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At least 19 records

Isotopic Signatures of Lithium Carbonate and Lithium Hydroxide Monohydrate Measured Using Raman Spectroscopy

Lithium isotopic ratios have wide ranging applications as chemical signatures, including improved understanding of geochemical processes and battery development. Measurement of isotope ratios using optical spectroscopies would provide an alternative to traditional mass spectrometric methods, which are expensive and often limited to a chemical laboratory. In this work, Raman spectra of 7 Li 2 CO 3 , 6 Li 2 CO 3 , 7 LiOH*H 2 O and 6 LiOH*H 2 O have been measured to determine the effect of lithium isotope substitution on the Raman molecular vibrations. Thirteen peaks were observed in the spectrum of lithium carbonate, with discernable isotopic shifts occurring in eleven of the thirteen vibrations, two of which have not been previously reported in the literature. The spectrum of lithium hydroxide monohydrate contained nine peaks, with discernable isotopic shifts occurring in eight of the nine vibrations, four of which have not been previously reported in the literature. The Raman spectral data reported here for lithium carbonate and lithium hydroxide monohydrate are in agreement with the previously reported works in the literature, in which the Raman active modes of these molecules were first identified and assigned. However, due to the stability and resolution of the detection system used in this work, isotopic shifts with a magnitude less than one wavenumber have been identified. Principal Component Regression was used to evaluate the sensitivity to isotopic content of small Raman peak shifts in Li 2 CO 3 and indicates differences greater than 2 atom-% could be reliably determined. These measurements add to the body of work on lithium isotope Raman spectroscopy for these two compounds and increases the number of Raman bands which could be used for lithium isotope content analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rechargeable lithium-hydroxide based non-aqueous lithium oxygen batteries

An electrochemical device includes an air cathode; a lithium-containing anode metal; a porous separator; and a non-aqueous electrolyte comprising a lithium salt, a sodium salt, and a solvent; wherein the electrochemical device is a lithium-air battery. A total concentration of the lithium salt and the sodium salt in the non-aqueous electrolyte may be from about 0.001 M to about 7 M.

25 ENERGY STORAGE↗

Energy, greenhouse gas, and water life cycle analysis of lithium carbonate and lithium hydroxide monohydrate from brine and ore resources and their use in lithium ion battery cathodes and lithium ion batteries

Life cycle analyses (LCAs) were conducted for battery-grade lithium carbonate (Li 2 CO 3 ) and lithium hydroxide monohydrate (LiOH·H 2 O) produced from Chilean brines (Salar de Atacama) and Australian spodumene ores. The LCA was also extended beyond the production of Li 2 CO 3 and LiOH·H 2 O to include battery cathode materials as well as full automotive traction batteries to observe the effect that the lithium production pathways had on these end products. The LCA here covers material, water, and energy flows associated with lithium acquisition; lithium concentration; production of lithium chemicals, battery cathode powders, and batteries; and associated transportation activities along the supply chain. Based on battery cathode material, the difference in lithium source represents a difference of up to 20% for NMC811 cathode greenhouse gases (GHGs) and up to 45% for NMC622 cathode GHGs. For full batteries, this represents a difference of up to 9% for NMC811 batteries and 20% for NMC622 batteries. Production of Li 2 CO 3 from brine-based resources had less life cycle GHG emissions and freshwater consumption per tonne of Li 2 CO 3 than Li 2 CO 3 from ore-based resources. And LiOH·H 2 O produced from brine-based lithium also had less life cycle GHG emissions and freshwater consumption per tonne of LiOH·H 2 O than LiOH·H 2 O from ore-based resources.

25 ENERGY STORAGE↗

Root Cause Assessment of Pressure Drop Rise of a Packed Bed of Lithium Hydroxide in the International Space Station Trace Contaminant Control System

The trace contaminant control system (TCCS) located in the International Space Station s (ISS) U.S. laboratory module employs physical adsorption, thermal catalytic oxidation, and chemical adsorption to remove trace chemical contamination produced by equipment offgassing and anthropogenic sources from the cabin atmosphere. The chemical adsorption stage, consisting of a packed bed of granular lithium hydroxide (LiOH), is located after the thermal catalytic oxidation stage and is designed to remove acid gas byproducts that may be formed in the upstream oxidation stage. While in service on board the ISS, the LiOH bed exhibited a change in flow resistance that leading to flow control difficulties in the TCCS. Post flight evaluation revealed LiOH granule size attrition among other changes. An experimental program was employed to investigate mechanisms hypothesized to contribute to the change in the packed bed s flow resistance. Background on the problem is summarized, including a discussion of likely mechanisms. The experimental program is described, results are presented, and implications for the future are discussed.

Aguilera, Tatiana↗

Bipolar Membrane Capacitive Deionization for the Selective Capture of Lithium Ions from Brines and Conversion to Lithium Hydroxide

Meeting the increasing demand for lithium in vehicle electrification and renewable energy storage requires innovations in lithium-ion (Li + ) separations. Traditional solar evaporation methods for lithium recovery are slow and consume tremendous volumes of water and secondary chemicals (acids and bases). This study introduces a bipolar membrane capacitive deionization (BPM-CDI) unit for direct lithium extraction and LiOH production without the external addition of acids and bases. Utilizing de-lithiated lithium-iron-phosphate (LFP) coated carbon cloth electrodes, the BPM-CDI unit demonstrates selective Li + capture over competing ions. Molecular dynamics simulations and H-cell experiments elucidate pH inversion mechanisms during Li + release, yielding LiOH. The BPM-CDI platform efficiently removes Li + from synthetic brines featuring 8x higher Mg 2+ concentrations (200 ppm Mg 2+ ) and 26x higher Na + concentrations (682 ppm Na + ), achieving a LiOH concentration of 124 ppm (36 ppm Li + ) after 8 cycles of recirculation. Post-mortem analysis confirms electrode integrity and stability. BPM-CDI integrated with selective electrodes is a promising electrochemical separation-reactor platform for lithium recovery while producing LiOH.

Kulkarni, Tanmay↗

Synthesis of Single Crystal Li 2 NpO 4 and Li 4 NpO 5 from Aqueous Lithium Hydroxide Solutions under Mild Hydrothermal Conditions

The ternary oxides, Li 2 NpO 4 and Li 4 NpO 5 , were synthesized under mild hydrothermal conditions using concentrated LiOH solutions containing NpO 2 (NO 3 )( 2 ). The reactions resulted in the formation of single crystals of both compounds, enabling the determination of their single crystal structures for the first time. Further, exploration of the synthetic phase space demonstrates that the resulting neptunate phases are dependent on the concentration of LiOH, transitioning from Li 2 NpO 4 , containing a typical octahedral neptunyl geometry with two shorter Np≡O bonds, at lower LiOH concentrations to Li 4 NpO 5 with two long and four short Np-O bonds under saturated solution conditions. Reactions exploring the same synthetic conditions are also reported for uranyl(VI) for comparison. Raman spectra of the compounds were collected and analyzed to evaluate the Np-O bonding in these compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surprising Relationship between Silicon Anode Calendar Aging and Electrolyte Components in a Localized High-Concentration Electrolyte System

Although localized high-concentration electrolytes (LHCEs) have been shown to improve the calendar lifetime of silicon anodes, the roles of the electrolyte constituents in calendar aging are not well understood. Here, in this work, we utilize a voltage hold protocol and an LHCE with varying molar ratios of lithium bis(fluorosulfonyl)imide (LiFSI), tetramethylene sulfone (TMS), and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) to probe the component roles during aging. Interestingly, the estimated calendar lifetime and irreversible lithium losses from the V-hold experiments are independent of the electrolyte formulations. Contrarily, the solid electrolyte interphase (SEI) composition depends on the electrolyte formulation. X-ray photoelectron spectroscopy shows that TMS-coordinated species decompose to form insoluble alkanes and lithium hydroxide (LiOH), while lithium fluoride (LiF) originates from the anion-coordination complex. The SEI composition does not appear to play a significant role in the silicon anode passivity, as measured by parasitic current, suggesting that the SEI-electrolyte interactions dictate the calendar aging mechanisms.

Si anode↗

Carbon Dioxide Removal via Passive Thermal Approaches

A paper describes a regenerable approach to separate carbon dioxide from other cabin gases by means of cooling until the carbon dioxide forms carbon dioxide ice on the walls of the physical device. Currently, NASA space vehicles remove carbon dioxide by reaction with lithium hydroxide (LiOH) or by adsorption to an amine, a zeolite, or other sorbent. Use of lithium hydroxide, though reliable and well-understood, requires significant mass for all but the shortest missions in the form of lithium hydroxide pellets, because the reaction of carbon dioxide with lithium hydroxide is essentially irreversible. This approach is regenerable, uses less power than other historical approaches, and it is almost entirely passive, so it is more economical to operate and potentially maintenance- free for long-duration missions. In carbon dioxide removal mode, this approach passes a bone-dry stream of crew cabin atmospheric gas through a metal channel in thermal contact with a radiator. The radiator is pointed to reject thermal loads only to space. Within the channel, the working stream is cooled to the sublimation temperature of carbon dioxide at the prevailing cabin pressure, leading to formation of carbon dioxide ice on the channel walls. After a prescribed time or accumulation of carbon dioxide ice, for regeneration of the device, the channel is closed off from the crew cabin and the carbon dioxide ice is sublimed and either vented to the environment or accumulated for recovery of oxygen in a fully regenerative life support system.

Lawson, Michael↗

Enabling Ambient Stability of LiNiO 2 Lithium-Ion Battery Cathode Materials via Graphene–Cellulose Composite Coatings

Nickel-rich layered oxides are widely used as cathode materials for energy-dense lithium-ion batteries. These chemistries, based on the parent compound LiNiO 2 (LNO), are highly sensitive to ambient environments and are known to readily react with moisture and carbon dioxide. As a result, impurities such as lithium hydroxides and lithium carbonates are formed at the LNO surface, compromising electrochemical behavior. Here, we address this issue by coating LNO cathode particles with a hydrophobic barrier layer composed of graphene and ethyl cellulose (GrEC). This coating limits contact between atmospheric moisture and the LNO surface, which minimizes the generation of lithium impurities. This scheme is evaluated by exposing coated LNO to humidified CO 2 for 24 h as an accelerated ambient degradation test. Subsequent spectroscopy, microscopy, and electrochemical characterization show no detectable signatures of carbonates on the LNO surface, thus verifying that the GrEC coating prevents ambient degradation. In conclusion, by demonstrating this methodology for the ultimate nickel-rich chemistry, this approach can likely be generalized to a wide range of ambient-sensitive battery materials.

25 ENERGY STORAGE↗

Performance Characterization and Simulation of Amine-Based Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and water (H2O) concentrations in the vapor phase of a space suit is critical to ensuring an astronauts safety, comfortability, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxides (MetOx). Lithium hydroxide is a consumable material and requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications which control atmospheric concentrations of both CO2 and H2O through a fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed and documented from experimental and theoretical perspectives. To support developmental efforts, a first principles model has also been established for the vacuum swing adsorption technology. The efforts documented herein summarize performance characterization and simulation results for several variable metabolic profiles subjected to the RCA. Furthermore, a variety of control methods are explored including timed swing cycles, instantaneous CO2 feedback control, and time-averaged CO2 feedback control. A variety of off-nominal tests are also explored including high/low suit temperatures, increasingly high humidity cases, and dynamic pressure cases simulating the suit pre-breathe protocol. Consequently, this work builds on efforts previous efforts to fully bound the performance of the rapid cycle amine under a variety of nominal and off-nominal conditions.

Swickrath, Michael J.↗

Round-robin analysis of highly depleted lithium for Generation IV nuclear reactor applications

Lithium reference materials containing unnaturally high abundances of 7 Li are not currently available, which poses quality control problems for highly depleted lithium materials (i.e., depleted in 6 Li) required for Generation IV nuclear reactors. This study presents an interlaboratory comparison of a lithium carbonate (NIST SRM924a) containing nominally natural isotopic abundances (~92.4 % Li-7) and a highly depleted lithium hydroxide material (~99.95 % Li-7). The natural lithium isotope abundances of NIST SRM924a are confirmed, and the 6 Li/ 7 Li ratio of the lithium hydroxide ranged from 0.000399 to 0.000436 with an average of 0.000428 ± 0.000023 (2SD, n = 9). Finally, going forward this material can be used as quality control for analytical work involving highly depleted lithium.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Performance Characterization and Simulation of Amine-Based Vacuum Swing Sorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and water (H2O) vapor concentrations in a space suit is critical to ensuring an astronauts safety, comfort, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxide (MetOx) canisters. Lithium hydroxide is a consumable material that requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications. The vacuum swing units control atmospheric concentrations of both CO2 and H2O through fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed experimentally and documented in previous reports. To support developmental e orts, a first principles model has also been established for the vacuum swing sorption technology. For the first time in several decades, a major re-design of Portable Life Support System (PLSS) for the extra-vehicular mobility unit (EMU) is underway. NASA at Johnson Space Center built and tested an integrated PLSS test bed of all subsystems under a variety of simulated EVA conditions of which the RCA prototype played a significant role. The efforts documented herein summarize RCA test performance and simulation results for single and variable metabolic rate experiments in an integrated context. In addition, a variety of off-nominal tests were performed to assess the capability of the RCA to function under challenging circumstances. Tests included high water production experiments, degraded vacuum regeneration, and deliberate valve/power failure and recovery.

Swickrath, Michael J.↗

Dehydrohalogenation of atmospheric contaminants in the space cabin

A total of nine chlorinated ethanes and ethenes were circulated over lithium hydroxide in a laboratory scale closed system simulator. System volume and lithium hydroxide temperature were varied from that intended to maximize possible reactions to conditions approximating those of a space cabin environment. Of the nine compounds tested, seven were found to be dehydrohalogenated (viz., loss of hydrogen chloride) in the course of one or more experimental treatments. Of particular significance was the conversion of 1,2-dichloroethane to chloroethene, a known carcinogen, and of trichloroethene to dichloroethyne, a highly toxic substance. It is therefore concluded that a potentially hazardous situation exists for the inhabitants of closed ecological systems such as spacecraft, one for which precautions must continue to be taken.

Spain, M. A.↗

Life-cycle analysis of battery metal recycling with lithium recovery from a spent lithium-ion battery

Demand for critical materials (nickel, cobalt, manganese [NCM], and lithium) for use in batteries is increasing rapidly due to the expansion of the battery-electric vehicles market. Battery metal recycling (BMR) is an important technology that can potentially realize environmental and economic benefits in cathode active material (LiNi x Mn y Co z O 2 ) production using recycled materials. While current major battery recycling technologies recover cathode materials (NCM) and other metals (steel, aluminum, copper, etc.) from the spent battery, the lithium (Li) recovery rate is less than 1% in the world. In this study, we analyze the environmental benefits of a BMR process that recovers lithium in the form of lithium hydroxide monohydrate (LiOH∙H 2 O) along with other cathode materials. Using life-cycle analysis (LCA), we evaluate the life-cycle greenhouse gas (GHG) emissions, criteria air pollutant emissions, and water consumption of the new BMR technology in terms of lithium hydroxide production and cathode active material production. The LCA results show that the life-cycle GHG emissions recycled LiOH are 37–72% lower than those of virgin LiOH production from Chilean brine and Australian ore, respectively. In addition, the life-cycle GHG emissions of NCM811 produced using the recycled materials are 40–48% lower compared to virgin cathode active material production. Furthermore, recovering lithium from the spent batteries reduces associated air pollutant emissions and water consumption relative to using the virgin materials or materials from other recycling technologies without LiOH recovery.

25 ENERGY STORAGE↗

Lessons Learned—Lithium Silicide Hydration Fire

Alkali metals, such as lithium, sodium, potassium, etc., are highly reactive elements. While researchers generally handle these metals with caution, less caution is taken when these elements have been “reacted”. In this work, a recent incident is examined in which a pair of researchers ignited a lithium silicide alloy sample that was assumed to be fully hydrated to lithium hydroxide and, thereby, no longer water-reactive. However, variations in the original chemical composition of the lithium compounds examined resulted in select mixtures failing to hydrate and react completely to lithium hydroxide in the time frame allowed. This gave rise to residual unreacted, water-sensitive lithium silicide which resulted in a violent exothermic reaction with water and autoignition of the produced hydrogen gas. This Article describes this incident and improvements that can be implemented to prevent similar incidents from occurring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Apollo 13 LiOH canister breakthrough test

The Apollo 13 lithium hydroxide canister test was conducted to evaluate emergency measures designed to enable the Apollo 13 crew to use command module lithium hydroxide canisters in the lunar module. The test verified the effectiveness of the emergency system and established that the canisters in the command module would provide ample carbon dioxide removal for the return of the Apollo 13 crew. The time interval between canister changes on the flight was also determined in the test. This reduced power demand on the lunar module by eliminating the need for telemetry in determining canister replacement times. Details of the canister modifications were relayed to the flight crew and a replica of the test system was assembled in the flight vehicle. Graphs of the parameters which were measured during the simulation are presented.

Leblanc, J. C.↗

Flight prototype CO2 and humidity control system

A regenerable CO2 and humidity control system is presently being developed for potential use on the space shuttle as an alternative to the baseline lithium hydroxide system. The system utilizes a sorbent material (designated HS-C) to adsorb CO2 and water vapor from the cabin atmosphere and desorb the CO2 and water vapor overboard when exposed to a space vacuum. Continuous operation is achieved by utilizing two beds which are alternately cycled between adsorption and desorption. A shuttle vehicle integration study showed that the HS-C system offers substantial weight advantages compared to the baseline shuttle orbiter expendable lithium hydroxide CO2 removal system for extended missions beyond the nominal design of four men for seven days. This study defined a system packaging envelope in the area presently occupied by the LiOH cartridges.

Rudy, K. M.↗