivity and Li dendrite formation limits the success of SSLBs. Here, by diluting the electronic conductor from the interphase to bulk Li during annealing of the aluminium nitride (AlN) interlayer, we changed the interphase from mixed ionic/electronic conductive to solely ionic conductive, and from lithiophilic to lithiophobic to fundamentally understand the correlation among electronic conductivity, Li dendrite, and interfacial resistance. During the conversion-alloy reaction between AlN and Li, the lithiophilic and electronic conductive Li x Al diffused into Li, forming a compact lithiophobic and ionic conductive Li 3 N, which achieved an ultrahigh critical current density of 2.6/14.0 mA/cm 2 in the time/capacity-constant mode, respectively. The fundamental understanding on the effect of interphase nature on interfacial resistance and Li dendrite suppression will provide guidelines for designing high-performance SSLBs.

25 ENERGY STORAGE↗
DOE OSTI2024

Using data-science approaches to unravel insights for enhanced transport of lithium ions in single-ion conducting polymer electrolyte

Solid polymer electrolytes have yet to achieve the an ionic conductivity > 1 mS/cm at room temperature for realistic applications. This target implies the need to reduce the effective energy barriers of ion transport in polymer electrolytes to around 20 kJ/mol. In this work, we combine information extracted from existing experimental results with theoretical calculations to provide insights into ion transport in single-ion conductors (SICs) with a focus on lithium ion SICs. Through the analysis of temperature-dependent ionic conductivity data obtained from the literature, we evaluate different methods of extracting energy barriers for lithium transport. The traditional Arrhenius fit to the temperature-dependent ionic conductivity data indicates that the Meyer-Neldel rule holds for SICs. However, the values of the fitting parameters remain unphysical. Our modified approach based on recent work (Macromolecules, 56, 15, 6051(2023)), which incorporates a fixed pre-exponential factor, reveals that the energy barriers exhibit temperature dependence over a wide range of temperatures. Using this approach, we identify a series of anions leading to the energy barriers less than 30 kJ/mol, which include trifluoromethane sulfonimide (TFSI), fluoromethane sulfonimide (FSI), and boron-based organic anions. In our efforts to design the next generation of anions, which can exhibit the energy barriers less than 20 kJ/mol, we focused on boron-containing SICs, and performed density functional theory (DFT) based calculations to connect the chemical structures via the binding energy of cation (lithium)-anion pairs with the experimentally derived effective energy barriers for ion transport. Not only have we identified a correlation between the binding energy and the energy barriers, but we also propose a strategy to design new boron-based anions by using the correlation. This combined approach involving experiments and theoretical calculations is capable of facilitating the identification of promising new anions, which can exhibit ionic conductivity $> 1$ mS/cm near room temperature, thereby expediting the development of novel superionic single-ion conducting polymer electrolytes. The published datasets include all the temperature-dependent ionic conductivity collected from the literature with literature DOIs, DFT calculated binding energies, and python scripts to analyze data, construct statistical models, and generate plots.

36 MATERIALS SCIENCE↗
DOE OSTI2018

A quaternary sodium superionic conductor - Na 10.8 Sn 1.9 PS 11.8

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3 PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8 Sn 1.9 PS 11.8 , exhibiting a high ionic conductivity of 0.67mS cm -1 at 25 °C. This high ionic conductivity originates from the presence of a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. The Na 10.8 Sn 1.9 PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.

Yu, Zhaoxin↗
DOE OSTI2022

Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors

Here, we report on a new family of halide-deficient and Li-rich argyrodite fast-ion conductors, Li 6+x PS 5+x (Cl/Br/I) 1–x (0 ≤ x ≤ 0.85). Exploration of the influence of aliovalent anion substitution in Li 6 PS 5 X (X = Cl, Br, I)–using a combination of high-resolution powder neutron diffraction and electrochemical impedance spectroscopy–reveals that aliovalent anion substitution induces higher Li-ion concentration and Li site disorder, and creates S 2– /I – anion site disorder on the 4a site. In the series Li 6+x PS 5+x I 1–x (0 ≤ x ≤ 0.4), the resulting conductivity for Li 6.4 PS 5.4 I 0.6 (0.13 mS·cm –1 ) represents almost a 100-fold increase over that of the parent phase, Li 6 PS 5 I (0.0033 mS·cm –1 ), and establishes one of the first fast-ion conducting argyrodite thiophosphate iodides. For Cl-argyrodites, the ionic conductivity decreases a little with lower halide-content but ionic conductivity for the Br-argyrodites is almost unchanged. Overall, all Cl/Br-argyrodites Li 6 +xPS 5+x (Cl/Br) 1–x (0 ≤ x ≤ 0.75) with a low halide content exhibit surprisingly high ionic conductivities > 1 mS·cm –1 despite a very low degree of sulfur/halogen anion site disorder. Our findings highlight the importance of attaining a disordered Li-ion sublattice and sulfur/halogen anion site disorder (anionic charge homogeneity) in argyrodites, where Li ions occupy high energy sites and activate concerted ion migration that drives the ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Enhanced Conductivity via Homopolymer-Rich Pathways in Block Polymer-Blended Electrolytes

The optimization of ionic conductivity and lithium-ion battery stability can be achieved by independently tuning the ion transport and mechanical robustness of block polymer (BP) electrolytes. However, the ionic conductivity of BP electrolytes is inherently limited by the covalent attachment of the ionically conductive block to the mechanically robust block, among other factors. Herein, the BP electrolyte polystyrene-block-poly(oligo-oxyethylene methacrylate) [PS-b-POEM] was blended with POEM homopolymers of varying molecular weights. The incorporation of a higher molecular weight homopolymer additive (α > 1 state) promoted a “dry brush-like” homopolymer distribution within the BP self-assembly and led to higher lithium salt concentrations in the more mobile homopolymer-rich region, increasing overall ionic conductivity relative to the “wet brush-like” (α < 1 state) and unblended composites, where α is the molecular weight ratio between the POEM homopolymer and the POEM block in the copolymer. Here, neutron and X-ray reflectometry (NR and XRR, respectively) provided additional details on the lithium salt and polymer distributions. From XRR, the α > 1 blends showed increased interfacial widths in comparison to their BP (unblended) or α < 1 counterparts because of the more central distribution of the homopolymer. This result, paired with NR data that suggested even salt concentrations across the POEM domains, implied that there was a higher salt concentration in the homopolymer POEM-rich regions in the dry brush blend than in the wet brush blend. Furthermore, using 7 Li solid-state nuclear magnetic resonance spectroscopy, we found a temperature corresponding to a transition in lithium mobility (T Li mobility ) that was a function of blend type. T Li mobility was found to be 39 °C above T g in all cases. Interestingly, the ionic conductivity of the blended BPs was highest in the α > 1 composites, even though these composites had higher T g s than the α < 1 composites, demonstrating that homopolymer-rich conducting pathways formed in the α > 1 assemblies had a larger influence on conductivity than the greater lithium ion mobility in the α < 1 blends.

25 ENERGY STORAGE↗
DOE OSTI2023

Interface-enhanced conductivities in surfactant-mediated, solution-grown ionic crystalline complexes

Renewable energy is increasingly relying on optimized electrolytes and interfaces. In this work, Tween 20 and sodium chloride are selected as a model system to reveal the effects of surfactants on salt crystallization in the context of ionic conductivity and interface optimization. At a varied crystallization speed and mix ratio, it is demonstrated that the resultant solution-grown ionic crystalline complexes can achieve a highly tunable ion transport with a controllable crystalline interface. X-ray diffraction results rule out the possibility of polymorphism in the NaCl/Tween 20 systems, which further supports the importance of an optimized crystalline network for optimizing permittivity or ionic conductivity. Raman mapping and machine learning techniques are used to perform semantic segmentation on highly heterogeneous NaCl/Tween 20 complexes. Furthermore, FTIR measurements demonstrate that inter- and intra-molecular interactions play critical roles in the formation of these crystals. This work lays a foundation toward future optimization of such complex ion systems for a specific salt or crystallization modifier in energy storage or ion transport applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Design principles for NASICON super-ionic conductors

Na Super Ionic Conductor (NASICON) materials are an important class of solid-state electrolytes owing to their high ionic conductivity and superior chemical and electrochemical stability. In this paper, we combine first-principles calculations, experimental synthesis and testing, and natural language-driven text-mined historical data on NASICON ionic conductivity to achieve clear insights into how chemical composition influences the Na-ion conductivity. These insights, together with a high-throughput first-principles analysis of the compositional space over which NASICONs are expected to be stable, lead to the successful synthesis and electrochemical investigation of several new NASICONs solid-state conductors. Among these, a high ionic conductivity of 1.2 mS cm ₋1 could be achieved at 25 °C. We find that the ionic conductivity increases with average metal size up to a certain value and that the substitution of PO 4 polyanions by SiO 4 also enhances the ionic conductivity. While optimal ionic conductivity is found near a Na content of 3 per formula unit, the exact optimum depends on other compositional variables. Surprisingly, the Na content enhances the ionic conductivity mostly through its effect on the activation barrier, rather than through the carrier concentration. These deconvoluted design criteria may provide guidelines for the design of optimized NASICON conductors.

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

Room-temperature cycling of metal fluoride electrodes: Liquid electrolytes for high-energy fluoride ion cells

Fluoride ion batteries are potential “next-generation” electrochemical storage devices that offer high energy density. At present, such batteries are limited to operation at high temperatures because suitable fluoride ion–conducting electrolytes are known only in the solid state. We report a liquid fluoride ion–conducting electrolyte with high ionic conductivity, wide operating voltage, and robust chemical stability based on dry tetraalkylammonium fluoride salts in ether solvents. Pairing this liquid electrolyte with a copper–lanthanum trifluoride (Cu@LaF 3 ) core-shell cathode, we demonstrate reversible fluorination and defluorination reactions in a fluoride ion electrochemical cell cycled at room temperature. Fluoride ion–mediated electrochemistry offers a pathway toward developing capacities beyond that of lithium ion technology.

Davis, Victoria K.↗