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At least 865 records · Page 48

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DOE OSTI2020

Engineering Solid Electrolyte Interphase Composition by Assessing Decomposition Pathways of Fluorinated Organic Solvents in Lithium Metal Batteries

Studies have shown fluorinated electrolyte solvents can form desirable solid electrolyte interphase (SEI) in lithium metal batteries. In this study, we develop a detailed mechanistic understanding of two high performing electrolytes, Fluoroethylene Carbonate (FEC) and Difluoroethylene Carbonate (DFEC) to demonstrate minimal structural variations can lead to different decomposition products, and thereby the nature of the SEI. Using density functional theory (DFT) calculations, we find different initial bond-breaking mechanisms between FEC and DFEC. We develop free energy diagrams for the decomposition pathways including both electrochemical and chemical steps. Using the computational Li electrode, we identify the largest limiting potential of 1.77 V for FEC decomposition, associated with the formation of lithium fluoride, lithium oxide and FEC oligomers, and 1.53 V for DFEC, which correspond to the formation of polymerized vinylene carbonate and lithium fluoride. We suggest the formation of oligomers in the case of FEC instead of long polymers may lead to better SEI compactness. We also demonstrate the SEI components of FEC and DFEC are not stable on typical cathode voltage (3.87 V). This study presents a unified electrocatalytic perspective on SEI formation and decomposition.

25 ENERGY STORAGE↗

DOE OSTI2023

A Three-Dimensional, Thermodynamically and Variationally Consistent, Fully Coupled, Electro-Chemo-Thermo-Mechanical Model of Solid-State Batteries

Here we present a theoretical framework for high fidelity modeling of three-dimensional electro-chemo-thermo-mechanical coupled systems such as solid-state batteries. The framework provides a useful means of utilizing molecular level information to predict the overall performance of the system at the continuum level. The central statement of the theoretical framework is a thermodynamically consistent inf-sup problem. The total potential of the coupled system consists of the Helmholtz free energy, the electrical kinetic potential, the chemical potential, the Fourier potential, the chemical reaction potential, and the external power expenditure. All governing equations derive from variational principles. We also show that the resulting initial-boundary-value problem (IBVP) is consistent with existing, widely adopted equations for modeling batteries. Moreover, the IBVP can be naturally discretized using the (variational) finite element method to simulate practical solid-state batteries with arbitrary geometries. Several examples illustrate multiphysics coupling between pairs of the physical field equations, culminating in a comprehensive three-dimensional model of charge-discharge in a solid state battery.

25 ENERGY STORAGE↗

DOE OSTI2020

Substitution of Co with Ni in Co/Al 2 O 3 Catalysts for Fischer–Tropsch Synthesis

The effect of cobalt substitution with nickel was investigated for the Fischer–Tropsch synthesis reaction. Catalysts having different Ni/Co ratios were prepared by aqueous incipient wetness co-impregnation, characterized, and tested using a continuously stirred tank reactor (CSTR) for more than 200 h. The addition of nickel did not significantly modify the morphological properties measured. XRD, STEM, and TPR-XANES results showed intimate contact between nickel and cobalt, strongly suggesting the formation of a Co-Ni solid oxide solution in each case. Moreover, TPR-XANES indicated that nickel addition improves the cobalt reducibility. This may be due to H 2 dissociation and spillover, but is more likely the results of a chemical effect of intimate contact between Co and Ni resulting in Co-Ni alloying after activation. FTS testing revealed a lower initial activity when nickel was added. However, CO conversion continuously increased with time on-stream until a steady-state value (34%–37% depending on Ni/Co ratio) was achieved, which was very close to the value observed for undoped Co/Al 2 O 3 . This trend suggests nickel can stabilize cobalt nanoparticles even at a lower weight percentage of Co. Currently, the cobalt price is 2.13 times the price of nickel. Thus, comparing the activity/price, the catalyst with a Ni/Co ratio of 25/75 has better performance than the unpromoted catalyst. Finally, nickel-promoted catalysts exhibited slightly higher initial selectivity for light hydrocarbons, but this difference typically diminished with time on-stream; once leveling off in conversion was achieved, the C 5+ selectivities were similar (≈ 80%) for Ni/Co ratios up to 10/90, and only slightly lower (≈ 77%) at Ni/Co of 25/75.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Post-Calibration Uncertainty Analysis for Travel Times at a Naval Weapons Industrial Reserve Plant

The Naval Weapons Industrial Reserve Plant (NWIRP) in McGregor, Texas began manufacturing explosives in 1980 and several hazardous chemicals were discovered in lakes and streams surrounding the site in 1998. Contaminants traveled to local lakes and streams much faster than initially predicted. This research estimated contaminant travel times and identified locations where monitoring wells should be installed to yield the greatest reductions in uncertainties in travel-time predictions. To this end, groundwater and particle-tracking models for NWIRP site were built to predict hydraulic heads and contaminant travel times. Next, parameter (hydraulic conductivities) uncertainties, parameter identifiabilities, observation (hydraulic heads) worth, and predictive (contaminant travel times) uncertainties were quantified. Parameter uncertainties were reduced by up to 92%; a total of 19 of 158 parameters were at least moderately identifiable; travel-time uncertainties were reduced up to 92%. Additionally, travel-time predictions and post-calibration parameter distributions were generated using the null-space Monte Carlo (NSMC) technique. NSMC predicted that conservative tracers exited the flow system within a year, which matches with field data. Finally, an observations-worth analysis found that additional 11 more measurements would reduce travel-time uncertainties by factors from 1.04 to 4.3 over existing data if monitoring wells were installed at the suggested locations.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

NASA NTRS1973

Molecule formation. I - In normal H I clouds. II - In interstellar shock waves.

The formation of simple molecules and their role in the chemistry and physics of the interstellar medium is considered. The requirements for recombination reactions to occur on interstellar grains with the subsequent buildup of a molecular mantle are discussed. Together with a discussion of depletion and heating of the evolving gas, this forms the basis for a treatment of the precollision history of dust and gas. All the chemical reactions included in the calculations are given, as well as the results of calculations for two values of the intercloud pressure and for a range of cloud masses. Shock waves in clouds whose precollision history has been calculated are treated, followed by discussion of the shock structure and the dynamics of the grains. The process of sputtering is treated, and expressions are given for the cooling rates, including cooling due to the molecules formed behind the shock front. All the chemical reactions included in the calculations are given, as well as the results of calculations for a range of shock velocities and initial molecular hydrogen abundances.

Aannestad, P. A.↗

NASA NTRS1975

Chemical equilibrium of ablation materials including condensed species

Equilibrium is determined by finding chemical composition with minimum free energy. Method of steepest descent is applied to quadratic representation of free-energy surface. Solution is initiated by selecting arbitrary set of mole fractions, from which point on free-energy surface is computed.

Stroud, C. W.↗

NASA NTRS1974

Io - A surface evaporite deposit

A model is suggested for Io's surface composition involving evaporite salt deposits, rich in sodium and sulfur. According to this model, these deposits were produced as a result of the migration of salt-saturated aqueous solutions to Io's surface from a warm or hot interior followed by loss of the water to space. This model satisfies cosmochemical constraints based on Io's initial composition, current density, and thermal history. Salt-rich assemblages are easily derivable from the leaching of carbonaceous chondritic material. The chemical and optical properties of such deposits, after modification by irradiation, can be used to explain Io's overall albedo and spectral reflectance, its dark reddish poles, and the observed sodium emission as well as or better than other currently suggested materials.

Fanale, F. P.↗

NASA NTRS1977

Ignition of magnesium powders in shock wave induced flows

Ignition of magnesium powders, resulting from an interaction with incident shock wave-induced flows, has been studied. A numerical analysis of particle dynamics and heating is presented and compared with experimental measurements. The induction period is strongly dependent on convective heat transfer and not on chemical reaction rate. Experimentally observed ignition delays were on the order of 100 microns and were inversely dependent on shock strength and initial pressure, directly dependent on particle size and cloud concentration, and independent of oxygen concentration down to 2.3 percent oxygen. Good agreement between experiment and theory was realized.

Fox, T. W.↗

NASA NTRS1982

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

A computer model which simulates, in principle, the chemical changes in the photooxidation of hydrocarbons using as input data a set of elementary reactions, corresponding kinetic rate data and appropriate initial conditions was developed. The Model was refined and exploited to examine more closely the photooxidation and photostabilization of a hydrocarbon polymer. The results lead to the following observations. (1) The time to failure, tau sub f (chosen as the level of 5% C-H bond oxidation which is within the range anticipated for marked change in mechanical properties) varies as the inverse square root of the light intensity. However, tau sub f is almost unaffected by both the photoinitiator type and concentration. (2) The time to failure decreases with the rate of abstraction of C-H by peroxy radicals but increases with the rate of bimolecular radical termination controlled by diffusion. (3) Of the various stabilization mechanisms considered, the trapping of peroxy radicals is distinctly the most effective, although the concommitant decomposition of hydroperoxide is also desirable.

Somersall, A. C.↗

NASA NTRS1983

Modelling of photodegradation in solar cell modules of substrate and superstrate design made with ethylene-vinyl acetate as pottant material

A computer model was developed which can generate realistic concentration versus time profiles of the chemical species formed during photooxidation of hydrocarbon polymers using as input data a set of elementary reactions with corresponding rate constants and initial conditions. The results of computer simulation have been shown to be consistent with the general experimental observations of the photooxidation of polyethylene exposed to sunlight at ambient temperatures. The useful lifetime (5% oxidation) of the unstabilized polyethylene is predicted to vary from a few months in hot weather (100 F) to almost two years in cool weather (45 F) with an apparent net activation energy of 10 kcal/mol. Modelling studies of alternate mechanisms for stabilization of clear, amorphous, linear polyethylene suggest that the optimum stabilizer would be a molecularly dispensed additive in very low concentration which can trap peroxy radicals and also decompose hydroperoxides.

Somersall, A. C.↗

NASA NTRS1990

Nuclear power systems for lunar and Mars exploration

Initial studies of a variety of mission scenarios for the new Space Exploration Initiative, and the technologies necessary to enable or significantly enhance them, have identified the development of advanced space power systems whether solar, chemical or nuclear to be of prime importance. Lightweight, compact, reliable power systems for planetary rovers and a variety of surface vehicles, utility surface power, and power for advanced propulsion systems have been identified as critical needs for these missions. These mission scenarios, the concomitant power system requirements, and power system options considered are discussed. The significant potential benefits of nuclear power are identified for meeting the power needs of the above applications.

Sovie, R. J.↗

NASA NTRS1991

Making Ultrathin Solar Cells

Process produces extremely thin silicon solar cells - only 50 micrometers or less in thickness. Electrons and holes have less opportunity to recombine before collected at cell surfaces. Efficiency higher and because volume of silicon small, less chance of radiation damage in new cells. Initial steps carried out at normal thickness to reduce breakage and avoid extra cost of special handling. Cells then thinned mechanically and chemically. Final cell includes reflective layer on back surface. Layer bounces unabsorbed light back into bulk silicon so it absorbs and produces useful electrical output.

Cogan, George W.↗

NASA NTRS1990

High pressure Mach 10 to 20 electrothermal hypersonic wind tunnel

A new technique is described for generating high enthalpy, long pulse flows for testing scramjet combustors at equivalent flight Mach numbers of 10 to 20. The approach derives from high pressure discharge technology developed for electrothermal guns and space thrusters. Cryogenic liquid air is heated with a high power electric discharge (500 MW for a 15 kg/sec test flow rate) in a capillary tube, generating a quasi-steady pressure of up to 6800 atm at 20,000 K. The heated air is mixed with additional cryogenic air and is expanded in a conventional supersonic nozzle to 0.5 to 1 atm at 3000 to 6000 m/sec. Combustion and nozzle expansion test time of approximately 300 m/sec are contemplated. Facility nozzle chemical kinetics calculations show that above Mach 16 increasing concentrations of argon and oxygen replenishment are required to obtain suitable test conditions. Initial experiments on a subscale test rig are described for 0.5 kg/sec and 300 atm pressure.

Burton, R. L.↗

NASA NTRS1990

Nuclear power systems for lunar and Mars exploration

Initial studies of a variety of mission scenarios for the new Space Exploration Initiative, and the technologies necessary to enable or significantly enhance them, have identified the development of advanced space power systems whether solar, chemical or nuclear to be of prime importance. Lightweight, compact, reliable power systems for planetary rovers and a variety of surface vehicles, utility surface power, and power for advanced propulsion systems have been identified as critical needs for these missions. These mission scenarios, the concomitant power system requirements, and the power system options considered are discussed. The significant potential benefits of nuclear power are identified for meeting the power needs of the above applications.

Sovie, R. J.↗

NASA NTRS1993

Mirror fusion propulsion system - A performance comparison with alternate propulsion systems for the manned Mars mission

The performance characteristics of several propulsion technologies applied to piloted Mars missions are compared. The characteristics that are compared are Initial Mass in Low Earth Orbit (IMLEO), mission flexibility, and flight times. The propulsion systems being compared are both demonstrated and envisioned: Chemical (or Cryogenic), Nuclear Thermal Rocket (NTR) solid core, NTR gas core, Nuclear Electric Propulsion (NEP), and a mirror fusion space propulsion system. The proposed magnetic mirror fusion reactor, known as the Mirror Fusion Propulsion System (MFPS), is described. The description is an overview of a design study that was conducted to convert a mirror reactor experiment at Lawrence Livermore National Lab (LLNL) into a viable space propulsion system. Design principles geared towards minimizing mass and maximizing power available for thrust are identified and applied to the LLNL reactor design, resulting in the MFPS. The MFPS' design evolution, reactor and fuel choices, and system configuration are described. Results of the performance comparison shows that the MFPS minimizes flight time to 60 to 90 days for flights to Mars while allowing continuous return-home capability while at Mars. Total MFPS IMLEO including propellant and payloads is kept to about 1,000 metric tons.

Deveny, M.↗

NASA NTRS1993

Mirror fusion propulsion system: A performance comparison with alternate propulsion systems for the manned Mars Mission

Schulze, Norman R.↗

NASA NTRS1995

Numerical Study of Contaminant Effects on Combustion of Hydrogen, Ethane, and Methane in Air

A numerical study was performed to assess the effects of vitiated air on the chemical kinetics of hydrogen, ethane, and methane combustion with air. A series of calculations in static reacting systems was performed, where the initial temperature was specified and reactions occurred at constant pressure. Three different types of test flow contaminants were considered: NP, H2O, and a combustion of H2O and CO2. These contaminants are present in the test flows of facilities used for hypersonic propulsion testing. The results were computed using a detailed reaction mechanism and are presented in terms of ignition and reaction times. Calculations were made for a wide range of contaminant concentrations, temperatures and pressures. The results indicate a pronounced kinetic effect over a range of temperatures, especially with NO contamination and, to a lesser degree, with H2O contamination. In all cases studied, CO2 remained kinetically inert, but had a thermodynamic effect on results by acting as a third body. The largest effect is observed with combustion using hydrogen fuel, less effect is seen with combustion of ethane, and little effect of contaminants is shown with methane combustion.

Lai, H. T.↗

NASA NTRS1995

Numerical study of contaminant effects on combustion of hydrogen, ethane, and methane in air

A numerical study was performed to assess the effects of vitiated air on the chemical kinetics of hydrogen, ethane, and methane combustion with air. A series of calculations in static reacting systems was performed, where the initial temperature was specified and reactions occurred at constant pressure. Three different types of test flow contaminants were considered: NO, H2O, and a combination of H2O and CO2. These contaminants are present in the test flows of facilities used for hypersonic propulsion testing. The results were computed using a detailed reaction mechanism and are presented in terms of ignition and reaction times. Calculations were made for a wide range of contaminant concentrations, temperatures and pressures. The results indicate a pronounced kinetic effect over a range of temperatures, especially with NO contamination and, to a lesser degree, with H2O contamination. In all cases studied, CO2 remained kinetically inert, but had a thermodynamically effect on results by acting as a third body. The largest effect is observed with combustion using hydrogen fuel, less effect is seen with combustion of ethane, and little effect of contaminants is shown with methane combustion.

Lai, H. T.↗