Engineering PapersSearch

SEARCH · Engineering Papers

Results for “electrolyte structure”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records

Freeze Casting of LAGP for 3D Textured Solid-State Structural Electrolytes

In this study, all-solid-state structural lithium-ion batteries, a type of load bearing electrochemical energy storage that provides systems-level weight savings is being pursued for the realization of inherently safe next generation hybrid-electric and all-electric green aerospace propulsion systems. Currently investigated all-solid-state batteries do not meet the requirements for specific power and mechanical stability. To address these issues, freeze casting of lithium aluminum germanium phosphate (LAGP) electrolyte material has been explored for the creation of a textured 3D electrolyte scaffold with large interfacial surface area for high power discharge and hierarchical porosity for accommodation of active material volume changes during electrochemical cycling. We report the effects of freeze casting processing parameters on the microstructural development and mechanical performance of the scaffolds, characterized through scanning electron microscopy and ring-on-ring mechanical testing. Slurry composition and casting parameters such as solids loading, casting speed, tape angle, and temperature gradients have been modified to determine the impact on density, lamellar morphology, and final load-bearing performance.

ceramics

Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

Bronstein, Lyudmila M.

Porous matrix structures for alkaline electrolyte fuel cells

A number of advancements have been realized by a continuing research program to develop higher chemically stable porous matrix structures with high bubble pressure (crossover resistance) for use as separators in potassium hydroxide electrolyte fuel cells. More uniform, higher-bubble-pressure asbestos matrices were produced by reconstituting Johns-Manville asbestos paper; Fybex potassium titanate which was found compatible with 42% KOH at 250 F for up to 3000 hr; good agreement was found between bubble pressures predicted by an analytical study and those measured with filtered structures; Teflon-bonded Fybex matrices with bubble pressures greater than 30 psi were obtained by filtering a water slurry of the mixture directly onto fuel cell electrodes; and PBI fibers have satisfactory compatibility with 42% KOH at 250 F.

Vine, R. W.

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

Tigelaar, Dean M.

Foaming-electrolyte fuel cell

Foam structure feeds fuel gas solution into electrolyte. Fuel gas reacts at static, three-phase interface between fuel gas, electrolyte, and electrode material. The foam forms an electrical contact between main body of electrolyte and the electrode, and aids in removal of by-products of the chemical reaction.

Nanis, L.

Mechanical Model Development for Composite Structural Supercapacitors

Novel composite structural supercapacitor concepts have recently been developed as a means both to store electrical charge and to provide modest mechanical load carrying capability. Double-layer composite supercapacitors are often fabricated by impregnating a woven carbon fiber fabric, which serves as the electrodes, with a structural polymer electrolyte. Polypropylene or a glass fabric is often used as the separator material. Recent research has been primarily limited to evaluating these composites experimentally. In this study, mechanical models based on the Multiscale Generalized Method of Cells (MSGMC) were developed and used to calculate the shear and tensile properties and response of two composite structural supercapacitors from the literature. The modeling approach was first validated against traditional composite laminate data. MSGMC models for composite supercapacitors were developed, and accurate elastic shear/tensile properties were obtained. It is envisioned that further development of the models presented in this work will facilitate the design of composite components for aerospace and automotive applications and can be used to screen candidate constituent materials for inclusion in future composite structural supercapacitor concepts.

Micromechanics

Survey on aging on electrodes and electrocatalysts in phosphoric acid fuel cells

The processes which contribute to the decay in performance of electrodes used in phosphoric acid fuel cell systems are discussed. Loss of catalytic surface area, corrosion of the carbon support, electrode structure degradation, electrolyte degradation, and impurities in the reactant streams are identified as the major areas for concern.

Stonehart, P.

(abstract) Mechanism of Selective Porosification at Heterojunctions in Group IV Multilayer Structures

Highly selective porosification of SiGe or Ge layers is observed in multilayer Si/SiGe or Si/Ge structures grown on (100)Si. These alternating porous/nonporous structures could potentially be used to fabricate light-emitting devices. The etch-selectivity appears to be dominated by band-structure effects and other factors such as lattice strain and electrochemical potential differences play a minor role. Additional structures and electrolytic etching are being examined to confirm these results.

porosification silicon Si Ge germanium light emitt

High power density proton exchange membrane fuel cells

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

Murphy, Oliver J.

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI] and [EMIM][BF4]

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-Nbutylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-Npropylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of x(sub Li) we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing x(sub Li), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of x(sub Li) is approximately 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 - 0.3 mS/cm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

lithium batteries

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4]

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

ionic liquids

Investigation of Structure and Transport in Li-Doped Ionic Liquid Electrolytes: [pyr14][TFSI], [pyr13][FSI], [EMIM][BF4]

Ionic liquid electrolytes have been proposed as a means of improving the safety and cycling behavior of advanced lithium batteries; however, the properties of these electrolytes under high lithium doping are poorly understood. Here, we employ both polarizable molecular dynamics simulation and experiment to investigate the structure, thermodynamics and transport of three potential electrolytes, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N- methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-- methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li (-) salt concentration and temperature. Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi we find the presence of lithium aggregates. Furthermore, the computed density, diffusion, viscosity, and ionic conductivity show excellent agreement with experimental data. While the diffusion and viscosity exhibit a systematic decrease and increase, respectively, with increasing xLi, the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions, which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, we comment on the relative kinetics of Li(+) transport in each liquid and we present strong evidence for transport through anion exchange (hopping) as opposed to the net motion of Li(+) with its solvation shell (vehicular).

molecular dynamics

Electrodeionization Using Microseparated Bipolar Membranes

An electrochemical technique for deionizing water, now under development, is intended to overcome a major limitation of prior electrically-based water-purification techniques. The limitation in question is caused by the desired decrease in the concentration of ions during purification: As the concentration of ions decreases, the electrical resistivity of the water increases, posing an electrical barrier to the removal of the remaining ions. In the present technique, this limitation is overcome by use of electrodes, a flowfield structure, and solid electrolytes configured to provide conductive paths for the removal of ions from the water to be deionized, even when the water has already been purified to a high degree. The technique involves the use of a bipolar membrane unit (BMU), which includes a cation-exchange membrane and an anion-exchange membrane separated by a nonconductive mesh that has been coated by an ionically conductive material (see figure). The mesh ensures the desired microseparation between the ion-exchange membranes: The interstices bounded by the inner surfaces of the membranes and the outer surfaces of the coated mesh constitute a flow-field structure that allows the water that one seeks to deionize (hereafter called "process water" for short) to flow through the BMU with a low pressure drop. The flow-field structure is such that the distance between any point in the flow field and an ionically conductive material is small; thus, the flow-field structure facilitates the diffusion of molecules and ions to and from the ion-exchange membranes. The BMU is placed between an anode and a cathode, but not in direct contact with these electrodes. Instead, the space between the anion-exchange membrane and the anode is denoted the anode compartment and is filled with an ionic solution. Similarly, the space between the cation-exchange membrane and the cathode is denoted the cathode compartment and is filled with a different ionic solution. The electrodes are made of titanium coated with platinum.

Lyons, Donald

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

Stonehart, P.

Microgravity effects on electrodeposition of metals and metal-cermet mixtures

An experimental system, designed to investigate the potential advantages of electrodeposition in microgravity, is being developed by the McDonnell Douglas Astronautics Company-Huntsville Division and the University of Alabama in Huntsville. It is intended to fly as an Orbiter payload when NASA resumes STS operations. The system will provide power, thermal conditioning, command and control for the production of electrodeposits; system performance data will be recorded for post-flight analysis. Plated metal surfaces will be created using simple electrolytic cells with pure metal electrodes immersed in aqueous electrolytic solutions. Crystalline structure and other properties will be analyzed to identify differences between samples produced in flight and those obtained from ground-based operations.

Maybee, George W.

Interfacial Structure and Capacitance of Li-doped Ionic Liquid Electrolytes from Molecular Simulations

Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries, supercapacitors, and hybrid energy storage devices. Though Li-salt is often present in these systems, its influence on interfacial properties is largely uncharacterized. We, thereby, present an extensive computational analysis, supported by experimental comparisons, of the properties of a representative set of these electrolytesat an ideal carbon interface as a function of Li-salt doping and voltage. We have performed polarizable molecular (MD) dynamics simulations, using the APPLEP force field, to evaluate electric double layer (EDL) capacitance and distribution of Li+ in the EDL. Differential capacitance exhibits the characteristic camel profile and is insensitive to Li-doping. Li+ localizes in the second molecular layer of the EDL, which is a result of confinement from free energy barriers associated with ion layering. Joint MDelectronic structure computations show the electrochemical window of the electrolytes to be a weak function of Li-doping. Estimates of supercapacitor specific energy are made using the computed window and capacitance. The magnitude and trends in specific energy are in good agreement with experiment.

batteries