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At least 127 records · Page 7

Matrimid substrates with bicontinuous surface and macrovoids in the bulk: A nearly ideal substrate for composite membranes in CO 2 capture

Scalable fabrication of thin-film composite (TFC) membrane for post-combustion carbon capture is often limited by the availability of high-performance nanoporous substrate. Ideally, the substrate should allow for fast gas transport at the selective layer/substrate interface as well as in the bulk of the substrate. In this study, highly permeable Matrimid substrates were prepared via vapor- and nonsolvent-induced phase separations. The phase separation mechanism of the Matrimid®/N-methyl-2-pyrrolidone casting solution was modulated by the addition of LiCl to control the solution thermodynamic stability, and nanoporous Matrimid substrates were formed with a bicontinuous surface and macrovoids in the bulk. This hierarchically optimized structure resulted in a CO 2 permeance of 2.60 × 10 5 GPU (1 GPU = 1 × 10 –6 cm 3 (STP) cm –2 s –1 cmHg –1 = 3.349 × 10 –10 mol m –2 s –1 Pa –1 ), which was ca. 11 times more permeable than a benchmark polyethersulfone substrate with cellular pores. The benefit of using this new substrate was demonstrated by coating a 170-nm amine-containing polymer to form a TFC facilitated transport membrane. The membrane exhibited a CO 2 permeance of 932 GPU at 57°C, which was 72 GPU higher than the counterpart coated on the benchmark substrate. Meanwhile, the CO 2 /N 2 selectivity was remained at 158. This permeance improvement could be well explained by the resistance-in-series model, where the improved permeance was attributed to the reductions in substrate and lateral diffusion mass transfer resistances. The upper bound (UB) analysis indicates that the Matrimid substrate is nearly ideal for the state-of-the-art polymers for CO 2 /N 2 separation. Here, the substrate improvement could also reduce the parasitic energy associated with the membrane process due to the reduced membrane cost and flue gas compression requirement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast ionic conduction achieved through the design and synthesis of ceramic heterointerfaces

Lithium (Li) chloride and iron oxychloride (FeOCl), typically nonconductive, were combined to form a [Li 1+δ Cl] δ+ /[FeOCl] δ- heterointerface composite material (LFH), achieving ionic conductivities of >1 mS cm -1 . Analysis techniques (scanning transmission electron microscopy [STEM] and electron energy-loss spectroscopy [EELS]) indicated that the microstructure of LFH consisted of an amorphous LiCl-based shell surrounding a crystalline FeOCl-based core. Electrochemical measurements alongside solid-state 6,7 Li nuclear magnetic resonance (NMR) and molecular dynamic simulations revealed Li+ as the sole conductive species, with a diffusion barrier of ~0.25 eV. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) results further supported interstitial Li + diffusion at the heterointerface and within the LiCl phase, made possible by the heterointerface. Despite susceptibility to electronic conductivity, iron’s defects and multivalency (Fe³⁺, Fe²⁺) enable the Fe–O–Cl framework to accept Cl - , facilitating Li⁺ ionic conduction. Finally, a prototype solid-state cell (showing 97% Coulombic efficiency) demonstrated the viability of this heterointerface design for applications in energy storage.

36 MATERIALS SCIENCE↗

From Cation Order to Disorder: Unlocking Ion Transport Pathways in Li–Zn–Zr–Cl Halospinels

Lithium metal chloride halospinels of the general formula Li 2 MCl 4 are a promising class of earth-abundant ion conductors for all-solid-state batteries. However, poor roomtemperature ionic conductivity has historically limited their use in practical applications. Here, we substitute Zr 4+ into Li 2 ZnCl 4 along the series Li 2−2x/3 Zn 1−x Zr 2x/3 Cl 4 (x = 0, 0.1, 0.3, 0.4, 0.6, 0.9, and 1.0) to understand how cation disorder and vacancy tuning impact ion transport in “normal” halospinels. Aliovalent Zr 4+ substitution increases ionic conductivity by nearly 5 orders of magnitude, from 1.320(3) × 10 −9 S cm −1 in Li 2 ZnCl 4 to 6.74(1)× 10 −5 S cm −1 for x = 0.6. Average and local structure characterization through synchrotron X-ray diffraction (SXRD) and neutron pair distribution function (nPDF) analysis reveal that Zr 4+ redistributes the Zn 2+ and Li + sublattices into previously unoccupied interstitial sites, which form new low-energy hopping pathways that facilitate ion transport. We rationalize the dramatic rearrangement of the cation local structure by considering the coordination preferences of the cations and the potential electrostatic penalties incurred by the higher-valent Zr 4+ cations. This work delivers an atomistic understanding of substitution-induced cation disorder and ion transport properties in a new family of earth-abundant halospinels.

Cardoza, Abby M. [Colorado School of Mines, Golden↗

Li 3– x Zr x (Ho/Lu) 1– x Cl 6 Solid Electrolytes Enable Ultrahigh-Loading Solid-State Batteries with a Prelithiated Si Anode

We report two new families of lithium metal chloride solid electrolytes Li 3–x Zr x (M) 1–x Cl 6 (0 ≤ x ≤ 0.8; M = Ho or Lu) with ionic conductivities of up to 1.8 mS cm –1 and a low activation energy of 0.34 eV. Structural elucidation via high-resolution neutron diffraction determines the Li ion distribution in trigonal Li 3 HoCl 6 , orthorhombic-I Li 3 LuCl 6 , and orthorhombic-II Li 2.4 Zr 0.6 (Ho/Lu) 0.4 Cl 6 . The last compound exhibits well-connected Li-ion pathways and abundant Li-ion carriers/vacancies to promote diffusion. All-solid-state batteries with Li 2.6 Zr 0.4 (Ho/Lu) 0.6 Cl 6 solid electrolytes and NCM85 cathodes exhibit stable cycling up to 4.6 V vs Li + /Li, which is even preserved up to 4.8 V. Stable cathode interphases are formed for both electrolytes upon cycling to 4.3, 4.6, and 4.8 V cutoff potentials, as identified by a ToF-SIMS analysis. Solid-state cells with a prelithiated Li 0.7 Si anode exhibit a significantly increased initial coulombic efficiency of 94.5% compared to Si and a high areal capacity of up to 16.3 mAh·cm –2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic Parameters and Diffusivity of Uranium in FLiNaK and ClLiK

Anodic stripping voltammetry (ASV) and cyclic voltammetry (CV) measurements at 773, 823, and 873 K were made of uranium trifluoride (UF 3 ) in lithium fluoride-sodium fluoride-potassium fluoride eutectic (FLiNaK) and uranium trichloride (UCl 3 ) in lithium chloride-potassium chloride eutectic (ClLiK). ASV data were used to estimate the charge transfer coefficients, exchange current densities, and activation energies of the uranium reactions. Charge transfer coefficients of both salt systems were within the range of 0.17 to 0.38. Exchange current densities in the fluoride and chloride salts were estimated within the range of 0.060 to 0.12 A cm -2 . Activation energy of uranium exchange current was 16.0 kJ mol -1 in the fluoride salt and 28.9 kJ mol -1 in the chloride salt. Kinetics of charge transfer were found to be faster in FLiNaK. Analyses of the CV data suggest the electrochemical system was diffusion controlled and irreversible in the chloride and fluoride salt mixtures. Diffusion coefficients of uranium in the range of temperatures were on the order of 10-5 cm 2 s -1 in both systems. Greater values of diffusivity in ClLiK are attributed to its lower density compared with FLiNaK. Activation energy of uranium diffusion in the fluoride and chloride salt mixtures were 53.4 and 89.4 kJ mol -1 , respectively.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

LiCl–Based Aqueous Electrolytes for Efficient Iron Electrodeposition

This study investigates room temperature, aqueous electrolytes for efficient iron electrodeposition. Specifically, a novel lithium chloride-based electrolyte was identified to suppress hydrogen evolution while promoting fast kinetics of iron electrodeposition, achieving high coulombic efficiency (>90%) at high current densities (>400 mA cm −2 ). Electrochemical analysis of the partial current densities of iron deposition and hydrogen co-evolution revealed that water reduction is kinetically suppressed in this electrolyte, resulting in an increase in the measured coulombic efficiency. Furthermore, a detailed investigation of the iron speciation and their complexation was performed, which revealed that, in concentrated LiCl-containing electrolytes, the ferrous (Fe 2+ ) species coordinate with chloride rather than water, enhancing deposition kinetics. The combined effect of enhanced electrodeposition kinetics and suppressed water activity provide elevated coulombic efficiency. Overall, this paper develops an understanding of anion and cation effects on the mechanism of electrodeposition and hydrogen co-evolution in concentrated electrolytes in search of improved aqueous media (e.g., concentrated LiCl) for efficient metal electro-synthesis.

Lvovich, William [Case Western Reserve University,↗

Structure-Property Relationships of Hydrogel-Salt Composites for Extreme Sorption Performance

Hydrogel-salt composites have emerged as a promising low-cost material for a wide range of sorption applications including thermal energy storage, atmospheric water harvesting, and dehumidification. Despite significant efforts devoted to the synthesis of novel hydrogels and their implementation in sorption devices, very little is known about the fundamental connection between the hydrogel structure and composition with their material-level properties. This knowledge, however, is critical to enable the rational design of high-performance hydrogels targeted at the various applications. In this work, we elucidate via experiments and modeling the link between the hydrogel structure, including its salt content and polymer nanostructure, and its sorption properties. Using lithium chloride-embedded polyacrylamide hydrogels as model systems, we demonstrate that the hydrogel uptake and its kinetics are dominated by the content and properties of the salt. In fact, the polymer nanostructure has no a minor effect in its sorption performance. Based on our experimental insights, we develop a model for the simultaneous diffusion of water and salts in hydrogels, which helps to explain the observed relationship between hydrogel structure and its sorption properties. Furthermore, we leverage these insights to synthesize hydrogels with record-high water vapor uptakes of 1.79 g/g, 2.58 g/g, 3.86 g/g, and 8.51 g/g at 30%, 50%, 70%, and 90% relative humidity, respectively, owing to the use of large amounts of highly hygroscopic salts. By demonstrating the structure-property relationships, this work enables the rational design of salt-embedded hydrogels for low-cost and high-performance thermal energy storage, atmospheric freshwater production, and space conditioning.

Díaz-Marín, Carlos D↗

An ellipsometer with variable angle of incidence for studies in ultrahigh vacuum

The windows for the vacuum chamber are incorporated into the optical bench system by means of flexible bellows which allow measurements to be made over a large range of angle of incidence, one of which is chosen so that maximum sensitivity is obtained. The principal angle of incidence was determined, and straightforward corrections for strain birefringence of vacuum chamber windows were made. Atomically clean surfaces of sodium chloride and lithium fluoride were investigated to verify the performance of the system. Submonolayer and monolayer coverage of water on these surfaces could be detected. On cleavage planes of NaCl, a first monolayer of adsorbed water is complete at about one torr only.

Walter, H. U.↗

Safety and abuse testing

A series of abuse tests on large lithium thionyl chloride cells was initiated. Performance data obtained in testing rectangular 2,000 and 10,000 ampere-hour cells are discussed and graphically presented.

Younger, G.↗

Applications and safety data

A general overview of activities involving lithium batteries, which shows the various applications and data that were performed for numerous industry and government sponsors is presented. Brief discussions on electrochemical criteria selection, and typical storage and performance data obtained from three systems being developed are presented. Current safety work being done on high-rate, D, SO2 cells is also discussed. Three chemistries were developed and are discussed: lithium vanadium pentoxide, lithium sulfur dioxide, and lithium thionyl chloride. Storage, performance and safety data are graphically presented.

Berlangieri, N. J.↗

A study on various methods of supplying propellant to an orbit insertion rocket engine

Various types of pumps and pump drives were evaluated to determine the lightest weight system for supplying propellants to a planetary orbit insertion rocket engine. From these analyses four candidate propellant feed systems were identified. Systems Nos. 1 and 2 were both battery powered (lithium-thionyl-chloride or silver-zinc) motor driven pumps. System 3 was a monopropellant gas generator powered turbopump. System 4 was a bipropellant gas generator powered turbopump. Parameters considered were pump break horsepower, weight, reliability, transient response and system stability. Figures of merit were established and the ranking of the candidate systems was determined. Conceptual designs were prepared for typical motor driven pumps and turbopump configurations for a 1000 lbf thrust rocket engine.

Boretz, J. E.↗

Altus small button cell performance

Results of testing performed on Altus lithium thionyl chloride cells are presented. The test plan followed simulates the mine environment. It involves nondestructive testing, ruggedness testing and destructive testing. The nondestructive testing involves open circuit voltage measurements initially on all the cells, alternating current resistance measurements initially on all the cells and closed circuit voltage pulses, 20s on and 20s through 1000, 100, 10 and 1 ohms at temperatures of -54 to 71 C. The ruggedness testing involves low frequency vibration, high frequency vibration, and two-phase water entry shock at temperatures of -54, 25 and 71 C. It also involves thermal shock tests.

Freeman, C.↗

Catastrophic event modeling

A mathematical model for the catastrophic failures (venting or explosion of the cell) in lithium thionyl chloride batteries is presented. The phenomenology of the various processes leading to cell failure is reviewed.

Frank, H. A.↗

Safety of Li-SOCl2 cells

The safety of lithium thionyl chloride cells has been a concern of JPL for some time in the development of these cells for NASA's use. Because the safety problems are complex and several issues are interrelated it was decided that it would be best to put together an organized review of the safety issues, which are reviewed here. Hazards are classified in three categories: (1) cell leakage, a problem dealing with construction or materials; (2) venting of toxic gases through seals and welds, considered a mild hazard in which electrolyte and gas is released; and (3) violent rupture or controlled rupture of cells with the possibility of explosion of the materials inside. These hazards and their effects are detailed along with possible ways of dealing with them.

Subbarao, S.↗

Preliminary test results for Li-SOCl2 high-rate D cells

The performance and abuse characteristics of 55 D-size lithium-thionyl chloride (Li-SOCl2) cells are evaluated at relatively high rates. Results from the following tests are presented: shock test, vibration test, capacity performance, uninsulated short circuit, high temperature exposure, and overdischarge.

Bragg, Bobby J.↗

Resonant mode controllers for launch vehicle applications

Electro-mechanical actuator (EMA) systems are currently being investigated for the National Launch System (NLS) as a replacement for hydraulic actuators due to the large amount of manpower and support hardware required to maintain the hydraulic systems. EMA systems in weight sensitive applications, such as launch vehicles, have been limited to around 5 hp due to system size, controller efficiency, thermal management, and battery size. Presented here are design and test data for an EMA system that competes favorably in weight and is superior in maintainability to the hydraulic system. An EMA system uses dc power provided by a high energy density bipolar lithium thionyl chloride battery, with power conversion performed by low loss resonant topologies, and a high efficiency induction motor controlled with a high performance field oriented controller to drive a linear actuator.

Schreiner, Ken E.↗

The NASA space power technology program

NASA has a broad technology program in the field of space power. This paper describes that program, including the roles and responsibilities of the various NASA field centers and major contractors. In the power source area, the paper discusses the SP-100 Space Nuclear Power Project, which has been under way for about seven years and is making substantial progress toward development of components for a 100-kilowatt power system that can be scaled to other sizes. This system is a candidate power source for nuclear electric propulsion, as well as for a power plant for a lunar base. In the energy storage area, the paper describes NASA's battery- and fuel-cell development programs. NASA is actively working on NiCd, NiH2, and lithium batteries. A status update is also given on a U.S. Air Force-sponsored program to develop a large (150 ampere-hour) lithium-thionyl chloride battery for the Centaur upper-stage launch vehicle. Finally, the area of power management and distribution (PMAD) is addressed, including power system components such as solid-state switches and power integrated circuits. Automated load management and other computer-controlled functions offer considerable payoffs. The state of the art in space power is described, along with NASA's medium- and long-term goals in the area.

Stephenson, R. Rhoads↗