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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

An Improved Microwave Semiempirical Model for the Dielectric Behavior of Moist Soils

Soil semiempirical dielectric models (SEMs) are powerful, and they are generally considered a useful hybrid of both empirical and physical models. In this work, the Wang-Schmugge dielectric model is improved to more accurately estimate the relative complex dielectric constants (CDCs) of moist soils. Instead of the Debye relaxation spectrum of liquid water located outside of the soil (i.e., free out-of-soil water) adopted in the Wang-Schmugge model, the Debye relaxation formula related to the free-water component inside the soil [i.e., free soil water (FSW)], which is correlated with the soil texture, is employed in the improved SEM. In addition, the effective conductivity loss term related to both soil texture and soil moisture is introduced to explain the ionic conductivity losses of FSW. Since the soil moisture influence is reduced at high frequencies, the effective conductivity loss term related to only the soil texture is also analyzed for 14-18 GHz. As in the Wang-Schmugge model, the relative CDC of bound soil water varies with the soil volumetric moisture content when the soil moisture is lower than the maximum bound water fraction in the new model, which takes a different approach than the Mironov mineralogy-based SEM. The proposed model obtains better fitting results than the three most widely employed SEMs. Lastly, the improved model exhibits a significantly improved accuracy with a higher correlation coefficient (R²), a closer 1:1 relationship, and a lower root-mean-square error, including in the L-band, and especially in the imaginary part of the L-band.

semiempirical dielectric model (SEM)↗
DOE OSTI2019

Correlations from Ion Pairing and the Nernst-Einstein Equation

In this work, we present a new approximation to ionic conductivity well suited to dynamical atomic-scale simulations, based on the Nernst-Einstein equation. In our approximation, ionic aggregates constitute the elementary charge carriers, and are considered as noninteracting species. This approach conveniently captures the dominant effect of ion-ion correlations on conductivity, short range interactions in the form of clustering. In addition to providing better estimates to the conductivity at a lower computational cost than exact approaches, this new method allows us to understand the physical mechanisms driving ion conduction in concentrated electrolytes. As an example, we consider Li + conduction in poly(ethylene oxide), a standard solid-state polymer electrolyte. Using our newly developed approach, we are able to reproduce recent experimental results reporting negative cation transference numbers at high salt concentrations, and to confirm that this effect can be caused by a large population of negatively charged clusters involving cations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Structure and properties of solid polymer electrolyte based on chitosan and ZrO{sub 2} nanoparticle for lithium ion battery

In order to develop all solid lithium ion battery, study on the structure and properties of solid polymer electrolytes (SPE) based on chitosan has been done. The SPE were prepared by adding Zirconia (ZrO{sub 2}) nanoparticle and LiClO{sub 4} as lithium salt into the chitosan solution followed by casting method. Effect of the ZrO{sub 2} and salt concentration to the structure and properties of SPE were elaborated using several methods. The structure of the SPE cast film, were characterized mainly by using X-ray diffractometer (XRD). While the electrical properties of SPE were studied by electrochemical impedance spectrometer (EIS) and ion transference number measurement. XRD profiles show that the addition of ZrO{sub 2} and LiClO{sub 4} disrupts the crystality of chitosan. The decrease in sample crytalinity with the nanoparticle and salt addition may increase the molecular mobility result in the increasing sample conductivity and cathionic transference number as determined by EIS and ion transference number measurement, respectively. The highest ionic conductivity (3.58×10{sup −4} S cm{sup −1}) was obtained when 4 wt% of ZrO{sub 2} nanoparticle and 40 wt% of LiClO{sub 4} salt were added to the chitosan. The ion transference number with that composition was 0.55. It is high enough to be used as SPE for lithium ion battery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Framework Short-Range Order Observed in a Spinel-Type Li Superionic Conductor

Solid-state superionic conductors are characterized by rich structural disorders. Though structural complexities are central to their functionalities, they often give rise to short-range order that eludes detection by conventional diffraction-based techniques and is thus overlooked in establishing precise structure-property relationships. In this work, we synthesized single crystals of a recently discovered lithium (Li) superionic conductor Li16.2(1)In9.00(2)Sn1.10(1)O23.8 (LISO) for in-depth characterizations of structural subtleties. LISO exhibits an unusual spinel-like phase with significant Li overstoichiometry and a face-sharing Li network. Single-crystal neutron diffraction confirms significant Li disorder, as manifested in Li site splitting and partial occupancy. More importantly, synchrotron diffuse scattering combined with 3D-ΔPDF analysis and Monte Carlo simulations reveal short-range order in the nonalkali framework that might contribute to the phase stability and ionic conductivity. This work showcases an example in which subtle local energetics can be directly visualized in structurally disordered ionic conductors.

Chen, Yu↗
DOE OSTI2024

Probing the potential of type V Deep eutectic solvents as sustainable electrolytes

The increasing interest within the scientific community in environmentally friendly solvents has led to a focus on Deep Eutectic Solvents (DES), which have natural components. DES are viewed as alternatives to traditional organic solvents and have the potential to be used as electrolytes. For the first time, transport properties of four Type V Deep Eutectic Salt Solutions (DESS) were accessed to investigate the potential of this technology, selecting precursors ranked as excellent in Eco-Scale metrics. The DESS were composed of terpene and trioctylphosphine oxide (TOPO), and varying concentrations of lithium bis(trifluoromethane)sulfonimide (LiTFSI), and their properties were assessed through self-diffusion, viscosity, density, and conductivity measurements. While Type V DESS are capable of dissolving significant amounts of LiTFSI (up to 30 % molar), their ionic conductivity is low, with values ranging from 3.6·10 –3 to 9.3·10 –2 mS·cm –1 at 25 °C, thus limiting their suitability as electrolytes, for instance, for lithium-ions batteries applications. Similar diffusion coefficients for Li + and TFSI – ions suggest the formation of long-lived ion pairs moving as a neutral species. As a result, future research aims to introduce additives to disrupt contact ion pairs and enhance transport properties, leveraging the sustainable appeal of DES and their use in advanced energy storage technologies.

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

Polycarbonate‐Based Solid‐Polymer Electrolytes for Solid‐State Sodium Batteries

Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1 mS cm −1 at 80 °C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83 mA h g −1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60 °C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. In conclusion, these results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.

25 ENERGY STORAGE↗
DOE OSTI2025

Infiltrated electrodes for metal supported solid oxide electrolysis cells

Metal-supported solid oxide cells (MSOCs) are an alternative to conventional solid oxide cells (SOCs) based on ceramic cermets, offering lower material costs and higher operational flexibility. In this study symmetric MSOCs with infiltrated electrodes are explored for steam electrolysis operation to understand the underlying operation and degradation principles and suggest a direction for future MSOCs development. Two different fuel electrode backbones are used: an electronically-conductive lanthanum strontium co-doped iron nickel titanate (LSFNT) infiltrated with cerium-gadolinium oxide (CGO), or an ionic conductive zirconia based backbone (10ScYSZ) infiltrated with Ni:CGO. At the oxygen side, the backbone is 10ScYSZ, which is infiltrated with lanthanum-strontium co-doped cobalt oxide (LSC), or praseodymium oxide as cobalt-free alternative for comparison. This study suggests that the backbone electronic conductivity is key for good electrochemical performance as well as for boosting cell durability. Highly electronically conductive nanoparticles, especially nickel, were observed to irreversibly agglomerate driven by thermal conditions, whereas CGO proved to be a very stable electrocatalyst. At the fuel side, CGO (LSFNT) electrode showed lower ASR and degradation rate than Ni:CGO(ScYSZ) configuration with measured values of 0.50 Ω cm2 and 11 %/1000 h (at 0.60 A/cm2), and 0.70 Ω cm2 and 26 %/1000 h (at 0.50 A/cm2) at 1.30 V, respectively (700 °C, 50 % steam in hydrogen at the fuel side and air at the oxygen electrode side, LSC(ScYSZ) oxygen electrode).

25 ENERGY STORAGE↗
DOE OSTI2021

Limiting Current in Nanostructured Block Copolymer Electrolytes

The next-generation electrolytes for lithium batteries must be able to conduct ions at sufficiently high current densities; yet this regime is rarely studied directly. The limiting current density of an electrolyte quantifies the highest possible rate of ion transport under an applied dc potential. Herein, we report on the limiting current density in twelve nanostructured polystyrene-block-poly(ethylene oxide) (PS-b-PEO, or SEO) copolymer electrolytes. We find that the limiting current at a given salt concentration increases systematically with increasing volume fraction of the PEO block (φ EO ). In contrast, the effective-medium theory, commonly used to analyze conductivity in block copolymer electrolytes, predicts that limiting current is independent of φ EO . To resolve this conundrum, the ionic conductivity, the mutual diffusion coefficient of the salt, and the steady-state current fraction of the block copolymer electrolytes were measured. These measurements enable predictions of limiting current with no adjustable parameters using the concentrated solution theory. We found quantitative agreement between experimentally measured limiting current densities and predictions based on the concentrated solution theory. This work sheds light on how to reliably measure and predict limiting current density in composite electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2015

Study and characterization of the irreversible transformation of electrically stressed planar Ti/TiO{sub x}/Ti junctions

We investigate the properties and characteristics of planar Ti/TiO{sub x}/Ti junctions, which consist of transverse TiO{sub x} lines drawn on Ti test patterns. Junctions are elaborated by means of local anodic oxidation using atomic force microscopy. An irreversible morphological transformation occurring in a reproducible manner is observed when these planar junctions are electrically stressed under ambient atmosphere. Structural and chemical analyses based on transmission electron microscopy techniques reveal the extension of the initial amorphous TiO{sub x} into a crystalline rutile phase. This irreversible transformation is proven to vanish completely if the electrical stress occurs under vacuum atmosphere. Finally, we carry out temperature dependent electrical measurements in order to elucidate their conduction mechanism: Schottky emission above an ultra-low potential barrier is assumed to dominate under vacuum atmosphere whereas ionic conduction seems to prevail in air.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO 2 Electrolyzer Cathode

Electrochemical CO 2 reduction is a promising technology to capture and convert CO 2 to valuable chemicals. High Faradaic efficiencies of CO 2 reduction products are achieved with zero-gap alkaline CO 2 electrolyzers with a supporting electrolyte at the anode (anolyte). Herein, we investigate the effect of anolyte on the electrode properties such as catalyst utilization, ionic accessibility etc. of a CO 2 reduction cathode using electrochemical techniques and cell configurations that avoid the complexities related to co-electrolysis. Using 1M KOH as the anolyte and a Cu gas-diffusion-electrode with low Nafion content as the model CO 2 reduction electrode, we find that electrode capacitance (proxy for electrochemically active surface area) and ionic conductivity inside the cathode increase approximately 4 and 447 times, respectively, in presence of KOH. Liquid anolyte wets the electrode’s pore structure more efficiently than capillary condensation of feed water vapor. The ionomer coverage is very low, and its distribution inside the electrode is highly fragmented. Surface ion conduction mechanisms inside the electrode are orders of magnitude lower than the bulk ion conduction in presence of anolyte. This study shows that when an anolyte (e.g., KOH) is used, catalyst utilization and ionic accessibility inside the electrode increase significantly.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2017

Predictive Design of Shear-Thickening Electrolytes for Safety Considerations

Non-Newtonian, shear-thickening lithium-ion battery electrolytes show promise for improved safety in high impact events by exhibiting a reversible transition to a solid-like phase under high shear. This aids in the prevention of shorting and subsequent combustion of volatile electrolyte under such conditions. In this work, we investigate the electrodynamics of shear-thickening electrolytes using conductivity under shear measurements, as well as finite-element modeling. We observe an order of magnitude drop in ionic conductivity under shear-thickening conditions. We suggest a working model to explain substantial drops in conductivity observed in shear-thickening electrolytes under shear. Here the results here can be generally applied to any electrolyte that exhibits non-Newtonian hydrodynamic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Measurement of Ionic and Electronic Conductivities of Yttria-Stabilized Zirconia by an Embedded Electrode Method

A new technique is presented for the measurement of ionic and electronic conductivities in predominantly oxygen ion conducting materials such as 8YSZ. Cylindrical disc samples of 8YSZ with an embedded Pt wire electrode in the center and two surface porous Pt electrodes were fabricated. When a DC electrical potential is applied across one surface electrode and the embedded electrode, oxygen ions migrate through the YSZ toward the embedded electrode, while electrons transport in the external circuit. In this manner, neutral oxygen is electrochemically pumped to the embedded electrode raising the local oxygen chemical potential. Under the pressure built up, oxygen permeation occurs from the embedded electrode, through the YSZ sample, to the outer surfaces of the sample. In steady state, the electrochemical oxygen flux to the embedded electrode under applied voltage is exactly balanced by out permeation of oxygen governed by the electronic conductivity. Here, using this technique both the ionic and the electronic conductivities of YSZ were measured at a temperature as low as 500°C.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Flexocoupling impact on size effects of piezoresponse and conductance in mixed-type ferroelectric semiconductors under applied pressure

Here, we explore the role of flexoelectric effect in functional properties of nanoscale ferroelectric films with mixed electronic-ionic conductivity. Using a coupled Ginzburg-Landau model, we calculate spontaneous polarization, effective piezoresponse, elastic strain and compliance, carrier concentration, and piezoconductance as a function of thickness and applied pressure. In the absence of flexoelectric coupling, the studied physical quantities manifest well-explored size-induced phase transitions, including transition to paraelectric phase below critical thickness. Similarly, in the absence of external pressure flexoelectric coupling affects properties of these films only weakly. However, the combined effect of flexoelectric coupling and external pressure induces polarizations at the film surfaces, which cause the electric built-in field that destroys the thickness-induced phase transition to paraelectric phase and induces the electretlike state with irreversible spontaneous polarization below critical thickness. Interestingly, the built-in field leads to noticeable increase of the average strain and elastic compliance in this thickness range. We further illustrate that the changes of the electron concentration by several orders of magnitude under positive or negative pressures can lead to the occurrence of high- or low-conductivity states, i.e., the nonvolatile piezoresistive switching, in which the swing can be controlled by the film thickness and flexoelectric coupling. The obtained theoretical results can be of fundamental interest for ferroic systems, and can provide a theoretical model for explanation of a set of recent experimental results on resistive switching and transient polar states in these systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

3D Ion-Conducting, Scalable, and Mechanically Reinforced Ceramic Film for High Voltage Solid-State Batteries

Concerning the safety aspects of Li+ ion batteries, an epoxy-reinforced thin ceramic film (ERTCF) is prepared by firing and sintering a slurry-casted composite powder film. The ERTCF is composed of Li + ion conduction channels and is made of high amounts of sintered ceramic Li 1+ x Ti 2-x Al x (PO 4 ) 3 (LATP) and epoxy polymer with enhanced mechanical properties for solid-state batteries. The two- and three-dimensional characterizations are conducted not only for showing continuous Li+ ion channels thorough LATP ceramic channels with over 10-4 S cm-1 of ionic conductivity but also to investigate small amounts of epoxy polymer with enhanced mechanical properties. Solid-state Li + ion cells are fabricated using the ERTCF and they show initial charge–discharge capacities of 139/133 mAh g -1 . Furthermore, the scope of the ERTCF is expanded to high-voltage (>8 V) solid-state Li + ion batteries through a bipolar stacked cell design. Hence, it is expected that the present investigation will significantly contribute in the preparation of the next generation reinforced thin ceramic film electrolytes for high-voltage solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2013

Synthesis, structural, magnetic and electrical properties of Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (x = 0.0, 0.2) nanoparticles

Graphical abstract: The variations of imaginary part of dielectric permittivity (ε″) of TEG@Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} nanocomposite as a function of temperature and frequency for (A) x = 0.0 and (B) x = 0.2. Display Omitted Highlights: ► Nearly monodisperse Zn{sub x}Co{sub 1−x}Fe{sub 2}O{sub 4} nanocomposite were prepared via hydrothermal method. ► The ac conductivity showed a temperature dependent behavior at low frequencies. ► dc conductivity of Co{sub 0.8}Zn{sub 0.2}Fe{sub 2}O{sub 4} nanoparticle are found to obey the Arrhenius plot. ► Also these materials may be used in electronic devices and microwave devices. -- Abstract: Co{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} spinel nanoparticles with Zn concentrations of x = 0.0, 0.2 were prepared by a hydrothermal route in the presence of triethylene glycol (TEG). The structural, magnetic, electrical and dielectric properties of the prepared nanoparticles were studied. The XRD results confirmed the formation of single spinel ferrite structure with crystallite size 9 and 10 nm for x = 0.0 and 0.2 compositions respectively. The lattice parameter (a) increased with increasing Zn concentration. Temperature and frequency dependent electrical and dielectric properties of the prepared ferrites have also been investigated. Our findings show that overall conductivity of Co{sub 0.8}Zn{sub 0.2}Fe{sub 2}O{sub 4} nanoparticle is lower than that of CoFe{sub 2}O{sub 4} and roughly in the range of 10{sup −11}–10{sup −7} S cm{sup −1} depending strongly temperature and frequency owing to the formation of stable electric bonds between the Zn{sup 2+} and Fe{sup 2+} ions, which localizes Fe{sup 2+} charge carriers. The ac conductivity showed a temperature dependent behavior at low frequencies and temperature independent behavior at high frequencies, which is an indication of ionic conductivity. dc conductivity of Co{sub 0.8}Zn{sub 0.2}Fe{sub 2}O{sub 4} nanoparticle are found to obey the Arrhenius plot and can be classified into two regions over with activation energy of 0.113 and 0.163 eV in the ranges of 20–40 °C and 70–120 °C, respectively when CoFe{sub 2}O{sub 4} has an activation energy of 0.245 eV.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Defects clustering and ordering in di- and trivalently doped ceria

Graphical abstract: Display Omitted Highlights: ► Defect structures in trivalently and divalently doped ceria has been elucidated. ► Dumbbell structure is a universal basic vacancy structure in fluorite oxides. ► Electrostatic attraction dominates elastic interaction in doped ceria. ► Provide a physical picture of conductivity behavior in aliovalently doped ceria. -- Abstract: The formation and growth of defect clusters in CeO{sub 2}-M{sub 2}O{sub 3} (M = La{sup 3+}, Pr{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Dy{sup 3+}, Y{sup 3+}, Yb{sup 3+}) and CeO{sub 2}-DO (N = Cd{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, Ba{sup 2+}) binary solid solutions have been comparatively studied by atomistic simulations based on energy minimization of atomic interactions. The calculation ensemble, including both divalent and trivalent dopants, shows a similar energetic tendency for defect species (dopants and associated oxygen vacancies) to aggregate and grow. The dumbbell structure has been verified as a universal vacancy structure in oxygen deficient fluorite lattice. Nevertheless, it also demonstrates different tendencies of dopant–vacancy associations that depend on dopant valence and radius. The dopant is site-selective in trivalent defect clusters correlated with dopant size. While in divalent solid solutions, clusters adopt similar dopant–vacancy locations. Furthermore, all clusters in divalently doped ceria have stronger dopant–vacancy associations/interactions compared to those in trivalent ones. As a consequence, the correlation of the dopant size as well as valence effects on oxygen-ion conductivity has been illustrated based on an ordered defect cluster model. This study thereby offers insight into the physical picture of ionic conductivity behavior experimentally obtained in aliovalently doped ceria.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites

Optimizing proton conduction in solids remains the most promising solution for achieving intermediate temperature (~750–1000 K) solid oxide fuel cell devices, and enabling selective membranes for H 2 separation. Proton conduction, a thermally activated process, exhibits its highest rates in yttrium (Y) acceptor doped BaZrO 3 at an optimal doping level of 20% Y. The presence of extended defects such as grain boundaries has typically generated a wide variability in reported conductivity values. This has hindered a fundamental mechanistic understanding of how (acceptor) doping levels correlate with the activation energy of protons to produce an optimal doping level for fast proton transport. While isolated dopants have been suggested as the primary source of proton trapping, our results indicate that it is the local dopant-density that matters. Here in this work, we show that increasing the local dopant density promotes localized lattice distortions in the presence of point defects such as oxygen-vacancies or proton interstitials. An increasing distortion amplitude traps the point defects more strongly in the form of polarons, forming defect-clusters at higher concentrations. This leads to a monotonic increase in the activation energy (and hence a decrease in proton mobility) as observed in our measurements. The optimum doping level can now be explained as a competition between increasing proton concentration with doping levels and increasing activation energy due to defect-clusters formed by defect-polarons. Based on our findings, we demonstrate how to improve proton conductivity in doped BaZrO 3 , by inhibiting this dopant-lattice polaronic interaction. Finally, this approach should be generally applicable for ionic conduction in perovskite oxides such as oxygen-ion conduction in solid-oxide fuel cells and alkali-ion conduction in solid-state batteries where carriers might get trapped as defect-polarons.

36 MATERIALS SCIENCE↗