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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Finite linear diffusion model for design of overcharge protection for rechargeable lithium batteries

The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. The model has been experimentally verified using 1,1-prime-dimethylferrocene as a redox additive. The theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

Narayanan, S. R.↗
NASA NTRS1993

Electrochemical impedance spectroscopy of lithium-titanium disulfide rechargeable cells

The two-terminal alternating current impedance of Li/TiS2 rechargeable cells was studied as a function of frequency, state-of-charge, and extended cycling. Analysis based on a plausible equivalent circuit model for the Li/TiS2 cell leads to evaluation of kinetic parameters for the various physicochemical processes occurring at the electrode/electrolyte interfaces. To investigate the causes of cell degradation during extended cycling, the parameters evaluated for cells cycled 5 times were compared with the parameters of cells cycled over 600 times. The findings are that the combined ohmic resistance of the electrolyte and electrodes suffers a tenfold increase after extended cycling, while the charge-transfer resistance and diffusional impedance at the TiS2/electrolyte interface are not significantIy affected. The results reflect the morphological change and increase in area of the anode due to cycling. The study also shows that overdischarge of a cathode-limited cell causes a decrease in the diffusion coefficient of the lithium ion in the cathode.

Narayanan, S. R.↗
NASA NTRS1972

A study of beryllium and beryllium-lithium complexes in single crystal silicon

When beryllium is thermally diffused into silicon, it gives rise to acceptor levels 191 MeV and 145 meV above the valence band. Quenching and annealing studies indicate that the 145-MeV level is due to a more complex beryllium configuration than the 191-MeV level. When lithium is thermally diffused into a beryllium-doped silicon sample, it produces two acceptor levels at 106 MeV and 81 MeV. Quenching and annealing studies indicate that these levels are due to lithium forming a complex with the defects responsible for the 191-MeV and 145-MeV beryllium levels, respectively. Electrical measurements imply that the lithium impurity ions are physically close to the beryllium impurity atoms. The ground state of the 106-MeV beryllium level is split into two levels, presumably by internal strains. Tentative models are proposed.

Crouch, R. K.↗
NASA NTRS2000

The limits of low-temperature performance of Li-ion cells

The results of electrode and electrolyte studies reveal that the poor low-temperature (<-30 degrees C) performance of Li-ion cells is mainly caused by the carbon electrodes and not the organic electrolytes and solid electrolyte interphase, as previously suggested. It is suggested that the main causes for the poor performance in the carbon electrodes are (i) the low value and concentration depedence of the Li diffusivity and (ii) limited Li capacity.

Diffusion Electrolytes Lithium Secondary cells↗
NASA NTRSDate not supplied

Predicting Thermal Response in a Li-ion Cell on a UAV Fight Profile

As the energy storage devices continue to "pack" more energy in a small space, any damage, battery component failure, manufacturing defect, or electrically abusing the battery can lead to catastrophic thermal runaway events. A catastrophic thermal event in a cell leads to high temperature, in some instances spewing of battery materials due to gas development from side reactions initiated due to high internal temperatures. Also, a thermal runaway event can propagate from a single "failed" cell to the pack in a battery pack, leading to a more significant event. Mitigating a thermal runaway event is important in the commercial and automotive sectors. However, preventing such events in an electric aircraft (or air taxis) is paramount due to the lack of alternatives in the event of a failure. Battery prognostics algorithms allow the prediction of state-of-charge (SOC) and end-of-life (EOL) of a Li-ion battery in a UAV (unmanned air vehicle) [1]. For this presentation, we will extend this two-level battery predictive algorithm to predict SOC, EOL, and estimated maximum temperature during a simulated flight. The model is extended by integrating a lumped physics-driven thermal model for high current densities [2]. The parameters used to control SOC and EOL are maximum storable charge, time constant for Li-ion diffusivity in the carbon particles, and internal cell resistance. Cycling leads to an increase in the heat generated by an aged Li-ion cell with a LiyCoO2 (LCO) cathode and a LixC6 (MCMB) anode. The aging of a cell leads to increase in SEI layer thickness, the diffusion time for the lithium ions inside the electrodes, and the local reaction rates, in addition to the thermodynamic abuse caused by fixed cycling voltages controlled by a Battery Management System. As the battery ages, the cell resistance increases, while the onset temperature of the thermal runaway decreases (depends on the cell chemistry and cell abuse history). Any large deviation of the cell temperature from the estimated (expected) value can identify a faulty cell. Since SEI decomposition has the lowest onset temperature in the series of reactions leading to thermal runaway, the model considers the self-heating rate of the SEI decomposition as onset temperature (similar to Ref. [3]). The parameters in the Arrhenius equation for the SEI heating rate depend on the number of cycles, the cell's operating temperature, and the cell's abuse history [4,5]. Coupling the electrochemical, thermal, and aging model allow the prognostic algorithm to estimate a typical cell voltage and temperature as a function of age (cycling and calendar), whose departure from measured values from the BMS is used to identify a safety event. In addition, we will present the results from two simulated flight scenarios for a UAV: typical and extreme, since the power requirements vary significantly during take-off, landing, and changing altitudes, while the power requirements remain low during the cruise. For this presentation, the power requirement for a battery pack in a UAV is scaled to a single cell. This cell is cycled through a simulated profile, and the data is collected and used to predict a safety event.

Li-ion↗
NASA NTRS1972

Study of beryllium and beryllium-lithium complexes in single-crystal silicon.

When beryllium is thermally diffused into silicon, it gives rise to acceptor levels 191 and 145 meV above the valence band. Quenching and annealing studies indicate that the 145-meV level is due to a more complex beryllium configuration than the 191-meV level. When lithium is thermally diffused into a beryllium-doped silicon sample, it produces two new acceptor levels at 106 and 81 meV. Quenching and annealing studies indicate that these new levels are due to lithium forming a complex with the defects responsible for the 191- and 145-meV beryllium levels, respectively. Electrical measurements imply that the lithium impurity ions are physically close to the beryllium impurity atoms. The ground state of the 106-meV beryllium-lithium level is split into two levels, presumably by internal strains. Tentative models are proposed to explain these results.

Crouch, R. K.↗
NASA NTRS1973

Startup analysis for a high temperature gas loaded heat pipe

A model for the rapid startup of a high-temperature gas-loaded heat pipe is presented. A two-dimensional diffusion analysis is used to determine the rate of energy transport by the vapor between the hot and cold zones of the pipe. The vapor transport rate is then incorporated in a simple thermal model of the startup of a radiation-cooled heat pipe. Numerical results for an argon-lithium system show that radial diffusion to the cold wall can produce large vapor flow rates during a rapid startup. The results also show that startup is not initiated until the vapor pressure p sub v in the hot zone reaches a precise value proportional to the initial gas pressure p sub i. Through proper choice of p sub i, startup can be delayed until p sub v is large enough to support a heat-transfer rate sufficient to overcome a thermal load on the heat pipe.

Sockol, P. M.↗
NASA NTRS1991

Failure analysis of the lithium battery: A study of the header deposit on the cell top and diffusion within the electrode glass seal using nuclear microanalysis and FFTIR spectroscopy

The Solid Rocket Booster Range Safety System (SRBRSS) uses a lithium/poly-carbon monofluoride primary battery as a source of electrical power. After cell fabrication and activation, some battery cells have shown self discharge. One possible source of this cell discharge has been suggested to be the formation and growth of a conducting crystallized chemical compound across the glass bead insulator, electrically shorting the glass bead to the casing. This laboratory has begun an analysis of this compound, the glass seal holding the cathode into place, and the cell electrolyte, using Fast Fourier Transform Infrared (FFTIR) Analysis, Rutherford Backscattering Spectroscopy (RBS), and Nuclear Reaction Microanalysis. Preliminary measurements have confirmed the existence of lithium, nitrogen, fluorine, and oxygen on a reddish-brown deposit covering parts of the glass seal holding the positive electrode in place. Cells using Li metal electrodes, have many advantages over conventional primary batteries. One principal disadvantage of using Li batteries on a commercial basis would be the environmental impact of the fluorocarbon material. Another would be the relatively high expense of (CF)n.

Hassan, Razi A.↗
NASA NTRS1987

Fiber optic gyro development at the Jet Propulsion Laboratory

A low-level, but continuing, fiber-gyro development activity has been carried on at the Jet Propulsion Laboratory since 1977. The activity was originated because of a recognition of the potential for low-cost high-performance gyros suitable for interplanetary spacecraft. An early decision was made to concentrate available resources on supporting the development of electrooptically active channel waveguide components which could be fabricated by mask diffusion processes. Titanium-indiffused lithium niobate waveguide components used at 0.83 micron wavelength were first tested and then abandoned because of instabilities caused by so-called optical damage. Components fabricated for use at 1.3-micron wavelength have proven to be stable. A gyro configuration concept based upon 1.3 micron channel waveguide components has evolved, and a baseline 1.3-micron all-fiber gyro has been assembled and tested.

Goss, Willis C.↗
NASA NTRS2014

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↗
NASA NTRS2014

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↗
NASA NTRS2014

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↗
NASA NTRS1987

AC impedance analysis of polypyrrole thin films

The AC impedance spectra of thin polypyrrole films were obtained at open circuit potentials from -0.4 to 0.4 V vs SCE. Two limiting cases are discussed for which simplified equivalent circuits are applicable. At very positive potentials, the predominantly nonfaradaic AC impedance of polypyrrole is very similar to that observed previously for finite porous metallic films. Modeling of the data with the appropriate equivalent circuit permits effective pore diameter and pore number densities of the oxidized film to be estimated. At potentials from -0.4 to -0.3 V, the polypyrrole film is essentially nonelectronically conductive and diffusion of polymer oxidized sites with their associated counterions can be assumed to be linear from the film/substrate electrode interface. The equivalent circuit for the polypyrrole film at these potentials is that previously described for metal oxide, lithium intercalation thin films. Using this model, counterion diffusion coefficients are determined for both semi-infinite and finite diffusion domains. In addition, the limiting low frequency resistance and capacitance of the polypyrrole thin fims was determined and compared to that obtained previously for thicker films of the polymer. The origin of the observed potential dependence of these low frequency circuit components is discussed.

Penner, Reginald M.↗
NASA NTRS2011

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12-LiNi-CoAlO2 prototype cells. These electrolytes have enabled high rate performance at low temperature (i.e., up to 2.0C rates at -50 C and 5.0C rates at -40 C), and good cycling performance over a wide temperature range (i.e., from -40 to +70 C). Current efforts are focused upon improving the high temperature resilience of the methyl propionatebased system through the use of electrolyte additives, which are envisioned to improve the nature of the solid electrolyte interphase (SEI) layers.

Smart, Marshall C.↗
NASA NTRS1971

Damage and recovery characteristics of lithium-containing solar cells.

Damage and recovery characteristics were measured on lithium-containing solar cells irradiated by 1-MeV electrons. Empirical expressions for cell recovery time, diffusion-length damage coefficient immediately after irradiation, and diffusion-length damage coefficient after recovery were derived using results of short-circuit current, diffusion-length, and reverse-bias capacitance measurements. The damage coefficients were expressed in terms of a single lithium density parameter, the lithium gradient. A fluence dependence was also established, this dependence being the same for both the immediate-post-irradiation and post-recovery cases. Cell recovery rates were found to increase linearly with lithium gradient.

Faith, T. J.↗