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NASA NTRS2009

Carbon Dioxide - Our Common "Enemy"

Health effects of brief and prolonged exposure to carbon dioxide continue to be a concern for those of us who manage this pollutant in closed volumes, such as in spacecraft and submarines. In both examples, considerable resources are required to scrub the atmosphere to levels that are considered totally safe for maintenance of crew health and performance. Defining safe levels is not a simple task because of many confounding factors, including: lack of a robust database on human exposures, suspected significant variations in individual susceptibility, variations in the endpoints used to assess potentially adverse effects, the added effects of stress, and the fluid shifts associated with micro-gravity (astronauts only). In 2007 the National Research Council proposed revised Continuous Exposure Guidelines (CEGLs) and Emergency Exposure Guidelines (EEGLs) to the U.S. Navy. Similarly, in 2008 the NASA Toxicology Group, in cooperation with another subcommittee of the National Research Council, revised Spacecraft Maximum Allowable Concentrations (SMACs). In addition, a 1000-day exposure limit was set for long-duration spaceflights to celestial bodies. Herein we examine the rationale for the levels proposed to the U.S. Navy and compare this rationale with the one used by NASA to set its limits. We include a critical review of previous studies on the effects of exposure to carbon dioxide and attempt to dissect out the challenges associated with setting fully-defensible limits. We also describe recent experiences with management of carbon dioxide aboard the International Space Station with 13 persons aboard. This includes the tandem operations of the Russian Vozduk and the U.S. Carbon Dioxide Removal System. A third removal system is present while the station is docked to the Shuttle spacecraft, so our experience includes the lithium hydroxide system aboard Shuttle for the removal of carbon dioxide. We discuss strategies for highly-efficient, regenerable removal of carbon dioxide that could meet the 1000-day SMAC of 0.5%, which would apply to long-duration voyages to Mars.

James, John T.↗

NASA NTRS2010

Simulation and Optimization of Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and humidity levels in a spacesuit is critical to ensuring both the safety and comfort of an astronaut during extra-vehicular activity (EVA). Traditionally, this has been accomplished utilizing non-regenerative lithium hydroxide (LiOH) or regenerative metal oxide (MetOx) canisters which pose a significant weight burden. Although such technology enables air revitalization, the volume requirements to store the waste canisters as well as the mass to transport multiple units become prohibitive as mission durations increase. Consequently, motivation exists toward developing a fully regenerative technology for environmental control. The application of solid amine materials with vacuum swing adsorption technology has shown the capacity to control CO2 and concomitantly manage humidity levels through a fully regenerative cycle eliminating mission constraints imposed with non-regenerative technologies. Experimental results for full-size and sub-scale test articles have been collected and are described herein. In order to accelerate the developmental efforts, an axially-dispersed plug ow model with an accompanying energy balance has been established and correlated with the experimental data. The experimental and simulation results display good agreement for a variety of ow rates (110-170 SLM), replicated metabolic challenges (100-590 Watts), and atmosphere pressures under consideration for the spacesuit (248 and 760 mm Hg). The relationship between swing adsorption cycles for an outlet criterion of 6.0 mm Hg of CO2 partial pressure has been established for each metabolic challenge. In addition, variable metabolic profiles were imposed on the test articles in order to assess the ability of the technology to transition to new operational constraints. The advent of the model provides the capacity to apply computer-aided engineering practices to support the ongoing efforts to optimize and mature this technology for future application to space exploration.

Swickrath, Michael J.↗

NASA NTRS2011

Crew Health and Performance Improvements with Reduced Carbon Dioxide Levels and the Resource Impact to Accomplish Those Reductions

Carbon dioxide (CO2) removal is one of the primary functions of the International Space Station (ISS) atmosphere revitalization systems. Primary CO2 removal is via the ISS s two Carbon Dioxide Removal Assemblies (CDRAs) and the Russian carbon dioxide removal assembly (Vozdukh); both of these systems are regenerable, meaning that their CO2 removal capacity theoretically remains constant as long as the system is operating. Contingency CO2 removal capability is provided by lithium hydroxide (LiOH) canisters, which are consumable, meaning that their CO2 removal capability disappears once the resource is used. With the advent of 6 crew ISS operations, experience showing that CDRA failures are not uncommon, and anecdotal association of crew symptoms with CO2 values just above 4 mmHg, the question arises: How much lower do we keep CO2 levels to minimize the risk to crew health and performance, and what will the operational cost to the CDRAs be to do it? The primary crew health concerns center on the interaction of increased intracranial pressure from fluid shifts and the increased intracranial blood flow induced by CO2. Typical acute symptoms include headache, minor visual disturbances, and subtle behavioral changes. The historical database of CO2 exposures since the beginning of ISS operations has been compared to the incidence of crew symptoms reported in private medical conferences. We have used this database in an attempt to establish an association between the CO2 levels and the risk of crew symptoms. This comparison will answer the question of the level needed to protect the crew from acute effects. As for the second part of the question, operation of the ISS s regenerable CO2 removal capability reduces the limited life of constituent parts. It also consumes limited electrical power and thermal control resources. Operation of consumable CO2 removal capability (LiOH) uses finite consumable materials, which must be replenished in the long term. Therefore, increased CO2 removal means increased resource use, with increased logistical capability to maintain necessary resources on board ISS. We must strike a balance between sufficiently low CO2 levels to maintain crew health and CO2 levels which are operationally feasible for the ISS program

James, John T.↗

NASA NTRS2010

Carbon Dioxide Control System for a Mars Space Suit Life Support System

Carbon dioxide (CO2) control during Extravehicular Activities (EVAs) on Mars will be challenging. Lithium hydroxide (LiOH) canisters have impractical logistics penalties, and regenerable metal oxide (MetOx) canisters weigh too much. Cycling bed systems and permeable membranes that are regenerable in space vacuum cannot vent on Mars due to the high partial pressure of CO2 in the atmosphere. Although sweep gas regeneration is under investigation, the feasibility, logistics penalties, and failure modes associated with this technique have not been fully determined. TDA Research, Inc. is developing a durable, high-capacity regenerable adsorbent that can remove CO2 from the space suit ventilation loop. The system design allows sorbent regeneration at or above 6 torr, eliminating the potential for Martian atmosphere to leak into the regeneration bed and into the ventilation loop. Regeneration during EVA eliminates the consumable requirement related to the use of LiOH canisters and the mission duration limitations imposed by MetOx system. The concept minimizes the amount of consumable to be brought from Earth and makes the mission more affordable, while providing great operational flexibility during EVA. The feasibility of the concept has been demonstrated in a series of bench-scale experiments and a preliminary system analysis. Results indicate that sorbent regeneration can be accomplished by applying a 14 C temperature swing, while regenerating at 13 torr (well above the Martian atmospheric pressure), withstanding over 1,000 adsorption/regeneration cycles. This paper presents the latest results from these sorbent and system development efforts.

Alptekin, Gokhan↗

NASA NTRS2011

Carbon Dioxide Control System for a Mars Space Suit Life Support System

Carbon dioxide (CO2) control during Extravehicular Activities (EVAs) on Mars will be challenging. Lithium hydroxide (LiOH) canisters have impractical logistics penalties, and regenerable metal oxide (MetOx) canisters weigh too much. Cycling bed systems and permeable membranes that are regenerable in space vacuum cannot vent on Mars due to the high partial pressure of CO2 in the atmosphere. Although sweep gas regeneration is under investigation, the feasibility, logistics penalties, and failure modes associated with this technique have not been fully determined. TDA Research, Inc. is developing a durable, high-capacity regenerable adsorbent that can remove CO2 from the space suit ventilation loop. The system design allows sorbent regeneration at or above 6 torr, eliminating the potential for Martian atmosphere to leak into the regeneration bed and into the ventilation loop. Regeneration during EVA minimizes the amount of consumables to be brought from Earth and makes the mission more affordable, while providing great operational flexibility during EVA. The feasibility of the concept has been demonstrated in a series of bench-scale experiments and a preliminary system analysis. This paper presents the latest results from these sorbent and system development efforts.

Alptekin, Gokhan↗

NASA NTRS2011

Simulation and Optimization of Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and humidity levels in a spacesuit is critical to ensuring both the safety and comfort of an astronaut during extra-vehicular activity (EVA). Traditionally, this has been accomplished utilizing either non-regenerative lithium hydroxide (LiOH) or regenerative but heavy metal oxide (MetOx) canisters which pose a significant weight burden. Although such technology enables air revitalization, the volume requirements to store the waste canisters as well as the mass to transport multiple units become prohibitive as mission durations increase. Consequently, motivation exists toward developing a fully regenerative technology for spacesuit environmental control. The application of solid amine materials with vacuum swing adsorption technology has shown the capacity to control CO2 while concomitantly managing humidity levels through a fully regenerative cycle eliminating constraints imposed with the traditional technologies. Prototype air revitalization units employing this technology have been fabricated in both a rectangular and cylindrical geometry. Experimental results for these test articles have been collected and are described herein. In order to accelerate the developmental efforts, an axially-dispersed plug flow model with an accompanying energy balance has been established and correlated with the experimental data. The experimental and simulation results display good agreement for a variety of flow rates (110-170 ALM), replicated metabolic challenges (100-590 Watts), and atmosphere pressures under consideration for the spacesuit (248 and 760 mm Hg). The testing and model results lend insight into the operational capabilities of these devices as well as the influence the geometry of the device has on performance. In addition, variable metabolic profiles were imposed on the test articles in order to assess the ability of the technology to transition to new metabolic conditions. The advent of the model provides the capacity to apply computer-aided engineering practices to support the ongoing efforts to optimize and mature this technology for future application to space exploration.

Swickrath, Michael J.↗

NASA NTRS2016

HESTIA Phase I Test Results: The Air Revitalization System

In any human spaceflight mission, a number of Environmental Control & Life Support System (ECLSS) technologies work together to provide the conditions astronauts need to live healthily, productively, and comfortably in space. In a long-duration mission, many of these ECLSS technologies may use materials supplied by In-Situ Resource Utilization (ISRU), introducing more interactions between systems. The Human Exploration Spacecraft Test-bed for Integration & Advancement (HESTIA) Project aims to create a test-bed to evaluate ECLSS and ISRU technologies and how they interact in a high-fidelity, closed-loop, human-rated analog habitat. Air purity and conditioning are essential components within any ECLSS and for HESTIA's first test they were achieved with the Air Revitalization System (ARS) described below. The ARS provided four essential functions to the test-bed chamber: cooling the air, removing humidity from the air, removing trace contaminants, and scrubbing carbon dioxide (CO2) from the air. In this case, the oxygen supply function was provided by ISRU. In the current configuration, the ARS is a collection of different subsystems. A fan circulates the air, while a condensing heat exchanger (CHX) pulls humidity out of the air. A Trace Contaminant Removal System (TCRS) filters the air of potentially harmful contaminants. Lastly, a Reactive Plastic Lithium Hydroxide (RP-LiOH) unit removes CO2 from the breathing air. During the HESTIA Phase I test in September 2015, the ARS and its individual components each functioned as expected, although further analysis is underway. During the Phase I testing and in prior bench-top tests, the energy balance of heat removed by the CHX was not equal to the cooling it received. This indicated possible instrument error and therefore recalibration of the instruments and follow-up testing is planned in 2016 to address the issue. The ARS was tested in conjunction with two other systems: the Human Metabolic Simulator (HMS) and the Electrolyzer. They behaved as anticipated as well. The HMS added humidity, CO2, and heat to the chamber while removing oxygen, and the Electrolyzer (an ISRU technology) added oxygen. The objective for HESTIA in 2015 was achieved: the creation of a high-fidelity test-bed for ECLSS and ISRU technologies. With the 'backbone' technologies installed, more technologies will be added to increase the analog habitat's fidelity over the next few years. The ARS was designed with this in mind, and as new technologies develop and mature, the strategic installation of the existing components will allow for them to be replaced with the new technologies.

Wright, Sarah E.↗

NASA NTRS2018

NASA ISS Portable Fan Assembly Acoustics

The Portable Fan Assembly (PFA) is a variable speed fan that can be used to provide additional ventilation inside International Space Station (ISS) modules as needed for crew comfort or for enhanced mixing of the ISS atmosphere. This fan can also be configured with a Shuttle era lithium hydroxide (LiOH) canister for CO2 removal in confined areas partially of fully isolated from the primary Environmental Control and Life Support System (ECLSS) on ISS which is responsible for CO2 removal. This report documents noise emission levels of the PFA at various speed settings and configurations. It also documents the acoustic attenuation effects realized when circulating air through the PFA inlet and outlet mufflers and when operating in its CO2 removal configuration (CRK) with a LiOH canister (sorbent bed) installed over the fan outlet.

Boone, Andrew↗

NASA NTRS2017

Much Lower Launch Costs Make Resupply Cheaper than Recycling for Space Life Support

The development of commercial launch vehicles by SpaceX has greatly reduced the cost of launching mass to Low Earth Orbit (LEO). Reusable launch vehicles may further reduce the launch cost per kilogram. The new low launch cost makes open loop life support much cheaper than before. Open loop systems resupply water and oxygen in tanks for crew use and provide disposable lithium hydroxide (LiOH) in canisters to remove carbon dioxide. Short human space missions such as Apollo and shuttle have used open loop life support, but the long duration International Space Station (ISS) recycles water and oxygen and removes carbon dioxide with a regenerative molecular sieve. These ISS regenerative and recycling life support systems have significantly reduced the total launch mass needed for life support. But, since the development cost of recycling systems is much higher than the cost of tanks and canisters, the relative cost savings have been much less than the launch mass savings. The Life Cycle Cost (LCC) includes development, launch, and operations. If another space station was built in LEO, resupply life support would be much cheaper than the current recycling systems. The mission most favorable to recycling would be a long term lunar base, since the resupply mass would be large, the proximity to Earth would reduce the need for recycling reliability and spares, and the launch cost would be much higher than for LEO due to the need for lunar transit and descent propulsion systems. For a ten-year lunar base, the new low launch costs make resupply cheaper than recycling systems similar to ISS life support.

launch costs↗

NASA NTRS2018

Axiomatic Design Based Analysis and Equivalent Mass Comparison of Alternate Air Revitalization Systems

A proposed Photocatalytic Air Processor (PAP) would combine two atmosphere revitalization functions for a crewed spacecraft, carbon dioxide removal and oxygen provision. The axiomatic design method is used to develop the general requirements and alternate system designs that combine these two atmosphere revitalization functions. There are two current atmosphere revitalization approaches. Short missions such as the space shuttle use lithium hydroxide (LiOH) to remove carbon dioxide and tanks to provide oxygen. The ISS (International Space Station) uses the CDRA (Carbon Dioxide Removal Assembly) to remove carbon dioxide and a Sabatier reactor and OGA (Oxygen Generation Assembly) to provide oxygen. The PAP could replace either of these combined systems, LiOH and oxygen tanks or the CDRA, Sabatier, and OGA. Axiomatic design is used to investigate these alternate high level system designs for atmosphere revitalization. The axiomatic design approach develops the requirements and design together from higher to lower system level, using a back-and-forth and top-down process. One objective is to reduce the coupling between design elements, which is a measure of system complexity. The equivalent system mass of the alternate systems is compared.

Jones, Harry W.↗

NASA NTRS2020

NASA Exploration Systems & Habitation (X-Hab)Academic Innovation Challenge 2020: Microgravity Gas/Liquid Separator for the CO2 Revitalization System Final Report

This report outlines the efforts of UNT X-Hab Team on a project titled, Microgravity Gas/Liquid Separator for the CO2 Revitalization System. The project is executed as a senior design project during academic year 2019-2020. The X-Hab 2020 Academic Innovation Challenge has selected eleven senior design teams from colleges across the US to demonstrate working prototypes for exploration systems and habitation. UNT has been tasked with the creation of a gas-liquid separator for an air revitalization system. Air revitalization technology has been used to support spaceflight by removing CO2 from enclosed systems in order to maintain breathable air. Solid sorbents such as zeolites or lithium hydroxide have been used in the past for these systems but are difficult to handle in microgravity environments and require a large amount of energy. This challenge aims to demonstrate vortex phase separator (VPS) technology for removing H2O from a CO2 stream. However, VPS technology also has the capability of using liquid sorbents for removing CO2 from an air stream. Further research could be done on liquid sorbents, such as liquid amine, in use with VPS systems. This would potentially be an alternative technology in replacing use of solid sorbents in CO2 removal systems. In 2019, NASA proposed a design that uses a gas/liquid contactor to allow for efficient contact between the two fluid phase. This was integrated into an overall CO2 removal system. The subsystems for gas-liquid separation and storage in NASA’s previous models for CO2 removal system could be replaced with a VPS. Innovative vortex separator technology is expected to allow for high throughput flow and highly efficient CO2 removal compared to other gas-liquid separation technologies. VPS relies on centripetal driven buoyancy forces to form a gas-liquid vortex within a fixed, right circular cylinder. The gas stream enters the separator through a tangential nozzle and breaks into very small bubbles (<<1 mm) resulting in a very large contact surface area for interaction with the liquid stream via energy and mass exchange. VPS technology can handle mismatches in inlet and outlet flow rates and system volume changes through the range of liquid thickness held in the separator (i.e., buffering and accumulating capability), and requires low pressure differences (<5-10 in H2O in most cases) for operation. The X-Hab 2020 team leverages these characteristics to investigate VPS technology as an alternative CO2 removal technology.

Alyssa Sarvadi↗

DOE OSTI2024

Electrolytic recovery of metals from lithium battery cathodes in moisture-tolerant molten hydroxide salt

Lithium-ion battery recycling offers an opportunity to develop innovative technologies to close the loop on the battery materials cycle and increase the resilience of the battery supply chain. Here, in this study, we demonstrate a two-step pyroelectrochemical method for producing mixed-metals from lithium-ion cathodes in a molten hydroxide salt. Mixed metal oxides in the form of insoluble lithium-ion cathode materials of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and spent lithium-ion battery materials (black mass) were electrochemically reduced to a soluble form and dissolved into a molten hydroxide salt bath. Electrochemical characterization of the process salt indicated accumulation of dissolved transition metals in the salt. A separate cathode was used to produce alloys of Ni, Mn, and Co electrochemically from the dissolved lithium-ion cathode materials. Characterization by scanning electron microscopy fitted with an energy dispersive X-ray spectrometer showed transition metals present in the cathode materials were recovered at the separate cathode. This approach represents a scalable, low temperature pyroelectrochemical process that can potentially reduce the cost and close the loop of battery cathode recycling.

25 ENERGY STORAGE↗

DOE OSTI2020

Functional Ion Pair Receptors Targeting Cesium, Lithium, Sulfate, and Uranyl (Final Technical Report)

The major goal of this project was the synthesis and study of receptors for key ions of interest to the DOE mission, namely cesium, lithium, sulfate, hydroxide, carbon dioxide/bicarbonate, and early actinides. The work, fundamental in nature, had as its objective achieving an increased understanding of how changes in receptor design could be used to optimize binding energies, ion specificity, complex structure, extraction efficiency, and substrate release. Within this broad paradigm, particular emphasis was placed on systems that could be used to sense the cesium cation in mixed aqueous media and act as extractants for the lithium cation and, separately, the carbon dioxide/bicarbonate and hydroxide anions in the form of ion pairs likely to be encountered under conditions of putative use in the field. The development of new nitrogen-rich ligands that act as receptors for early, high-valent actinide cations was also a major point of emphasis. The first in-plane actinide complexes were synthesized using a hexa-aza porphyrin analogue. The complexes exhibited an increase in the ligand–metal bonding covalency on passing from thorium(IV) to uranium(IV) to neptunium(IV) and illustrates how the use of appropriate porphyrinoid-like ligands could be used to modulate the covalency interactions between an f-element metal center and a ligand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory

The description of strongly correlated systems interacting with quantized cavity modes poses significant theoretical challenges due to the combinatorial scaling of electronic and photonic degrees of freedom. Recent advances addressing this complexity include cavity quantum electrodynamics (QED) generalizations of complete active space configuration interaction and density matrix renormalization group methods. In this work, we introduce a QED extension of state-averaged complete active space self-consistent field theory, which incorporates cavity-induced correlations through a second-order orbital optimization framework with robust convergence properties. The method is implemented using both photon number state and coherent state representations, with the latter showing robust origin invariance in the energies regardless of the completeness of the photonic Fock space. The implementation enables symmetry-free orbital relaxations to account for photon-mediated symmetry breaking in polaritonic systems. Numerical validation on lithium hydride, hydroxide anion, and magnesium hydride cation demonstrates that this method achieves significantly improved accuracy in modeling ground-state and polariton potential energy surfaces compared to QED-CASCI in a fixed orbital basis. In these studies, we reach sub-kcal/mol accuracy in potential energy surface in much smaller active spaces than are required for QED-CASCI. This advancement provides a more robust approach for studying cavity-altered chemical landscapes for ground and exited strongly coupled systems.

CASSCF↗

DOE OSTI2025

Advanced Brine Processing to Enable U.S. Lithium Independence (CRADA Report)

Current production of LiOH, which is needed to make Li-ion battery cathode active materials, utilizes a multistep process including solar evaporation, precipitation with Na 2 CO 3 and then conversion to LiOH using Ca(OH) 2 . This process requires a large amount of land area for solar evaporation, the right weather conditions, and chemicals for the conversion process that result in NaCl and CaCO 3 waste products. The production of Ca(OH) 2 is very energy intensive and evolves significant quantities of CO 2 . An alternative process flow utilizing direct lithium extraction techniques, followed by a chemical free conversion process can have benefits in reducing the needed land requirements and chemicals for traditional brine processing. There are many potential direct lithium extraction technologies that are currently being developed. The direct lithium extraction process from typical brine sources will produce a LiCl solution with some impurities including typically high concentrations of Na. This brine then needs to be converted to LiOH for use in battery cathode production. Ideally this conversion could occur without the use of additional chemicals. Electrochemistry can do this conversion either via electrolysis or bipolar membrane electrodialysis (BPED) to produce LiOH and HCl in solution. BPED utilized bipolar membranes to split water, which has a reduced potential as compared to splitting water at electrodes into hydrogen and oxygen gas. This reduced potential required results in a significant energy savings for BPED over electrolysis methods. This CRADA project aimed to develop such an integrated process using direct lithium extraction followed by BPED to produce a LiOH solution. That solution can then be crystallized into battery grade LiOH. In particular, Albemarle utilized a direct lithium extraction process to produce a concentrated LiCl solution that could be used for the BPED process. The BPED process was first tested using various LiCl solutions with impurity ions added at bench scale to understand the effects of impurities and determine processing parameters. Then testing was performed using the direct lithium extracted brine at the bench scale before scaling the process up. After the process was scaled up a long duration test was carried out to estimate the lifetime of the membranes, which is key to the economics of the BPED process.

25 ENERGY STORAGE↗

NASA NTRS1974

The synthesis of higher oxides of alkali and alkaline earth metals in an electric discharge: Theoretical and experimental studies

Potassium hydroxide was subjected to the products of an electrical discharge sustained in oxygen and produced both potassium peroxide and superoxide. The conversion to higher oxides was shown to strongly depend upon the particle size of KOH, the position of KOH in the discharge zone, and the operating conditions of the discharge. Similar experiments were performed with hydroxides of lithium and calcium which do not form superoxides, but are converted to peroxides. The yields of peroxides were shown to strongly depend upon the operating conditions of the discharge. The absence of superoxides and the presence of peroxides of lithium and calcium was explained from the consideration of relative thermodynamic stability of the oxides of lithium and calcium. Thermogravimetric analysis was shown to provide a more accurate means for determining the amount of KO2 than previous methods.

Bell, A. T.↗

DOE OSTI2023

Integrated Circular Economy Model System for Direct Lithium Extraction: From Minerals to Batteries Utilizing Aluminum Hydroxide

Aluminum hydroxide, an abundant mineral found in nature, exists in four polymorphs: gibbsite, bayerite, nordstrandite, and doyleite. Among these polymorphs gibbsite, bayerite, and commercially synthesized amorphous aluminum hydroxide have been investigated as sorbent materials for lithium extraction from sulfate solutions. The amorphous form of Al(OH) 3 exhibits a reactivity higher than that of the naturally occurring crystalline polymorphs in terms of extracting Li + ions. This study employed high-temperature oxide melt solution calorimetry to explore the energetics of the sorbent polymorphs. The enthalpic stability order was measured to be gibbsite > bayerite > amorphous Al(OH) 3 . The least stable form, amorphous Al(OH) 3 , undergoes a spontaneous reaction with lithium, resulting in the formation of a stable layered double hydroxide phase. Consequently, amorphous Al(OH) 3 shows promise as a sorbent material for selectively extracting lithium from clay mineral leachate solutions. Further, this research demonstrates the selective direct extraction of Li + ions using amorphous aluminum hydroxide through a liquid–solid lithiation reaction, followed by acid-free delithiation and relithiation processes, achieving an extraction efficiency of 86%, and the maximum capacity was 37.86 mg·g –1 in a single step during lithiation. With high selectivity during lithiation and nearly complete recoverability of the sorbent material during delithiation, this method presents a circular economy model. Furthermore, a life cycle analysis was conducted to illustrate the environmental advantages of replacing the conventional soda ash-based precipitation process with this method, along with a simple operational cost analysis to evaluate reagent and fuel expenses.

25 ENERGY STORAGE↗

DOE OSTI2023

Effect of Anions on the Delithiation of [Li–Al] Layered Double Hydroxides: Thermodynamic Insights

The utilization of lithium aluminum [Li–Al] layered double hydroxides (LDHs) is explored for direct lithium extraction (DLE) from geothermal brines and minerals. Following extraction, the Li + ions need to be removed from the LDH structure and converted into LiOH or Li 2 CO 3 products, making them suitable for battery applications. The research investigates the delithiation of [Li–Al-X] LDHs (where X = Cl – , OH – , and SO 4 2– ), which were synthesized and dried under different conditions. Herein the study aims to understand how the choice of anions and drying conditions affects the delithiation process. To determine the stability of these [Li–Al] LDHs, high-temperature oxide melt solution calorimetry is employed. The results reveal that the stability of LDHs varies significantly based on postdrying conditions, anion choice, and the water content in the interlayer. The order of stability, as indicated by the enthalpy of formation values, is found to be OH-LDH-O > OH-LDH-A > SO 4 -LDH-O > SO4-LDH-A > Cl-LDH-O > Cl-LDH-A. This trend is attributed to the interactions among the interlayer species and the metal hydroxide layers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗