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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

High Li + Transference Number Electrolyte Enabled by Fluoride Acceptor for Low-Temperature Li-Ion Batteries

To enable wide-temperature operation of lithium-ion batteries (LIBs), new electrolyte formulations have been developed to enhance the performance, particularly at low temperatures. A key challenge lies in achieving both high ionic conductivity and a high lithium-ion transference number due to their inherent trade-off. In this study, we designed an electrolyte system comprising tris(pentafluorophenyl)borane (TPFPB), a fluoride acceptor, and LiF salt in ethylene carbonate (EC)-free solvents. TPFPB, with its electron-deficient boron center, facilitates fluoride transfer reactions that promote the dissociation of otherwise insoluble LiF. When methyl acetate (MA) was used as the solvent, the electrolyte exhibited a high transference number (t Li + = 0.85) and ionic conductivity (σ = 5.0 × 10 –3 S cm –1 ). The optimized electrolyte demonstrated excellent performance at −20 °C, with no evidence of lithium plating. This work presents a new strategy for electrolyte design by leveraging cation desolvation to achieve high-performance LIBs for low-temperature and high-power applications.

anions↗

Hydrocarbon-based membranes cost-effectively manage species transport and increase performance in thermally regenerative batteries

Low-temperature heat (T<130°C) can be utilized by thermally regenerative batteries (TRBs) for power production, allowing the thermal energy to be converted to storable chemical potential energy. However, TRBs suffer from high ohmic losses and ammonia crossover, which has slowed their development. In this study, we examined how the use of six different membranes influenced TRB performance, determined the most influential membrane parameters, and identified promising membrane candidates that cost-effectively increase TRB performance. Of the six membranes examined, an inexpensive, hydrocarbon CEM (Selemion CMVN) had low ammonia crossover without compromising resistance, resulting in good performance across all metrics studied. A thin anion exchange membrane (Sustainion, 50 microns) showed a high peak power density of 82 mW cm –2 due to low resistance, but the average power density and energy density were low due to high ammonia flux. Full discharge curves using Selemion CMVN provided an average power density of 26 ± 7 mW cm –2 with an energy density of 2.9 Wh L –1 , which were large improvements on previous TRBs. A techno-economic analysis showed that Selemion CMVN had the lowest levelized cost of storage ($410 per MWh) at an applied current density of 50 mA cm –2 .

25 ENERGY STORAGE↗

Improved Control of Charging Voltage for Li-Ion Battery

The protocol for charging a lithium-ion battery would be modified, according to a proposal, to compensate for the internal voltage drop (charging current internal resistance of the battery). The essence of the modification is to provide for measurement of the internal voltage drop and to increase the terminal-voltage setting by the amount of the internal voltage drop. Ordinarily, a lithium-ion battery is charged at constant current until its terminal voltage attains a set value equal to the nominal full-charge potential. The set value is chosen carefully so as not to exceed the lithium-plating potential, because plated lithium in metallic form constitutes a hazard. When the battery is charged at low temperature, the internal voltage drop is considerable because the electrical conductivity of the battery electrolyte is low at low temperature. Charging the battery at high current at any temperature also gives rise to a high internal voltage drop. In some cases, the internal voltage drop can be as high as 1 volt per cell. Because the voltage available for charging is less than the terminal voltage by the amount of the internal voltage drop, the battery is not fully charged (see figure), even when the terminal voltage reaches the set value. In the modified protocol, the charging current would be periodically interrupted so that the zero-current battery-terminal voltage indicative of the state of charge could be measured. The terminal voltage would also be measured at full charging current. The difference between the full-current and zero-current voltages would equal the internal voltage drop. The set value of terminal voltage would then be increased beyond the nominal full-charge potential by the amount of the internal voltage drop. This adjustment would be performed repeatedly, in real time, so that the voltage setting would track variations in the internal voltage drop to afford full charge without risk of lithium plating. If the charging current and voltage settings were controlled by a computer, then this method of charge control could readily be implemented in software.

Timmerman, Paul↗

Low Temperature Life-cycle Testing of a Lithium-ion Battery for Low-earth-orbiting Spacecraft

A flight-qualified, lithium-ion (Li-ion) battery developed for the Mars Surveyor Program 2001 lander is undergoing life-testing at low temperature under a low-Earth-orbit (LEO) profile to assess its capability to provide long term energy storage for aerospace missions. NASA has embarked upon an ambitious course to return humans to the moon by 2015-2020 in preparation for robotic and human exploration of Mars and robotic exploration of the moons of outer planets. Li-ion batteries are excellent candidates to provide power and energy storage for multiple aspects of these missions due to their low specific energy, low energy density, and excellent low temperature performance. Laboratory testing of Li-ion technology is necessary in order to assess lifetime, characterize multi-cell battery-level performance under aerospace conditions, and to gauge safety aspects of the technology. Life-cycle testing provides an opportunity to examine battery-level performance and the dynamics of individual cells in the stack over the entire life of the battery. Data generated through this testing will be critical to establish confidence in the technology for its widespread use in manned and unmanned mission. This paper discusses the performance of the 28 volt, 25 ampere-hour battery through 6000 LEO cycles, which corresponds to one year on LEO orbit. Testing is being performed at 0 C and 40% depth-of-discharge. Individual cell behaviors and their effect on the performance of the battery are described. Capacity, impedance, energy efficiency and end-of-discharge voltage at 1000 cycle intervals are reported. Results from this life-testing will help contribute to the database on battery-level performance of aerospace Li-ion batteries and low temperature cycling under LEO conditions.

Reid, Concha↗

Performance of Low Temperature Electrolytes in Experimental and Prototype Li-Ion Cells

Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with ethylene carbonate-based electrolytes optimized for low temperature in experimental MCMB-LiNixCo1_x0 2 cells. In addition to obtaining discharge and charge rate performance data at various temperatures, electrochemical measurements were performed on individual electrodes (made possible by the incorporation of Li reference electrodes), including EIS, linear polarization and Tafel polarization measurements. The combination of techniques enables the elucidation of various trends associated with electrolyte composition. In addition to investigating the behavior in experimental cells, the performance of many promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

Li-ion batteries↗

Electrolyte Design for NMC811||SiO x -Gr Lithium-Ion Batteries with Excellent Low-Temperature and High-Rate Performance

The use of high-nickel NMC811 cathode and SiO x -Gr anode can greatly improve the overall energy densities of lithium-ion batteries. However, the unfavorable solid electrolyte interphase (SEI) layer generated from the decomposition of EC-based electrolytes lead to the poor cycling stability of NMC811||SiO x -Gr cells. Here we report an electrolyte design of 1.5 M LiPF 6 dissolved in FEC/MA/BN 2:2:6 by volume, which can form thin, robust, and homogeneous SEI layer to greatly improve the charge transfer at the electrode-electrolyte interface. Importantly, the designed electrolyte shows an outstanding low temperature performance that it can deliver a capacity of 123.3 mAh g –1 after 50 cycles at −20 °C with a current density of 0.5 C, overwhelming the standard EC-based electrolyte (1.2 M LiPF 6 EC/EMC 3:7 by volume) with a capacity of 35.7 mAh g –1 . The electrolyte also has a superior rate performance that it achieves a capacity of 122.5 mAh g −1 at a high current density of 10 C. Moreover, the LTE electrolyte holds the great potential of extreme fast-charging ability because of the large part of CC contribution in the CCCV charging model at high charging current densities.

Electrochemistry↗

Mobile Sorption-based Thermal Battery for Harvesting Low-Temperature Geothermal Energy

Around 20% of the total primary energy in the United States is consumed for thermal demands of buildings such as space cooling, dehumidification, and space heating (EIA 2018). Low-temperature geothermal energy is abundant and can effectively satisfy buildings’ thermal demands. However, low-temperature geothermal energy is underutilized because the energy density of geothermal fluid is too low to justify the costs associated with transporting it between existing geothermal resources and buildings. The mobile sorption-based thermal battery (MSTB) system has been developed using three-phase (i.e., vapor–liquid, solution–solid, crystal) sorption technology to harvest low-temperature heat and store it with a much higher energy density than the geothermal fluid. The energy density of salt crystals is over six times higher than geothermal fluid, which makes long-distance transportation of salt crystals economically feasible. Salt crystals can be used to dehumidify air or provide space cooling in buildings, which alleviates peak demand on the electricity grid by offsetting electricity use for these end uses. This helps improve the grid’s stability and resilience. High-energy storage density, fast crystallization, and dissolution of salt crystals are all critical to the viability and performance of the MSTB system. Therefore, the design and operation of MSTB systems need to ensure effective generation and dissolution of salt crystals inside the MSTB. To achieve this target, this seedling project developed an experimental apparatus for characterizing the crystallization and dissolution processes. The energy density and potential latent cooling capacity of the MSTB are also evaluated based on lab test results. The crystallization results showed that the generated lithium chloride hydrate crystals are fluffy, the crystallization process lasts about 50 min, and the maximum crystal fraction (i.e., the ratio of crystal mass to the mass in the MSTB) can be up to 51.1% of the total mass in the MSTB at a solution flow rate of 1.58 g/s. The dissolution results show that the salt crystals in the MSTB can be fully dissolved within 15–28 min, based on different test conditions. Reducing solution flow rate and cooling water temperature can achieve increased energy storage density and crystal fraction. While the increase in the discharge rate (i.e., latent cooling capacity for dehumidifying air) is achieved by increasing flow rate and temperature of inlet diluted solution, as well as by using a pump for internal solution circulation, the discharge rate increases by 38%, from 0.95 kW to 1.31 kW. Compared with increasing the inlet solution flow rate, power consumption of salt solution transportation can be reduced by using a pump for internal solution circulation. The crystallization test results also showed that the maximum energy storage density is 981.8 kJ/kg, and the maximum discharge rate of the dissolution tests is ≤1.79 kW. Both are above the target values of 900 kJ/kg and 1.75 kW) for this project. The work reported here proves the feasibility and advancement of the MSTB system, which is helpful to the further study and improvement of the MSTB system.

15 GEOTHERMAL ENERGY↗

Development of Ultra Low Temperature, Impact Resistant Lithium Battery for the Mars Microprobe

The requirements of the power source for the Mars Microprobe, to be backpacked on the Mars 98 Spacecraft, are fairly demanding, with survivability to a shock of the order of 80,000 g combined with an operational requirement at -80 C. Development of a suitable power system, based on primary lithium-thionyl chloride is underway for the last eighteen months, together with Yardney Technical Products Inc., Pawcatuck, CT. The battery consists of 4 cells of 2 Ah capacity at 25 C, of which at least 25 % would be available at -80 C, at a moderate rate of C/20. Each probe contains two batteries and two such probes will be deployed. The selected cell is designed around an approximate 1/2 "D" cells, with flat plate electrodes. Significant improvements to the conventional Li-SOCl2 cell include: (a) use of tetrachlorogallate salt instead of aluminate for improved low temperature performance and reduced voltage delay, (b) optimization of the salt concentration, and (c) modification of the cell design to develop shock resistance to 80,000 g. We report here results from our several electrical performance tests, mission simulation tests, microcalorimetry and AC impedance studies, and Air gun tests. The cells have successfully gone through mission-enabling survivability and performance tests for the Mars Microprobe penetrator.

Frank, H.↗

Nickel-hydrogen battery state of charge during low rate trickle charging

Battery temperature increase, due to low rate trickle charging, has been determined experimentally, using a six cell battery module in a test setup simulating the anticipated AXAF-1 prelaunch environment. Test results indicate trickle charge rates less than or equal to the self discharge rate do not increase dissipation beyond that due to the self discharge. Significant trickle charge rates (approximately C/500) result in battery temperatures only a few degrees (F) higher than those observed during periods of open circuit stand.

Lurie, C.↗

Low-Cost All-Temperature Zinc-Pulp Battery for Stationary Storage

WH-Power Final Technical Report — Low-Cost All-Temperature Zinc-Pulp Battery This is the final scientific/technical report for ARPA-E CREATE program award DE-AR0001796, covering work from September 2023 through September 2025. The WHP–UMD–Yale team set out to develop a safe, low-cost, wide-temperature zinc battery for grid-scale stationary storage. What was built: A zinc-pulp (Zn/CNF) battery system pairing an aqueous high-entropy electrolyte (HEE) with a cellulose-derived ion-conducting membrane.

25 ENERGY STORAGE↗

A new cyclic carbonate enables high power/ low temperature lithium-ion batteries

The modern lithium-ion battery (LIB) configuration was enabled by the "magic chemistry" between ethylene carbonate (EC) and graphitic carbon anode. Despite the constant changes of cathode chemistries with improved energy densities, EC-graphite combination remained static during the last three decades. While the interphase generated by EC protects the fragile graphitic structure, the intrinsic disadvantages of EC (high viscosity, high melting point, excessive interphase growth) lead to mediocre power density and poor performances of LIB at sub-zero temperatures, where lithium depositions form upon charging. Such performance compromises arise from the fundamental dilemma between requiring effective interphase protection and high impedance from excessive growth of interphase. In this work, we designed and synthesized a "double EC" molecule as electrolyte additive to resolve the above dilemma. Erythritol bis(carbonate) (EBC) possesses lower LUMO energy level than EC and hence tends to decompose prior to EC reduction, but its weak solvation toward Li + restricts the extent of its reduction, thus minimizing the interphase thickness and the corresponding impedances. Electrolytes containing EBC enables both the charging and discharging of ampere-size LIB pouch cells at sub-zero temperatures from 0 to -20°C, demonstrating that the key approach to improve low temperature performances lies in how to tailor interphasial chemistry rather than the bulk electrolyte composition.

25 ENERGY STORAGE↗

Electrolyte design for Li-ion batteries under extreme operating conditions

The ideal electrolyte for the widely used LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811)||graphite lithium-ion batteries is expected to have the capability of supporting higher voltages (≥4.5 volts), fast charging (≤15 minutes), charging/discharging over a wide temperature range (±60 degrees Celsius) without lithium plating, and non-flammability. No existing electrolyte simultaneously meets all these requirements and electrolyte design is hindered by the absence of an effective guiding principle that addresses the relationships between battery performance, solvation structure and solid-electrolyte-interphase chemistry. Here we report and validate an electrolyte design strategy based on a group of soft solvents that strikes a balance between weak Li+-solvent interactions, sufficient salt dissociation and desired electrochemistry to fulfil all the aforementioned requirements. Remarkably, the 4.5-volt NMC811||graphite coin cells with areal capacities of more than 2.5 milliampere hours per square centimetre retain 75 per cent (54 per cent) of their room-temperature capacity when these cells are charged and discharged at -50 degrees Celsius (-60 degrees Celsius) at a C rate of 0.1C, and the NMC811||graphite pouch cells with lean electrolyte (2.5 grams per ampere hour) achieve stable cycling with an average Coulombic efficiency of more than 99.9 per cent at -30 degrees Celsius. The comprehensive analysis further reveals an impedance matching between the NMC811 cathode and the graphite anode owing to the formation of similar lithium-fluoride-rich interphases, thus effectively avoiding lithium plating at low temperatures. Additionally, this electrolyte design principle can be extended to other alkali-metal-ion batteries operating under extreme conditions.

25 ENERGY STORAGE↗

Low-Temperature Characterization of a Nonaqueous Liquid Electrolyte for Lithium Batteries

Rechargeable batteries exhibit poor performance at low temperatures due to sluggish ion transport through the electrolytic phase. Ion transport is governed by three transport parameters—conductivity, diffusion coefficient, and the cation transference number with respect to the solvent velocity—and the thermodynamic factor. Understanding how these parameters change with temperature is necessary for designing improved electrolytes. In this work, we combine electrochemical techniques with electrophoretic NMR to determine the temperature dependence of these parameters for a liquid electrolyte, LiTFSI salt dissolved in tetraglyme between −20 and 45 °C. At colder temperatures, all species in the electrolyte tend to move more slowly due to increasing viscosity, which translates to a monotonic decrease in conductivity and diffusion coefficient with decreasing temperature. Surprisingly, we find that the field-induced velocity of solvent molecules at a particular salt concentration is a nonmonotonic function of temperature. The cation transference number with respect to the solvent velocity thus exhibits a complex dependence on temperature and salt concentration. The measured thermodynamic and transport properties are used to predict concentration gradients that will form in a lithium-lithium symmetric cell under a constant applied potential as a function of temperature using concentrated solution theory. The calculated steady current at −20 °C is lower than that at 45 °C by roughly two orders of magnitude.

25 ENERGY STORAGE↗

Stable bismuth-antimony alloy cathode with a conversion-dissolution/deposition mechanism for high-performance zinc batteries

Although a large number of intercalation cathode materials for aqueous Zn batteries have been reported, limited intercalation capacity precludes achieving a higher energy density. Here, for this work, we develop a high-performance aqueous Zn battery based on BiSb alloy (Bi 0.5 Sb 0.5 ) using a high-concentrated strong-basic polyelectrolyte. We demonstrate that a conversion-dissolution/deposition electrochemical mechanism (BiSb ↔ Bi + SbO 2 – ↔ Bi + SbO 3 – ↔ Bi 2 O 3 ) through in situ X-ray diffraction (XRD), Raman, and ex-situ X-ray photoelectron spectrometry (XPS) characterizations with the help of density functional theory calculations. The BiSb cathode delivers large capacity of 512 mAh g –1 at 0.3 Ag –1 and superior rate capability of 90 mAh g –1 even at 20 Ag –1 , and long-term cyclability with capacity retentions of 184 mAh g –1 after 600 cycles at 0.5 Ag –1 and 130 mAh g –1 after 1300 cycles at 1 Ag –1 . Remarkably, even at temperatures as low as –10 and –20 °C, capacities of 210 and 197 mAh g –1 are reserved at 1 Ag –1 , respectively. Moreover, the prepared pouch Zn//BiSb battery delivers a high energy density of 303 Wh kg –1 BiSb at 0.3 Ag –1 . When coupled with a high concentration polyelectrolyte, the Zn/BiSb battery exhibits an excellent performance over a wide temperature range (–40 to 40 °C). Our research reveals the metal cathode is promising for Zn batteries to achieve a high performance with the unique mechanism and alloys can be an effective approach to stabilize metal electrodes for cycling.

25 ENERGY STORAGE↗

Extending the low-temperature operation of sodium metal batteries combining linear and cyclic ether-based electrolyte solutions

Nonaqueous sodium-based batteries are ideal candidates for the next generation of electrochemical energy storage devices. However, despite the promising performance at ambient temperature, their low-temperature (e.g., < 0 °C) operation is detrimentally affected by the increase in the electrolyte resistance and solid electrolyte interphase (SEI) instability. Here, to circumvent these issues, we propose specific electrolyte formulations comprising linear and cyclic ether-based solvents and sodium trifluoromethanesulfonate salt that are thermally stable down to –150 °C and enable the formation of a stable SEI at low temperatures. When tested in the Na||Na coin cell configuration, the low-temperature electrolytes enable long-term cycling down to –80 °C. Via ex situ physicochemical (e.g., X-ray photoelectron spectroscopy, cryogenic transmission electron microscopy and atomic force microscopy) electrode measurements and density functional theory calculations, we investigate the mechanisms responsible for efficient low-temperature electrochemical performance. We also report the assembly and testing between –20 °C and –60 °C of full Na||Na 3 V 2 (PO 4 ) 3 coin cells. The cell tested at –40 °C shows an initial discharge capacity of 68 mAh g –1 with a capacity retention of approximately 94% after 100 cycles at 22 mA g –1 .

25 ENERGY STORAGE↗