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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 1,225 records · Page 68
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Transient Nonlinear Response of Dynamically Decoupled Ionic Conductors

The present study demonstrates that large electric fields progressively enhance the conductivity of ionic systems up to timescales corresponding to those on which their structural rearrangements take place. Here, in many ionic materials, some regarded as candidates for electrical energy storage applications, the structural relaxation process can be tremendously slower than (or highly decoupled from) the charge fluctuations. Consequently, nonlinear dielectric spectroscopy may be employed to access rheological information in dynamically decoupled ionic conductors, whereas the combination of large electric power density and good mechanical stability, both technologically highly desired, imposes specific experimental constraints to reliably determine the steady-state conductivity of such materials.

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

A Coacervate-Based Mixed-Conducting Binder for High-Power, High-Energy Batteries

Polymer binders add crucial structural integrity to lithium ion battery composite cathodes, but industry standard binders, such as polyvinylidene fluoride (PVDF), are insulating to ions and electrons, detrimentally adding resistance to the overall system. In this work, we use electrostatics to stabilize a blend of a charged conjugated polymer with an oppositely charged polyelectrolyte, providing a processable, stable binder with high ionic and electronic conduction. Using LiFePO4 cathodes as a model system, we show significant improvement in rate capability and stability, with the conducting binder enabling a 39% utilization at 6C compared to 1.6% when PVDF is the binder. Additionally, the conducting binder affords a 63% capacity retention over 400 C/2 cycles, compared to only a 6% retention over 400 cycles when PVDF is the binder. These results show that electrostatically stabilized complexation is a promising strategy to integrate both electronic and ionic conductivity into a binder, while simultaneously maintaining stability and processability.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Investigative Studies toward the Extraction and Recovery of Praseodymium From Ionic Liquids Using Supercritical Carbon Dioxide

Recycle of rare earth elements requires the extraction and recovery of these metals from consumer products such as rechargeable batteries, electric motor magnets, and aircraft engines once the rare earths have been oxidatively dissolved. One approach to this is to combine the metal extraction and recovery steps into a continuous process. Such a scheme would involve direct-dissolution and ligand-assisted supercritical fluid extraction of the metal, followed by deposition of the extracted metal complex into an ionic liquid where it can be electrochemically reduced to its metallic state. Whereas supercritical fluid extraction of rare earth metals has been recently studied, deposition of rare earth metal-ligand complexes into an ionic liquid is not well known for many rare earth metal-ligand systems. In these studies we measured the solubility of several Praseodymium complexes in scCO2. We also measured the solubility of the Praseodymium complexes in ionic liquids with different physical properties of interest including polarizability, viscosity, and conductivity. The ionic liquids studied are from the pyrrolidinium family and include n-butyl-n-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide (BMPy TFSI). Upon completion of these experiments, we added an additional modifier to the ionic liquid solution in the form of a chelating agent and carbon dioxide. Overall, the additions of the various chelating agents and BMPy TFSI result in large changes to viscosity, conductivity, and metal complexation properties of the solutions. Here we report the results of our findings and discuss the possibility of tuning the extractive and reductive properties of the solutions by picking ionic liquids and chelating agents with physical properties conducive to the desired metal recovery scheme.

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

Proton Tunable Analog Transistor for Low Power Computing

This project was broadly motivated by the need for new hardware that can process information such as images and sounds right at the point of where the information is sensed (e.g. edge computing). The project was further motivated by recent discoveries by group demonstrating that while certain organic polymer blends can be used to fabricate elements of such hardware, the need to mix ionic and electronic conducting phases imposed limits on performance, dimensional scalability and the degree of fundamental understanding of how such devices operated. As an alternative to blended polymers containing distinct ionic and electronic conducting phases, in this LDRD project we have discovered that a family of mixed valence coordination compounds called Prussian blue analogue (PBAs), with an open framework structure and ability to conduct both ionic and electronic charge, can be used for inkjet-printed flexible artificial synapses that reversibly switch conductance by more than four orders of magnitude based on electrochemically tunable oxidation state. Retention of programmed states is improved by nearly two orders of magnitude compared to the extensively studied organic polymers, thus enabling in-memory compute and avoiding energy costly off-chip access during training. We demonstrate dopamine detection using PBA synapses and biocompatibility with living neurons, evoking prospective application for brain - computer interfacing. By application of electron transfer theory to in-situ spectroscopic probing of intervalence charge transfer, we elucidate a switching mechanism whereby the degree of mixed valency between N-coordinated Ru sites controls the carrier concentration and mobility, as supported by density functional theory (DFT) .

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Polymerized ionic liquids: Effects of counter-anions on ion conduction and polymerization kinetics

A novel imidazolium–containing monomer, 1–[ω–methacryloyloxydecyl]–3–(n–butyl)–imidazolium (1BDIMA), was synthesized and polymerized using free radical and controlled free radical polymerization followed by post–polymerization ion exchange with bromide (Br), tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), or bis(trifluoromethylsulfonyl)imide (Tf 2 N). The thermal properties and ionic conductivity of the polymers showed a strong dependence on the counter–ions and had glass transition temperatures ( T g ) and ion conductivities at room temperature ranging from 10 °C to –42 °C and 2.09 × 10 –7 S cm –1 to 2.45 × 10 –5 S cm –1 . In particular, PILs with Tf 2 N counter–ions showed excellent ion conductivity of 2.45 × 10 –5 S cm –1 at room temperature without additional ionic liquids (ILs) being added to the system, making them suitable for further study as electro–responsive materials. In addition to the counter–ions, solvent was found to have a significant effect on the reversible addition–fragmentation chain–transfer polymerization (RAFT) for 1BDIMA with different counter–ions. For example, 1BDIMATf2N would not polymerize in acetonitrile (MeCN) at 65 °C and only achieved low monomer conversion (< 5%) at 75 °C. However, 1BDIMA–Tf 2 N proceeded to high conversion in dimethylformamide (DMF) at 65 °C and 1BDIMABr polymerized significantly faster in DMF compared to MeCN. NMR diffusometry was used to investigate the kinetic differences by probing the diffusion coefficients for each monomer and counter–ion in MeCN and DMF. Furthermore, these results indicate that the reaction rates are not diffusion limited, and point to a need for deeper understanding of the role electrostatics plays in the kinetics of free radical polymerizations.

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

Blocking Ion Migration Stabilizes the High Thermoelectric Performance in Cu 2 Se Composites

The applications of mixed ionic–electronic conductors are limited due to phase instability under a high direct current and large temperature difference. Here, it is shown that Cu 2 Se is stabilized through regulating the behaviors of Cu + ions and electrons in a Schottky heterojunction between the Cu 2 Se host matrix and in-situ-formed BiCuSeO nanoparticles. The accumulation of Cu + ions via an ionic capacitive effect at the Schottky junction under the direct current modifies the space-charge distribution in the electric double layer, which blocks the long-range migration of Cu + and produces a drastic reduction of Cu + ion migration by nearly two orders of magnitude. Moreover, this heterojunction impedes electrons transferring from BiCuSeO to Cu 2 Se, obstructing the reduction reaction of Cu + into Cu metal at the interface and hence stabilizes the β-Cu 2 Se phase. Furthermore, incorporation of BiCuSeO in Cu 2 Se optimizes the carrier concentration and intensifies phonon scattering, contributing to the peak figure of merit ZT value of ≈2.7 at 973 K and high average ZT value of ≈1.5 between 400 and 973 K for the Cu 2 Se/ BiCuSeO composites. Here, this discovery provides a new avenue for stabilizing mixed ionic–electronic conduction thermoelectrics, and gives fresh insights into controlling ion migration in these ionic-transport-dominated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Multimodal hard x-ray imaging with resolution approaching 10 nm for studies in material science

We report multimodal scanning hard x-ray imaging with spatial resolution approaching 10 nm and its application to contemporary studies in the field of material science. The high spatial resolution is achieved by focusing hard x-rays with two crossed multilayer Laue lenses and raster-scanning a sample with respect to the nanofocusing optics. Various techniques are used to characterize and verify the achieved focus size and imaging resolution. Here, the multimodal imaging is realized by utilizing simultaneously absorption-, phase-, and fluorescence-contrast mechanisms. The combination of high spatial resolution and multimodal imaging enables a comprehensive study of a sample on a very fine length scale. In this work, the unique multimodal imaging capability was used to investigate a mixed ionic-electronic conducting ceramic-based membrane material employed in solid oxide fuel cells and membrane separations (compound of Ce 0.8 Gd 0.2 O 2–x and CoFe 2 O 4 ) which revealed the existence of an emergent material phase and quantified the chemical complexity at the nanoscale.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

PILBCP-IL Composite Ionomers for High Current Density Performance

Wide-spread commercialization of fuel cell electric vehicles using proton exchange membrane fuel cell (PEMFC) power sources requires that several existing limitations be addressed. These include: (1) a reduction in platinum (Pt) loading in the catalytic electrodes, (2) improvements in reactant and electronic mobility throughout the catalytic electrodes, (3) reduction in the reliance on materials derived from polluting “forever chemicals”, and (4) a significant improvement in the operational longevity of catalytic electrode components. In this project, a team of two universities, Drexel University and Texas A&M University, one national lab, National Renewable Energy Laboratory, and one company, General Motors, collaborated to develop a new cathode ionomer chemistry that would address these limitations and result in an improvement in performance over existing ionomer materials. The key technology developed through this collaborative project was a composite cathode ionomer encompassing an ionic liquid interlayer between Pt catalysts and a sulfonated polymerized ionic liquid block co-polymer (S-PILBCP) that possess the orthogonal properties of protonic conductivity and ionic liquid enhanced kinetics and durability (see schematic in Figure 1). The composite S-PILBCP ionomer eliminates many of the existing issues with perfluorosulfonic acid-based ionomers including active site blocking by sulfonate specific adsorption, restricted O 2 transport through ionomer films, limited humidity tolerance and active area loss for carbon pore confined catalyst particles, and use of polluting “forever chemicals”. Following successful integration of the developed composite ionic liquid into a PEMFC cathode catalyst layer, we demonstrate enhanced performance over Nafion containing cathodes with Pt/C and PtCo/C at both low and high current density. The performance with our composite S-PILBCP ionomer meets the Department of Energy (DOE) targets for light duty vehicle applications

08 HYDROGEN↗
DOE OSTI2020

Acceptor dopant mediated electrical property modification in Bi0.5Na0.5TiO3-based piezoceramic

The effect of Mn and Fe dopants on the electromechanical and electrochemical properties of 0.88[Bi 0.5 Na 0.5 ]TiO 3 –0.08[Bi 0.5 K 0.5 ]TiO 3 –0.04[Bi 0.5 Li 0.5 ]TiO 3 piezoceramic is investigated with particular emphasis on complex impedance in the temperature range from 450 to 600 °C. The impedance spectra have been simulated with equivalent circuits in order to extract bulk and grain boundary characteristics and to determine activation energies of conduction. Mn and Fe dopants considerably enhance the mechanical quality factor and decrease the dielectric loss compared to the undoped composition. Mn doping leads to dramatically higher resistivity in the bulk and a modest increase in the bulk activation energy. On the other hand, conductivity increases dramatically via Fe doping with a significant lowering of activation energy in the bulk and corresponding raising of the activation energy at grain boundaries in comparison to Mn-doped and undoped ceramic. The bulk conductivity of Fe-doped piezoceramic reaches as high as 0.01 S cm -1 at 600 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2017

An Investigation of LSF-YSZ Conductive Scaffolds for Infiltrated SOFC Cathodes

Porous composites of Sr-doped LaFeO 3 (LSF) and yttria-stabilized zirconia (YSZ) were investigated as conductive scaffolds for infiltrated SOFC cathodes with the goal of producing scaffolds for which only a few perovskite infiltration steps are required to achieve sufficient conductivity. While no new phases form when LSF-YSZ composites are calcined to 1623 K, shifts in the lattice parameters indicate Zr can enter the perovskite phase. Measurements on dense, LSF-YSZ composites show that the level of Zr doping depends on the Sr:La ratio. Because conductivity of undoped LSF increases with Sr content while both the ionic and electronic conductivities of Zr-doped LSF decrease with the level of Zr in the perovskite phase, there is an optimum initial Sr content corresponding to La 0.9 Sr 0.1 FeO 3 (LSF91). Although scaffolds made with 100% LSF had a higher conductivity than scaffolds made with 50:50 LSF-YSZ mixtures, the 50:50 mixture provides the optimal interfacial structure with the electrolyte and sufficient conductivity, providing the best cathode performance upon infiltration of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF).

36 MATERIALS SCIENCE↗
DOE OSTI2020

Na ion dynamics in P2-Na x [Ni 1/3 Ti 2/3 ]O 2 : a combination of quasi-elastic neutron scattering and first-principles molecular dynamics study

In this work, the P2-type layered material Na 2/3 [Ni 1/3 Ti 2/3 ]O 2 was studied as a promising bi-functional electrode material for sodium-ion batteries. To assess the electrochemical performance of this material, we investigated the diffusion mechanism as well as ionic and electronic conductivity with a combination of experimental and computational techniques. The quasi-elastic neutron scattering (QENS) experiments and first-principles molecular dynamics (FPMD) simulations were performed to identify the diffusion mechanism. The QENS data showed that Na ion diffusion can be well described by the Singwi–Sjölander jump diffusion model, where the obtained mean jump length matched the distances between the neighboring edge-share and face-share Na sites. FPMD predicted diffusivity values similar to those from QENS. The computed composition dependence of ionic and electronic conductivity of Na x [Ni 1/3 Ti 2/3 ]O 2 suggested that electronic conductivity changes significantly when x deviates from 2/3 as the redox couple of Ni and Ti is activated, while the change of ionic conductivity with x is relatively small.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhancement of Conjugated Polymer Microstructure and Mixed-Conducting Properties via Chalcogenophene Heteroatom Substitution

Heteroatom substitution is a powerful tool to tune the intra- and intermolecular structure of conjugated polymers as well as their resulting optoelectronic and electrochemical properties. Here, a series of oligoethylene glycol bithiophene chalcogenophene polymers (p(g3T2-X)) with systematically varied furan, thiophene, selenophene, and tellurophene comonomers have been synthesized for mixed ionic-electronic conducting applications. Their microstructures have been thoroughly characterized ex situ and in situ with X-ray scattering, and their mixed conducting properties have been probed in electrochemical transistor testbeds. Chalcogenophene heteroatom choice was found to clearly dictate the polymer microstructure (crystallite dimensionality and orientation) and tune mixed conducting properties. Proceeding down Group 16, from O to Se systematically directed the molecular ordering of 2D polymer crystallites from face-on (O) to mixed (S) to edge-on (Se) orientations, with Te driving the polymer to form well-oriented edge-on 3D crystallites. Heteroatom dictated crystallite quality, and orientation tuned relative ionic transport by 2 orders of magnitude. Hole mobility (μ hole ) and mixed conducting figure of merit (μC*) were each tuned over an order of magnitude depending on heteroatom choice, with the Te-containing polymer reaching μ hole = 3.60 cm 2 V –1 s –1 and μC* = 483 F cm –1 V –1 s –1 , due to improved molecular ordering. Insights from this polymer series highlight target microstructures for enhanced mixed conduction in future conjugated polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Thermodynamic assessment of an electrically-enhanced thermochemical hydrogen production (EETHP) concept for renewable hydrogen generation

A novel concept for coupling a thermochemical cycle with an electrochemical separation device for the generation of hydrogen from steam is reported and a thermodynamic analysis of the system is presented. In a conventional thermochemical cycle, an oxygen carrier material is thermally reduced, cooled, and then reoxidized in steam thereby generating hydrogen. However, this process often requires high temperatures (>1700 K) and/or low oxygen partial pressures (<0.001 atm) in order to meet thermodynamic requirements. Such extreme conditions can adversely affect the stability of the reactive oxides, reactor materials, and system efficiency. In our proposed technology, we seek to decrease the required reduction temperature by several hundred degrees Kelvin by relaxing the requirement for spontaneous oxidation reaction at atmospheric pressure. This is accomplished by incorporating a proton-conducting membrane (PCM) to separate hydrogen produced at equilibrium concentrations from reactant steam. We also suggest the use of mixed ionic-electronic conducting (MIEC) oxygen carrier materials that reduce through a continuum of oxidation states at lower temperatures (~1200 °C). In conclusion, this concept allows the generation of a high-quality hydrogen stream while avoiding the challenging high temperatures/low partial pressures required in conventional water-splitting reaction schemes.

08 HYDROGEN↗
DOE OSTI2023

Physics-Based Model to Represent Membrane-Electrode Assemblies of Solid-Oxide Fuel Cells Based on Gadolinium-Doped Ceria

This paper reports a physics-based model that predicts membrane-electrode assembly (MEA) performance of solid-oxide fuel cells (SOFCs) with Ce 0.9 Gd 0.1 O 2− δ (GDC10) electrolyte membranes. The paper derives self-consistent thermodynamic and transport properties for GDC1o mobile charged defects (oxide vacancies and reduced-ceria small polarons) by fitting published measurements of oxygen non-stoichiometry and conductivity over ranges of temperature and O 2 partial pressures. The button-cell model is applied to evaluate how mixed ionic-electronic conductivity influences the performance of an SOFC MEA with a GDC10 electrolyte sandwiched between a porous, composite Ni-GDC10 anode and a porous, composite cathode of Sm 0.5 Sr 0.5 CoO 3− δ (i.e., SSC) and GDC10. SSC properties are also derived by fitting published conductivity and oxygen non-stoichiometry measurements. Mixed conductivity of GDC10 and competing charge transfer reactions at both electrodes reduce open circuit voltages due to leakage current and buildup of defect concentrations at electrode-electrolyte interfaces. To fit polarization data, the button-cell model includes heterogeneous reaction rates for defect incorporation on the GDC10 surface along with Butler–Volmer expressions derived for competing charge transfer reaction rates from rigorous analyses assuming rate-limiting, elementary charge transfer reactions for each electrode. The calibrated MEA model can support rigorous SOFC modeling with GDC10 electrolytes over the range of conditions within a fully operating cell.

Electrochemistry↗
NASA NTRSDate not supplied

Considerations on Electrolytic Conductivity Measurement for Monitoring of Ionic Silver Biocide Dosing

NASA interest in ionic silver (Ag+) as a biocide for spacecraft potable water systems motivates the development of Ag+ concentration sensors to ensure nominal dosing. The electrolytic conductivity change of highly-purified potable water is linearly related to the concentration of chemically-dosed Ag+ and could serve as a useful proxy measurement, while the conductivity change during electrolytic dosing may be less so, depending on the influent water chemistry and electrolytic efficiency. Understanding and mitigating the potentially deleterious effects of Ag+ interaction with conductivity measurement systems requires investigation. Issues associated with traditional conductivity cells, which rely on wetted(typically metal or graphite) electrodes, and capacitively-coupled contactless conductivity detection (C4D) for this application are considered. Traditional conductivity cells may potentially be subject to significant excitation-induced or auto-galvanic reduction of Ag+. These may result in Ag+ depletion or electrode fouling and associated measurement error. Proper selection of electrode material, excitation parameters, and cell geometry may limit such effects. C4D uses electrodes placed outside an inert, insulating material, with dielectric polarization enabling the production of an electric field and resultant current across the analyte solution. This approach could potentially mitigate problems with Ag+ depletion and fouling by eliminating the possibility of auto-galvanic deposition and reducing the Faradaic current density. However, it is necessary to confirm C4D performance at very low conductivity levels and to determine if long-term operation produces conductive deposits, which could result in measurement error. A commercial C4D system with 1/16” (1.59 mm)outer diameter flow tubing and claimed performance in the conductivity range appropriate for this application was identified, and its sensitivity in the upper parts of this range was confirmed in a preliminary experiment. A concept for a C4D detector that could allow for full rate flow-through using planar electrodes and thin-film dielectric layers is discussed.

silver↗
DOE OSTI2019

Electric Conductivity of TiO{sub 2}-Ti{sub 2}O{sub 3}-FeO-CaO-SiO{sub 2}-MgO-Al{sub 2}O{sub 3} for High-Titania Slag Smelting Process

The electric conductivity of high-titania slag of TiO{sub 2}-Ti{sub 2}O{sub 3}-FeO-CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO slag system was measured by means of four-electrode alternating current (AC) impedance method. The results show that high-titania slag exhibits a good electric conductivity, around 45 to 141 S cm{sup −1} with slight dependence on the temperature, which is of several orders of magnitude higher than that of the silicate slags. Further, electric conductivity of high-titania slag decreased with the increasing FeO content, whereas, the increasing Ti{sup 3+}/Ti{sup 4+} and TiO{sub 2} contents caused a significant increase in the electric conductivity. Based on the experimental results and the calculated results, the conductive mechanism of high-titania slag was discussed in detail. It can be concluded that the high-titania slag exhibits a characteristic of electronic–ionic mixed conductivity, but the effect of electronic conduction dominates above the liquidus temperature; however, with the decreasing temperature, the electronic conductivity was gradually weakened. The mechanism was postulated to be a random walk of electrons between tetravalent titanium and trivalent titanium dispersed in the melt.

36 MATERIALS SCIENCE↗