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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 37 records · Page 2

Li-Ion Cell Development for Low Temperature Applications

JPL is involved in the development of rechargeable Li-ion cells for future Mars Exploration Missions. The specific objectives are to improve the Li-ion cell cycle life performance and rate capability at low temperature (<<-20 C) in order to enhance survivability of the Mars lander and rover batteries. Poor Li-ion rate capability at low temperature has been attributed to: (1) the electrolytes becoming viscous or freezing and/or (2) reduced electrode capacity that results from decreased Li diffusivity. Our efforts focus on increasing the rate capability at low temperature for Li-ion cells. In order to improve the rate capability we evaluated the following: (1) cathode performance at low temperatures, (2) electrode active material particle size on low temperature performance and (3) Li diffusivity at room temperature and low temperatures. In this paper, we will discuss the results of our study.

Huang, C.-K.↗

Characterization of Commercial Li-ion Cells in Pouch Format

The li-ion pouch design cells exhibit similar behavior under off-nominal conditions as those in metal cans that do not have the internal safety devices. Safety should be well characterized before batteries are designed. Some of the li-ion pouch cell designs studied in this program reacted most violently to overcharge conditions at the medium rates but were tolerant to overcharge at very low rates. Some pouch cell designs have higher tolerance to vacuum exposures than some others. A comparison of the pouch material itself does not show a correlation between this tolerance and the number of layers or composition of the pouch indicating that this is a property of the electrode stack design inside the pouch. Reduced pressure (8 to 10 psi) test environments show that the extent of capacity degradation under reduced pressure environments is much less than that observed under vacuum conditions. Lithium-ion Pouch format cells are not necessarily true polymer cells.

Jeevarajan, Judith↗

Improved Wide Operating Temperature Range of LiNiCoAiO2-based Li-ion Cells with Methyl Propionate-based Electrolytes

Demonstration of wide operating temperature range Li-ion electrolytes Methyl propionate-based wide operating temperature range electrolytes were demonstrated to provide dramatic improvement of the low temperature capability of Quallion prototype Li-ion cells (MCMB-LiNiCoAlO2). Some formulations were observed to deliver over 60% of the room temperature capacity using a 5C rate at - 40oC !! Represents over a 4-fold improvement over the baseline electrolyte system. Demonstrated operational capability of a number of systems over a wide temperature range (-40 to +70 C) Demonstrated reasonably good long term cycle life performance at high temperature (i.e., at +40deg and +50 C) A number of formulations containing electrolytes additives (i.e., FEC, VC, LiBOB, and lithium oxalate) have been shown to have enhanced lithium kinetics at low temperature and promising high temperature resilience. Demonstrated good performance in larger capacity (12 Ah) Quallion Li-ion cells with methyl propionate-based electrolytes. Current efforts focused upon performing life studies and the impact upon low temperature capability.

Li-ion electrolytes↗

Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells

Electrolytes comprising LiPF6 dissolved at a concentration of 1.0 M in three different mixtures of alkyl carbonates have been found well suited for use in rechargeable lithium-ion electrochemical cells at low temperatures. These and other electrolytes have been investigated in continuing research directed toward extending the lower limit of practical operating temperatures of Li-ion cells down to -60 C. This research at earlier stages was reported in numerous previous NASA Tech Briefs articles, the three most recent being "Ethyl Methyl Carbonate as a Cosolvent for Lithium-Ion Cells" (NPO-20605), Vol. 25, Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells No. 6 (June 2001), page 53; "Alkyl Pyrocarbonate Electrolyte Additives for Li-Ion Cells" (NPO-20775), Vol. 26, No. 5 (May 2002), page 37; and "Fluorinated Alkyl Carbonates as Cosolvents in Li-Ion Cells (NPO-21076), Vol. 26, No. 5 (May 2002), page 38. The present solvent mixtures, in terms of volume proportions of their ingredients, are 1 ethylene carbonate (EC) + 1 diethyl carbonate (DEC) + 1 dimethyl carbonate (DMC) + 3 ethyl methyl carbonate (EMC); 3EC + 3DMC + 14EMC; and 1EC + 1DEC + 1DMC + 4EMC. Relative to similar mixtures reported previously, the present mixtures, which contain smaller proportions of EC, have been found to afford better performance in experimental Li-ion cells at temperatures < -20 C.

Smart, Marshall↗

Parameters Inference and Model Reduction for the Single-Particle Model of Li Ion Cells

The Single-Particle Model (SPM) of Li ion cell is a computationally efficient model for simulating Li ion cell for weak to moderate currents. The model depends n a number of parameters describing the geometry and material properties of a cell components. In order to apply the model to simulating a cell, the best-fit parametric values have to be inferred from a constant discharge data. We report our efforts to determine the best-fit set for 18650 LP batteries. We found that rather than being best-fit by a particular point in the parametric space the data is fit equally well by an ensemble of points clustering about an effective multidimensional manifold in the parametric space. This property of the SPM is known to be shared by a multitude of the so-called "sloppy models" of complex systems, characterized by a few stiff directions in the parametric space, in which the predicted behavior varies significantly, and a number of sloppy directions in which the behavior doesn't change appreciably. Only the stiff parameters combinations are identifiable. Geometrical features of the BFM give insights to possible reduction of the SPM to a model having fewer sloppy parameters. We have constructed a hierarchy of such models. The fully reduced model depends on only stiff effective parameters which are identifiable and can be used for characterization of the battery's state of health.

Khasin, Michael↗

Electrolytes with Improved Safety Characteristics for High Voltage, High Specific Energy Li-ion Cells

(1) NASA is actively pursuing the development of advanced electrochemical energy storage and conversion devices for future lunar and Mars missions; (2) The Exploration Technology Development Program, Energy Storage Project is sponsoring the development of advanced Li-ion batteries and PEM fuel cell and regenerative fuel cell systems for the Altair Lunar Lander, Extravehicular Activities (EVA), and rovers and as the primary energy storage system for Lunar Surface Systems; (3) At JPL, in collaboration with NASA-GRC, NASA-JSC and industry, we are actively developing advanced Li-ion batteries with improved specific energy, energy density and safety. One effort is focused upon developing Li-ion battery electrolyte with enhanced safety characteristics (i.e., low flammability); and (4) A number of commercial applications also require Li-ion batteries with enhanced safety, especially for automotive applications.

improved safety↗

Performance Testing of Yardney Li-Ion Cells and Batteries in Support of Future NASA Missions

NASA requires lightweight rechargeable batteries for future missions to Mars and the outer planets that are capable of operating over a wide range of temperatures, with high specific energy and energy densities. Due to the attractive performance characteristics, Li-ion batteries have been identified as the battery chemistry of choice for a number of future applications. For example, JPL is planning to launch another unmanned rover mission to the planet Mars. This mission, referred to as the Mars Science Laboratory (MSL), will involve the use of a rover that is much larger than the previously developed Spirit and Opportunity Rovers for the 2003 Mars Exploration Rover (MER) mission, that are currently still in operation on the surface of the planet after more than five years. Part of the reason that the MER rovers have operated so successfully, far exceeding the required mission duration of 90 sols, is that they possess robust Li-ion batteries, manufactured by Yardney Technical Products, which have demonstrated excellent life characteristics. Given the excellent performance characteristics displayed, similar Li-ion batteries have been projected to successfully meet the mission requirements of the up-coming MSL mission. In addition to future missions to Mars, Li-ion technology is attractive for a number of other future NASA applications which require high specific energy, rechargeable batteries. To ascertain the viability of using Li-ion batteries for these applications, a number of performance validation tests have been performed on both Yardney cells and batteries of various sizes. These tests include mission simulation tests, charge and discharge rate characterization testing, cycle life testing under various conditions, and storage testing.

Smart, M. C.↗

Nanostructured MnO2-Based Cathodes for Li-Ion/Polymer Cells

Nanostructured MnO2-based cathodes for Li-ion/polymer electrochemical cells have been investigated in a continuing effort to develop safe, high-energy-density, reliable, low-toxicity, rechargeable batteries for a variety of applications in NASA programs and in mass-produced commercial electronic equipment. Whereas the energy densities of state-of-the-art lithium-ion/polymer batteries range from 150 to 175 W h/kg, the goal of this effort is to increase the typical energy density to about 250 W h/kg. It is also expected that an incidental benefit of this effort will be increases in power densities because the distances over which Li ions must diffuse through nanostructured cathode materials are smaller than those through solid bulk cathode materials.

Skandan, Ganesh↗

Factors Limiting Li+ Charge Transfer Kinetics in Li-ion Batteries

Understanding the factors limiting Li+ charge transfer kinetics in Li-ion batteries is essential in improving the rate performance, especially at lower temperatures. The Li+ charge transfer process involved in the lithium intercalation of graphite anode includes the step of de-solvation of the solvated Li+ in the liquid electrolyte and the step of transport of Li+ in the preformed solid electrolyte interphase (SEI) on electrodes until the Li+ accepts an electron at the electrode and becomes a Li in the electrode. Whether the de-solvation process or the Li+ transport through the SEI is a limiting step depends on the nature of the interphases at the electrode and electrolyte interfaces. Several examples involving the electrode materials such as graphite, lithium titanate (LTO), lithium iron phosphate (LFP), lithium nickel cobalt aluminum oxide (NCA) and solid Li+ conductor such as lithium lanthanum titanate or Li-Al-Ti-phosphate are reviewed and discussed to clarify the conditions at which either the de-solvation or the transport of Li+ in SEI is dominating and how the electrolyte components affect the activation energy of Li+ charge transfer kinetics. How the electrolyte additives impact the Li+ charge transfer kinetics at both the anode and the cathode has been examined at the same time in 3-electrode full cells. The resulting impact on Li+ charge transfer resistance, Rct, and activation energy, Ea, at both electrodes are reported and discussed.

Delp, Samuel A.↗

Screening Li-Ion Batteries for Internal Shorts

The extremely high cost of aerospace battery failures due to internal shorts makes it essential that their occurrence be very rare, if not eliminated altogether. With Li-ion cells/batteries, the potentially catastrophic safety hazard that some internal shorts present adds additional incentive for prevention. Prevention can be achieved by design, manufacturing measures, and testing. Specifically for NASA s spacesuit application, a Li-ion polymer pouch cell battery design is in its final stages of production. One of the 20 flight batteries fabricated and tested developed a cell internal short, which did not present a safety hazard, but has required revisiting the entire manufacturing and testing process. Herein are the details of the failure investigation that followed to get to root cause of the internal short and the corrective actions that will be taken. The resulting lessons learned are applicable to most Li-ion battery applications.

Darcy, Eric↗

Triggering TR in Li-ion Cells with Laser Radiation

Final Paper, not the Abstract, is attached. Johnson Space Center has been experimenting with various methods of igniting Li-ion cells into thermal runaway (TR). Recently, it was demonstrated that using a high power IR laser, an Li-ion cell can be successfully triggered into TR without perforating its can wall. This method creates a zone of highly localized heat energy that transfers through the can wall and melts nearby layers of the cell separator. Using this method, we are able to trigger various cell designs into a TR response. With unique test conditions, we've been able trigger TR in an elliptical cylindrical cell design without perforating its aluminum can. The method holds promise as an effective single cell TR trigger method in battery assemblies with minimal thermal biasing to adjacent cells.

Li-ion↗

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↗

Li-ion Battery Aging with Hybrid Physics-Informed Neural Networks and Fleet-wide Data

In this work, we propose a hybrid model for Li-ion battery discharge and aging prediction that leverages fleet-wide data to predict future capacity drops.The model is built upon an hybrid approach merging physics-based and empirical equations, as well as neural network models in a recurrent neural network cell. The hybrid physics-informed neural network can predict voltage discharge cycles given the loading profile, and estimate the used capacity of the battery under random-loading conditions by tracking aging parameters connected to the residual capacity of the battery. By merging information on the battery aging parameters with existing fleet-wide aging data, the model can predict the future residual capacity of the battery that is being monitored, and therefore enable predictions of voltage discharge curves far ahead in the battery life cycle. We validated the approach using the NASA Prognostics Data Repository Battery data-set, which contains experimental data on Li-ion batteries discharged at random loading conditions in a controlled environment. The approach also allows the identification of discrepancies between the battery aging trend and the trend observed at the fleet level, so that batteries behaving differently from the rest of the fleet can be subject to closer monitoring and further testing to refine predictions.

PINN↗

Predicting Maximum Temperatures of a Li-ion Battery on a Simulated Flight Profile using a Model-based Prognostics

One of the challenges in using Li-ion packs in aeronautics is their safety, and thermal runaway (TR) is a major concern. The current engineering solutions to prevent a Li-ion pack from a catastrophic TR require additional mass and volume to isolate cells. The excess mass could be reduced by improving detection and, thus, preventing a TR event. One of the possible early warning indicators of a TR is crossing a threshold temperature. We have developed an approach, based on the Unscented Kalman Filter (UKF), to predict the likelihood of reaching the threshold temperature for simulated flight profiles. The current battery prognostics algorithms for aerospace predict state-of-charge (SOC) and end-of-life (EOL) [1]. We extended this two-level algorithm to predict the maximum temperature during discharge. The amount of heat generated in a cell depends on factors such as cell chemistry, cell packaging, total cycles, operating temperature, and abuse history [2]. Our semi-empirical thermal model depends on three phenomenological parameters which account for those factors. In addition, a two-parameter reduced-order model is developed to predict the temperature rise for short bursts of “random-walk” (RW) discharge current sequence, which simulates a flight's current-loading profile. The performance of these models on different datasets and types of current loading will be presented. To predict the maximal temperatures for future cycles we must estimate the evolution of thermal parameters as the batteries age. It is found that the parameters of the 3-parametric thermal model cannot be estimated only from the RW data. To address the issue, we will present two alternative approaches: i) expanding the datasets to include discharge profiles beyond RWs; ii) model reduction to a two-parametric model. The two approaches will be illustrated by an application to the cycling data from a commercial LG 18650 cell. References: 1. M. Daigle, C.S. Kulkarni, End-of-discharge and End-of-life Prediction in Lithium-ion Batteries with Electrochemistry-based Aging Models, in: AIAA Infotech @ Aerospace, American Institute of Aeronautics and Astronautics, San Diego, California, USA, 2016. 2. M. Börner, et. al, Correlation of aging and thermal stability of commercial 18650-type lithium ion batteries, Journal of Power Sources. 342 (2017) 382–392.

Thermal runaway↗

An Update on the Performance of Li-Ion Rechargeable Batteries on Mars Rovers

NASA's Mars Rovers, Spirit and Opportunity have been exploring the surface of Mars for the last thirty months, far exceeding the primary mission life of three months, performing astounding geological studies to examine the habitability of Mars. Such an extended mission life may be attributed to impressive performances of several subsystems, including power subsystem components, i.e., solar array and batteries. The novelty and challenge for this mission in terms of energy storage is the use of lithium-ion batteries, for the first time in a major NASA mission, for keeping the rover electronics warm, and supporting nighttime experimentation and communications. The use of Li-ion batteries has considerably enhanced or even enabled these rovers, by providing greater mass and volume allocations for the payload and wider range of operating temperatures for the power subsystem and thus reduced thermal management. After about 800 days of exploration, there is only marginal change in the end-of discharge (EOD) voltages of the batteries or in their capacities, as estimated from in-flight voltage data and corroborated by ground testing of prototype batteries. Enabled by such impressive durability from the Li-ion batteries, both from a cycling and calendar life stand point, these rovers are poised to extend their exploration well beyond 1000 sols, though other components have started showing signs of decay. In this paper, we will update the performance characteristics of these batteries on both Spirit and Opportunity.

low temperatures↗

Performance of Li-Ion Cells Under Battery Voltage Charge Control

Li-ion cells manufactured by YTP, SAFT, and MSA have completed 6714, 6226, and 3441 cycles, respectively. An increase in the charge voltage limit was required in all cases to maintain the discharge voltage. SAFT and MSA cells were capable of cycling at -10 C and 0 C with an increase in the charge voltage limit, whereas Yardney cells could not be cycled. Reconditioning improved the discharge voltage of SAFT and MSA cells; it is important to note that the effect has been temporary as in Ni-H and Ni-Cd batteries. It was demonstrated that the charge operation with VT clamp at battery rather than at cell level is feasible. Continuation of testing depends on the health of the cells and on the funding situation.

Vaidyanathan, Hari↗

Performance of Li-Ion Cells Under Battery Voltage Charge Control

A study consisting of electrochemical characterization and Low-Earth-Orbit (LEO) cycling of Li-Ion cells from three vendors was initiated in 1999 to determine the cycling performance and to infuse the new technology in the future NASA missions. The 8-cell batteries included in this evaluation are prismatic cells manufactured by Mine Safety Appliances Company (MSA), cylindrical cells manufactured by SAFT and prismatic cells manufactured by Yardney Technical Products, Inc. (YTP). The three batteries were cycle tested in the LEO regime at 40% depth of discharge, and under a charge control technique that consists of battery voltage clamp with a current taper. The initial testing was conducted at 20 C; however, the batteries were cycled also intermittently at low temperatures. YTP 20 Ah cells consisted of mixed-oxide (Co and Ni) positive, graphitic carbon negative, LIPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 32 V. The low temperature cycling tests started after 4575 cycles at 20 C. The cells were not capable of cycling. at low temperature since the charge acceptance at battery level was poor. There was a cell in the battery that showed too high an end-of-charge (EOC) voltage thereby limiting the ability to charge the rest of the cells in the battery. The battery has completed 6714 cycles. SAFT 12 Ah cells consisted of mixed-oxide (Co and NO positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was for 30.8 V. The low temperature cycling tests started after 4594 cycles at 20 C. A cell that showed low end of discharge (EOD) and EOC voltages and three other cells that showed higher EOC voltages limited the charge acceptance at the selected voltage limit during charge. The cells were capable of cycling at 10 C and 0 C but the charge voltage limit had to be increased to 34.3 V (4.3 V per cell). The low temperature cycling may have induced poor chargeability since the voltage had to be increased to achieve the required charge input. The battery has completed 6226 cycles. MSA 10 Ah cells consisted of Co oxide positive, graphitic carbon negative, LiPF6 salt mixed with organic carbonate solvents. The battery voltage clamp was 30.8 V. The low temperature cycling tests were started after 2182 cycles at 20 C. The cells were capable of cycling at 10 C and 0 C. Like SAFT, the voltage limit on charge had to be increased to 36 V (4.5 V per cell). There was a cell (cell S/N 13) in the battery that showed poor performance features such as low EOD voltage and high EOC voltage. The battery has completed 3441 cycles. A reconditioning procedure that consisted of C15 charge to a taper current of C/100 and C/20 discharge improved the voltage behavior of SAFT and MSA cells with no significant effect on YTP cells. We have demonstrated that the charge operation with VT clamp at battery rather than at cell level is feasible for onboard Li-Ion battery operation.

Rao, Gopalakrishna M.↗

Mathematical Modeling of Ni/H2 and Li-Ion Batteries

The modelling effort outlined in this viewgraph presentation encompasses the following topics: 1) Electrochemical Deposition of Nickel Hydroxide; 2) Deposition rates of thin films; 3) Impregnation of porous electrodes; 4) Experimental Characterization of Nickel Hydroxide; 5) Diffusion coefficients of protons; 6) Self-discharge rates (i.e., oxygen-evolution kinetics); 7) Hysteresis between charge and discharge; 8) Capacity loss on cycling; 9) Experimental Verification of the Ni/H2 Battery Model; 10) Mathematical Modeling Li-Ion Batteries; 11) Experimental Verification of the Li-Ion Battery Model; 11) Integrated Power System Models for Satellites; and 12) Experimental Verification of Integrated-Systems Model.

Weidner, John W.↗