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At least 19 records

High-Pressure Equation of State for Partially Ionic Solids

Recently, we showed that the cohesive energy of partially ionic solids may be characterized by a two-term energy relationship consisting of a Coulomb term arising from the valence-charge transfer delta Z between the atoms, and a scaled universal energy function E(sup *)(a(sup *)), which accounts for the partially covalent character of the bond and for the repulsion between the atomic cores for small R; a(sup *) is a scaled length. Normalized cohesive-energy curves of alkali halide crystals and of Ti and Ag halide crystals were obtained, and the cohesive-energy-curve parameters were used to generate theoretical equation-of-state (EOS) curves for the Li, Na, K, Cs, and Ag halides. Good agreement was obtained with the experimental isothermal compression curves over a wide pressure range (0-90 kbar). In this paper we verify that the cohesive-energy relationship is valid for divalent partially ionic solids; physically reasonable charge-transfer values (1.80 less than delta Z less than 2.0) are obtained for MgO, CaO, and CaS. Next, EOS curves for LiF, NaF, Nal, CsCl, Csl, MgO, CaO, and CaS are generated in terms of the cohesive-energy parameters. These EOS's yield excellent fits to experimental isothermal-compression data and to shock-wave data to very high pressures (P(sub max)= 250-1350 kbar).

Schlosser, Herbert

Electrical screening procedure for solid ionic conductors

An electrical screening method has been developed for preliminary evaluation of polycrystalline specimens of candidates for use as solid ionic conductive electrolytes in batteries. The procedure measures dielectric loss and capacitance, from which are calculated an ac conductivity attributed provisionally to ions and an activation energy for that conductivity. Electronic conductivity is directly measured. The screening procedure applied to sodium beta-alumina yielded acceptable values for conductivity and activation energy.

Kautz, H. E.

High pressure far infrared spectroscopy of ionic solids

A high-pressure far-infrared cell operating at up to truly hydrostatic pressures of 8 kbar is described and used to determine the anharmonic self-energies associated with the transverse optic modes of ionic solids in which q approximately equals zero. The cell allows far-infrared studies in the spectral range below 120 reciprocal cm. The transverse optic modes were investigated to determine their mode Gruneisen constants and the pressure dependence of their inverse lifetimes in RbI, CsI, and TlCl.

Lowndes, R. P.

Using Holey Graphene for Improved Interfacial Contact in Solid Electrolyte Ionic Conductivity Measurements

Solid-state batteries (SSBs) are poised to become the batteries of the future with advantages such as higher energy density, lighter weight, versatile geometry, and greater safety due to low flammability risk. An important parameter of the solid electrolyte (SE) used is its ionic conductivity. The ionic conductivity is generally calculated from the bulk resistance of a SE pellet, measured from the electrochemical impedance spectroscopy data. The SE pellet is typically prepared from the electrolyte powder by dry compression and is sandwiched between two blocking current collectors to obtain the impedance spectroscopy data. One of the challenges in conducting this measurement is poor interfacial contacts between the SE pellet and the current collector surfaces. Therefore, measurements reported in the literature may underestimate the true ionic conductivity of a given electrolyte. Holey graphene is a carbon nanomaterial with high electrical conductivity and unique dry compressibility, which is unusual for carbon materials but similar to many oxide and sulfide SEs. In this work, it is demonstrated that adding a thin layer of holey graphene between the electrolyte and the stainless steel current collectors significantly improves the interfacial contact. The ionic conductivity values obtained in the effort were sometimes several times higher than the data measured for SEs without the holey graphene layers. This work calls for more standardized measurement procedures to reduce the discrepancies in reported ionic conductivity values.

Solid state battery

Ionic conductivity of solid mixtures

Ionic conductivities of solid mixtures of lithium fluoride-lithium chloride, lithium chloride- potassium chloride, lithium fluoride-sodium chloride, and sodium chloride-potassium chloride

Fielder, W. L.

Friction and wear behavior of glasses and ceramics

Adhesion, friction, and wear behavior of glasses and ionic solids are reviewed. These materials are shown to behave in a manner similar to other solids with respect to adhesion. Their friction characteristics are shown to be sensitive to environmental constituents and surface films. This sensitivity can be related to a reduction in adhesive bonding and the changes in surficial mechanical behavior associated with Rehbinder and Joffe effects. Both friction and wear properties of ionic crystalline solids are highly anisotropic. With metals in contact with ionic solids the fracture strength of the ionic solid and the shear strength in the metal and those properties that determine these will dictate which of the materials undergoes adhesive wear. The chemical activity of the metal plays an important role in the nature and strength of the adhesive interfacial bond that develops between the metal and a glass or ionic solid.

Buckley, D. H.

Friction and wear behavior of glasses and ceramics.

Adhesion, friction and wear behavior of glasses and ionic solids are reviewed. These materials are shown to behave in a manner similar to other solids with respect to adhesion. Their friction characteristics are shown to be sensitive to environmental constituents and surface films. This sensitivity can be related to a reduction in adhesive bonding and the changes in surficial mechanical behavior associated with Rehbinder and Joffe effects. Both friction and wear properties of ionic crystalline solids are highly anisotropic. With metals in contact with ionic solids, the fracture strength of the ionic solid, the shear strength in the metal, and those properties that determine these will dictate which of the materials undergoes adhesive wear.

Buckley, D. H.

Global expression for representing cohesive-energy curves. II

Schlosser et al. (1991) showed that the R dependence of the cohesive energy of partially ionic solids may be characterized by a two-term energy relationship consisting of a Coulomb term arising from the charge transfer, delta-Z, and a scaled universal energy function, E*(a *), which accounts for the partially covalent character of the bond and for repulsion between the atomic cores for small R; a* is a scaled length. In the paper by Schlosser et al., the normalized cohesive-energy curves of NaCl-structure alkali-halide crystals were generated with this expression. In this paper we generate the cohesive-energy curves of several families of partially ionic solids with different crystal structures and differing degrees of ionicity. These include the CsCl-structure Cs halides, and the Tl and Ag halides, which have weaker ionic bonding than the alkali halides, and which have the CsCl and NaCl structures, respectively. The cohesive-energy-curve parameters are then used to generate theoretical isothermal compression curves for the Li, Na, K, Cs, and Ag halides. We find good agreement with the available experimental compression data.

Schlosser, Herbert

Electrodeless electrolysis

Electrodeless electrolysis of solid ionic conductors and fused salts without contact leads, using electron beams and glow discharge

Brenner, A.

Matrix isolation technique for the study of some factors affecting the partitioning of trace elements

The factors that affect the preferred positions of cations in ionic solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La(+3) and Ca(+2) in a KBr host lattice were examined as a function of the polyvalent cation concentration. The cation-anion pairing process was found to be random for Ca(+2), whereas the formation of La(+3)-SO4(-2) ion pairs with a C2 sub v bonding geometry is highly preferential to any type of La(+3)-CrO4(-2) ion pair formation. The relative populations of ion pair site configurations are discussed in terms of an energy-entropy competition model which can be applied to the partition of trace elements during magmatic processes.

Grzybowski, J. M.

Thermoluminescence and lattice defects in LiF

The principal effect of thermal and optical treatments in an ionic solid is to alter the lattice defect equilibrium, including the concentration and arrangement of ion vacancies, impurities, impurity-vacancy associates, and assorted electrons and holes which may be associated with such defects. This paper examines the relationship between these defects and thermoluminescence in the case of lithium fluoride at and above room temperature. The discussion focuses on lattice defect equilibrium, thermoluminescent trapping centers, the relationship between recombination and luminescence, the supralinearity and sensitization of the dosimetry grade of LiF and activation energy parameters.

Stoebe, T. G.

Effect of microstructure on Na/+/ diffusion in beta alumina

The effect of microstructural features, such as grain size and orientation, on sodium ion diffusion in polycrystalline beta alumina is investigated; the ionic solid is suitable for use in high-energy and power density batteries. Two types of hot-pressed polycrystalline samples are studied, one with grains highly oriented in the direction normal to the pressing direction, the other with significantly less preferred orientation normal to the pressing direction. Results of the experimental assessments indicate that grain size and diffusion path tortuosity have little effect on diffusion kinetics, while grain boundary type and grain aspect ratio are important factors in determining the diffusion rate.

Sarian, S.

Survey of Materials Problems Resulting from Low-Pressure and Radiation Environment in Space

On the basis of our present knowledge of the space environment, one might state that the exposure of materials to the radiation environment will present problems mainly with the impairment of the transparency of plastics and ionic solids due to ultraviolet radiation and with surface sputtering effects on emissivity and other thin film properties. The high vacuum in space will be of greater consequence in that it will render useless some members of practically all of the material classes. However, adequate solutions to most problems can be anticipated if enough information is at hand. This survey indicates that information is lacking at levels from the basic to the applied. A partial list of research areas in need of attack is included.

Lad, Robert A.

Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

In an attempt to more completely understand the surface chemistry of the jovian icy satellites, we have investigated the effect of heating on two irradiated crystalline sulfuric acid hydrates, H2SO4 4H2O and H2SO4 H2O. At temperatures relevant to Europa and the warmer jovian satellites, post-irradiation heating recrystallized the amorphized samples and increased the intensities of the remaining hydrate's infrared absorptions. This thermal regeneration of the original hydrates was nearly 100% efficient, indicating that over geological times, thermally-induced phase transitions enhanced by temperature fluctuations will reform a large fraction of crystalline hydrated sulfuric acid that is destroyed by radiation processing. The work described is the first demonstration of the competition between radiation-induced amorphization and thermally-induced recrystallization in icy ionic solids relevant to the outer Solar System.

Loeffler, Mark J.

Lithium-Based High Energy Density Flow Batteries

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Bugga, Ratnakumar V.

New Polymer Electrolyte Cell Systems

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Smyrl, William H.