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At least 55 records · Page 3

Case-positive versus case-negative designs for low-rate lithium thionyl chloride cells

Case polarity design choices are discussed. Two examples of case-negative designs are presented. One battery is thionyl chloride limited and the other is lithium limited. The case-positive design is thionyl chloride limited. It is found that the case-positive/case-negative design consideration does not seem to have much bearing on storage. However, during low rate discharge, the case-negative cells show a steadily decreasing capacity as you go to lower and lower rates.

Mahy, T. X.↗

Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

Shah, Pinakin M.↗

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

A deep understanding of the interaction of the surface of cathode materials with solid electrolytes is crucial to design advanced solid-state batteries (SSBs). This is especially true for the new class of lithium metal chloride (Li-M-Cl) solid electrolytes which are receiving rapidly growing attention due to their very high oxidative stability (>4 V) in combination with good ionic conductivity that can enable long cell cycle life. While Li-M-Cl electrolytes typically contain resource-limited metals (M) such as indium or rare earths, work has focused on substituting M with more abundant elements such as zirconium. Via operando resistance measurements using intermittent current interruption we explore the dynamic evolution of the interphase at the surface of Ni-rich NCM85 or NCM111 cathode particles inside a working SSB with three different Li-(M 1 ,M 2 )-Cl catholytes (Li 3 InCl 6 , Li 2 Sc 1/3 In 1/3 Cl 4 and Li 5/2 Y 1/2 Zr 1/2 Cl 6 ) to reveal the impact of the cationic metal substitution on the interfacial chemistry. We show that the metal plays a critical role in determining high voltage stability, contrary to prior assumptions. Using a combination of cyclic voltammetry and ultraviolet photoelectron spectroscopy measurements of the electronic band structure to assess oxidative stability; coupled with DFT calculations and ToF-SIMS to evaluate products formed at the interface at different upper cutoff potentials and degrees of delithiation, we are able to differentiate between electrochemical and chemical degradation. We find that Li 2 Sc 1/3 In 1/3 Cl 4 yields the highest (and Li 3 InCl 6 the lowest) stability against electrochemical oxidation, while Li 5/2 Y 1/2 Zr 1/2 Cl 6 undergoes a detrimental chemical reaction with oxygen released from Ni-rich NCM85 at high potentials, resulting in fast capacity fading. Altogether, our work establishes a platform for the metrics and an approach that can be utilized to efficiently evaluate the stability of new halide SEs in SSB cells.

25 ENERGY STORAGE↗

Effects of heavy particle irradiation and diet on amphetamine- and lithium chloride-induced taste avoidance learning in rats

Rats were maintained on diets containing either 2% blueberry or strawberry extract or a control diet for 8 weeks prior to being exposed to 1.5 Gy of 56Fe particles in the Alternating Gradient Synchrotron at Brookhaven National Laboratory. Three days following irradiation, the rats were tested for the effects of irradiation on the acquisition of an amphetamine- or lithium chloride-induced (LiCl) conditioned taste avoidance (CTA). The rats maintained on the control diet failed to show the acquisition of a CTA following injection of amphetamine. In contrast, the rats maintained on antioxidant diets (strawberry or blueberry extract) continued to show the development of an amphetamine-induced CTA following exposure to 56Fe particles. Neither irradiation nor diet had an effect on the acquisition of a LiCl-induced CTA. The results are interpreted as indicating that oxidative stress following exposure to 56Fe particles may be responsible for the disruption of the dopamine-mediated amphetamine-induced CTA in rats fed control diets; and that a reduction in oxidative stress produced by the antioxidant diets functions to reinstate the dopamine-mediated CTA. The failure of either irradiation or diet to influence LiCl-induced responding suggests that oxidative stress may not be involved in CTA learning following injection of LiCl.

Non-NASA Center↗

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Tigelaar, Dean M.↗

Halogenation of used aluminum matrix test reactor fuel – a bench-scale demonstration with surrogate materials

In this work, experiments with surrogate materials were performed at bench scale to demonstrate a halogenation technique applicable to treatment of used aluminum matrix test reactor fuel. The technique involves dissolution and separation of aluminum from used aluminum matrix test reactor fuel in molten-halide salt systems prior to treatment and disposition of the fuel’s uranium and fission products. Demonstration of the halogenation technique was performed with neodymium metal as a non-radiological surrogate for uranium metal. Experiments involved blending forms of aluminum and neodymium metal with ammonium and lithium chloride or ammonium and lithium bromide, which upon heating decomposed into ammonia gas and the respective hydrogen chloride or bromide gas. The latter reacted with the metals to form the respective aluminum and neodymium halides. At elevated temperatures, aluminum halides gasified away from the respective neodymium halides, which fused with their respective lithium halides. Samples of fused and distillate salts were collected and analyzed, yielding extents of aluminum removal that ranged from 94.5–98.2% for chlorination runs and 91.4–97.8% for bromination runs. No neodymium was detected in the distillate fractions. Some experiments were repeated with excess reactants, and a portion of aluminum chloride distillate was processed into a consolidated waste form.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The 250AH/90A active lithium-thionyl chloride cell for Centaur-G application

A high rate active Li/SOCl2 cell was designed for use in a 28 volt, 250 amp-hour space battery system. The lithium battery is being considered as a replacement of its heavier silver-zinc counterpart on board the Centaur-G booster rocket which is used to launch payloads from the Space Shuttle cargo bay into deep-space. Basically a feasibility study, this development effort is demonstrating the ability of the lithium cell to deliver up to 90 amps safely at power densities of approximately 25 watts per pound. Test data on 4 prototype units is showing an energy density of 85 watt-hours per pound and 9.0 watt-hours/cu in. The cells tested typically delivered 280 to 300 amp-hours under ambient temperature test conditions using alternating continuous loads of 90, 55, and 20 amperes throughout life. Data from four cells tested are presented to demonstrate the capability of Li/SOCl2 technology for a C/3 discharge rate in active and hermetic cell units.

Zolla, A. E.↗

Conditioned taste aversion and motion sickness in cats and squirrel monkeys

The relationship between vomiting and conditioned taste aversion was studied in intact cats and squirrel monkeys and in cats and squirrel monkeys in which the area postrema was ablated by thermal cautery. In cats conditioned 7-12 months after ablation of the area postrema, three successive treatments with xylazine failed to produce either vomiting or conditioned taste aversion to a novel fluid. Intact cats, however, vomited and formed a conditioned aversion. In squirrel monkeys conditioned 6 months after ablation of the area postrema, three treatments with lithium chloride failed to produce conditioned taste aversion. Intact monkeys did condition with these treatments. Neither intact nor ablated monkeys vomited or evidenced other signs of illness when injected with lithium chloride. When the same ablated cats and monkeys were exposed to a form of motion that produced vomiting prior to surgery, conditioned taste aversion can be produced after ablation of the area postrema. The utility of conditioned taste aversion as a measure of subemetic motion sickness is discussed by examining agreement and disagreement between identifications of motion sickness by conditioned taste aversion and vomiting. It is suggested that a convincing demonstration of the utility of conditioned taste aversion as a measure of nausea requires the identification of physiological correlates of nausea, and caution should be exercised when attempting to interpret conditioned taste aversion as a measure of nausea.

area postrema↗

Performance of a Multifunctional Space Evaporator-Absorber-Radiator (SEAR)

The Space Evaporator-Absorber-Radiator (SEAR) is a nonventing thermal control subsystem that combines a Space Water Membrane Evaporator (SWME) with a Lithium Chloride Absorber Radiator (LCAR). The LCAR is a heat pump radiator that absorbs water vapor produced in the SWME. Because of the very low water vapor pressure at equilibrium with lithium chloride solution, the LCAR can absorb water vapor at a temperature considerably higher than the SWME, enabling heat rejection sufficient for most EVA activities by thermal radiation from a relatively small area radiator. Prior SEAR prototypes used a flexible LCAR that was designed to be installed on the outer surface of a portable life support system (PLSS) backpack. This paper describes a SEAR subsystem that incorporates a very compact LCAR. The compact, multifunctional LCAR is built in the form of thin panels that can also serve as the PLSS structural shell. We designed and assembled a 2 ft² prototype LCAR based on this design and measured its performance in thermal vacuum tests when supplied with water vapor by a SWME. These tests validated our models for SEAR performance and showed that there is enough area available on the PLSS backpack shell to enable rejection of metabolic heat from the LCAR. We used results of these tests to assess future performance potential and suggest approaches for integrating the SEAR system with future space suits.

Izenson, Michael G.↗

Performance of a Multifunctional Space Evaporator- Absorber-Radiator (SEAR)

The Space Evaporator-Absorber-Radiator (SEAR) is a nonventing thermal control subsystem that combines a Space Water Membrane Evaporator (SWME) with a Lithium Chloride Absorber Radiator (LCAR). The LCAR is a heat pump radiator that absorbs water vapor produced in the SWME. Because of the very low water vapor pressure at equilibrium with lithium chloride solution, the LCAR can absorb water vapor at a temperature considerably higher than the SWME, enabling heat rejection by thermal radiation from a relatively small area radiator. Prior SEAR prototypes used a flexible LCAR that was designed to be installed on the outer surface of a portable life support system (PLSS) backpack. This paper describes a SEAR subsystem that incorporates a very compact LCAR. The compact, multifunctional LCAR is built in the form of thin panels that can also serve as the PLSS structural shell. We designed and assembled a 2 sq ft prototype LCAR based on this design and measured its performance in thermal vacuum tests when supplied with water vapor by a SWME. These tests validated our models for SEAR performance and showed that there is enough area available on the PLSS backpack shell to enable heat rejection from the LCAR.

Izenson, Michael G.↗

Computing chemical potentials with machine-learning-accelerated simulations to accurately predict thermodynamic properties of molten salts

The successful design and deployment of next-generation nuclear technologies heavily rely on thermodynamic data for relevant molten salt systems. However, the lack of accurate force fields and efficient methods has limited the quality of thermodynamic predictions from atomistic simulations. Here we propose an efficient free energy framework for computing chemical potentials, which is the central free energy quantity behind many thermodynamic properties. We accelerate our simulations without sacrificing accuracy by using machine learning interatomic potentials trained on density functional theory (DFT) data. Using lithium chloride as our model system, we compute chemical potentials with DFT-accuracy for solid and liquid phases by transmuting ions into noninteracting particles. Notably, in the liquid phase, we demonstrate consistency whether we transmute one ion pair or the entire system into ideal gas particles. By locating the temperature where the chemical potential of solid and liquid phases cross, we predict a melting point of 880 ± 18 K for lithium chloride, which is remarkably close to the experimental value of 883 K. With this successful demonstration, we lay the foundation for high-throughput thermodynamic predictions of many properties that can be derived from the chemical potentials of the minority and majority components in molten salts.

Gibson, Luke D. [Oak Ridge National Laboratory (OR↗

Fabrication and Characterization of Composite Membranes for the Concentration of Lithium Containing Solutions Using Forward Osmosis

In this study, an energy and highly time efficient, cost effective, and scalable forward osmosis (FO) composite polyvinylidene fluoride (PVDF) membrane is developed to concentrate lithium chloride recovered from naturally occurring geothermal brine resources. Dense thin robust defect-free Kynar-PVDF membranes are fabricated on porous PVDF hollow fiber supports. Various membrane fabrication parameters such as membrane thickness, coating solution concentration, cross-linker concentration, and curing temperature are studied to develop a defect-free dense membrane. Advanced characterization tools such as FIB-SEM, Raman, FTIR spectroscopy, and XRD are used to study the surface and cross-sectional morphology, chemistry of crosslinking, crystallinity and chemical structure of the dense PVDF membrane. FO is utilized to concentrate LiCl in the solution from 36 to 175 g L -1 with an average water transfer rate of 0.450 L m -2 h -1 (LMH) at 85 °C. Furthermore, the membrane showed stable performance for more than 550 h while maintaining the purity of the concentrated lithium chloride solution of >99.99 wt%. Overall, the results suggest that the FO-based technology is an innovative, time and energy efficient approach compared to the conventional technologies for concentration of battery grade LiCl for application in lithium ion batteries and other clean energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heat generation rates in lithium thionyl chloride cells

An empirical equation that is useful for good first approximation in thermal modeling is presented. Indications and measurements of electrochemical heat effects were investigated. The particular cells of interest are of the D size, with spiral wound configuration and were instrumented with a thermocouple. It is found that cathode limited cells can explode on reversal at moderate temperatures.

Frank, H.↗

Discharge of 1400 AH lithium thionyl chloride cells into voltage reversal

The development of a high energy density battery is discussed. Tests were conducted on a 1400 AH cell and they include: drop tests, crush tests, vibration and shock tests, hydrostatic pressure effects, charge current tests, and discharge tests. None of these tests led to a venting or explosion of the cell. Criteria are presented for extending RV safety of a 1400 AH cell.

Zolla, A. E.↗

High-rate lithium thionyl chloride cells

A high-rate C cell with disc electrodes was developed to demonstrate current rates which are comparable to other primary systems. The tests performed established the limits of abuse beyond which the cell becomes hazardous. Tests include: impact, shock, and vibration tests; temperature cycling; and salt water immersion of fresh cells.

Goebel, F.↗

Performance and Abuse Testing of 5 Year Old Low Rate and Medium Rate Lithium Thionyl Chloride Cells

Most cells survived the 3 amp (A) over-discharge at room temperature for 2 hours. The cell that failed was the LTC-114 after high rate discharge of 500 mA similar to the results of the 1 A over-discharge test. Most cells opened during 0.05 Ohm short circuit test without incident but three LTC-111 cells exploded apparently due to a lack of a thermal cutoff switch. The LTC-114 cells exposed to a hard short of 0.05 Ohms recovered but the LTC-114 cells exposed to a soft short of 1 Ohm did not. This is probably due to the activation of a resetable fuse during a hard short. Fresh cells tend to survive exposure to higher temperatures than cells previously discharged at high rate (1 Amp). LTC-111 cells tend to vent at lower temperatures than the all LTC-114 cells and the LTC-115 cells that were previously discharged at rates exceeding 1 Amp.

Frerker, Rick↗