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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Data-driven search for promising intercalating ions and layered materials for metal-ion batteries

The rise in demand for lithium-ion batteries has led to a large-scale search for electrode materials and intercalating ion species to meet the demands of next-generation energy technologies. Recent efforts largely focus on searching for cathodes that can accommodate large amounts of intercalating ions, but similar work on anodes is relatively limited. This study utilizes machine learning methods to find alternative two-dimensional (2D) materials and intercalating ions beyond Li for metal-ion batteries with high-power efficiencies. The approach first uses density functional theory (DFT) calculations to estimate the theoretical capacities and voltages of various metal ions on 2D materials. The DFT-generated data also provide insights into the local structural accommodation upon ion intercalation on various 2D materials. Significant changes to the lattice can result in irreversible changes to the bonding environments in the anode material, resulting in poor cycling stability. Next, this study develops a binding energy and structural accommodation-based classification model to screen anode materials for next-generation batteries. The classification model selects intercalating ions and 2D material pairs suitable for batteries based on the calculated voltage and volumetric changes in the 2D material upon intercalation. Finally, this study builds a regression model to accurately predict the binding energies of the various intercalating ions on 2D materials. The approach highlights the importance of different elemental and structural features for classification and regression tasks. In conclusion, the insights gained from this study on the role of involved features, such as electronegativities of the constituent ions and the presence of unfilled electronic levels, will help to streamline further studies towards the search for future layered battery materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Understanding and Strategies for Controlled Interfacial Phenomena in Lithium-Ion Batteries and Beyond

Electrolyte chemistry and properties and electrode structure and chemical properties particularly at the interfaces are crucial for the development of advanced battery components. This project focused on elucidating the roles of the electrolyte and electrode on the formation and evolution of the SEI layer and cell electrochemical performance on silicon and on Li metal anodes. For Si nano/microstructures we evaluated lithiation, volume changes, reactivity, and chemo-mechanical transformations as functions of nanoparticle size, shape, presence of coatings, electrolyte composition, electron leakage to the electrolyte, and cycling. For Li metal anodes we provided detailed analyses of the electrode and electrolyte effects on interfacial reactivity and as a function of microstructural evolution and underlying stochasticity as dendrites nucleate and grow. We thoroughly investigated and simulated how the chemistry of the various components of the electrolyte and the electrode architecture may affect the electrochemical reactions as well as cell degradation. A multiscale modeling approach was utilized, where atomistic simulations informed about the microscopic behavior of the system, and intermediate time and length scales were investigated with mesoscopic models. Results were also tested against selected experiments from our collaborators. The combined theoretical-experimental strategy saves costs by utilizing predictions from computational analyses to guide experimentation.

25 ENERGY STORAGE↗
DOE OSTI2024

Impact of Mg Substitution on the Structure, Stability, and Properties of the Na 2 Fe 2 F 7 Weberite Cathode

Of the few weberite-type Na-ion cathodes explored to date, Na 2 Fe 2 F 7 exhibits the best performance, with capacities up to 184 mAh/g and energy densities up to 550 Wh/kg reported for this material. However, the development of robust structure–property relationships for this material is complicated by its tendency to form as a mixture of metastable polymorphs, and transform to a lower-energy Na y FeF 3 perovskite compound during electrochemical cycling. Our first-principles-guided exploration of Fe-based weberite solid solutions with redox-inactive Mg 2+ and Al 3+ predicts an enhanced thermodynamic stability of Na 2 Mg x Fe 2–x F 7 as the Mg content is increased, and the x = 0.125 composition is selected for further exploration. We demonstrate that the monoclinic polymorph (space group C2/c) of Na 2 Fe 2 F 7 (Mg0) and of a new Mg-substituted weberite composition, Na 2 Mg 0.125 Fe 1.875 F 7 (Mg0.125), can be isolated using an optimized synthesis protocol. The impact of Mg substitution on the stability of the weberite phase during electrochemical cycling, and on the extent and rate of Na (de)intercalation, is examined. Irrespective of the Mg content, we find that the weberite phase is retained when cycling over a narrow voltage window (2.8–4.0 V vs Na/Na+). Over a wider voltage range (1.9–4.0 V), Mg0 shows steady capacity fade due to its transformation to the NayFeF3 perovskite phase, while Mg0.125 displays more reversible cycling and a reduced phase transformation. Yet, Mg incorporation also leads to kinetically limited Na extraction and a reduced overall capacity. These findings highlight the need for the continued compositional optimization of weberite cathodes to improve their structural stability while maximizing their energy density.

25 ENERGY STORAGE↗
NASA NTRS1992

Elemental Analyses of Hypervelocity Microparticle Impact Sites on Interplanetary Dust Experiment Sensor Surfaces

The Interplanetary Dust Experiment (IDE) had over 450 electrically active ultra-high purity metal-oxide-silicon impact detectors located on the six primary sides of the Long Duration Exposure Facility (LDEF). Hypervelocity microparticles (approximately 0.2 to approximately 100 micron diameter) that struck the active sensors with enough energy to breakdown the 0.4 or 1.0 micron thick SiO2 insulator layer separating the silicon base (the negative electrode), and the 1000 A thick surface layer of aluminum (the positive electrode) caused electrical discharges that were recorded for the first year of orbit. The high purity Al-SiO2-Si substrates allowed detection of trace (ppm) amounts of hypervelocity impactor residues. After sputtering through a layer of surface contamination, secondary ion mass spectrometry (SIMS) was used to create two-dimensional elemental ion intensity maps of microparticle sites on the IDE sensors. The element intensities in the central craters of the impacts were corrected for relative ion yields and instrumental conditions and then normalized to silicon. The results classification resulted from the particles' origins as 'manmade', 'natural', or 'indeterminate'. The last classification resulted from the presence of too little impactor residue, analytical interference from high background contamination, the lack of information on silicon and aluminum residues, or a combination of these circumstances. Several analytical 'blank' discharges were induced on flight sensors by pressing down on the sensor surface with a pure silicon shard. Analyses of these blank discharges showed that the discharge energy blasts away the layer of surface contamination. Only Si and Al were detected inside the discharge zones, including the central craters, of these features. Thus far, a total of 79 randomly selected microparticle impact sites from the six primary sides of the LDEF were analyzed: 36 from tray C-9 (Leading (ram), or east, side), 18 from tray C-3 (Trailing (wake), or west, side), 12 from tray B-12 (north side), 4 from tray D-6 (south side), 3 from tray H-11 (space end), and 6 from tray G-10 (earth end). Residue from manmade debris was identified in craters on all trays (aluminum oxide particle residues were not detectable on the Al/Si substrates). These results were consistent with the IDE impact record which showed highly variable long term microparticle impact flux rates on the west, space, and Earth sides of the LDEF which could not be ascribed to astronomical variability of micrometeorite density. The IDE record also showed episodic bursts of microparticle impacts on the east, north, and south sides of the satellite, denoting passage through orbital debris clouds or rings.

Simon, C. G.↗
NASA NTRS1993

Elemental analyses of hypervelocity microparticle impact sites on Interplanetary Dust Experiment sensor surfaces

The Interplanetary Dust Experiment (IDE) had over 450 electrically active ultra-high purity metal-oxide-silicon impact detectors located on the six primary sides of the Long Duration Exposure Facility (LDEF). Hypervelocity microparticles (approximately 0.2 to approximately 100 micron diameter) that struck the active sensors with enough energy to break down the 0.4 or 1.0 micron thick SIO2 insulator layer separating the silicon base (the negative electrode), and the 1000 A thick surface layer of aluminum (the positive electrode) caused electrical discharges that were recorded for the first year of orbit. The high purity Al-SiO2-Si substrates allowed detection of trace (ppm) amounts of hypervelocity impactor residues. After sputtering through a layer of surface contamination, secondary ion mass spectrometry (SIMS) was used to create two-dimensional elemental ion intensity maps of microparticle impact sites on the IDE sensors. The element intensities in the central craters of the impacts were corrected for relative ion yields and instrumental conditions and then normalized to silicon. The results were used to classify the particles' origins as 'manmade,' 'natural,' or 'indeterminate.' The last classification resulted from the presence of too little impactor residue, analytical interference from high background contamination, the lack of information on silicon and aluminum residues, or a combination of these circumstances. Several analytical 'blank' discharges were induced on flight sensors by pressing down on the sensor surface with a pure silicon shard. Analyses of these blank discharges showed that the discharge energy blasts away the layer of surface contamination. Only Si and Al were detected inside the discharge zones, including the central craters of these features. Thus far a total of 79 randomly selected microparticle impact sites from the six primary sides of the LDEF have been analyzed: 36 from tray C-9 (Leading (ram), or East, side), 18 from tray C-3 (Trailing (wake), or West, side), 12 from tray B-12 (North side), 4 from tray D-6 (South side), 3 from tray H-11 (Space end), and 6 from tray G-10 (Earth end). Residue from manmade debris was identified in craters on all trays. (Aluminum oxide particle residues were not detectable on the Al/Si substrates.) These results were consistent with the IDE impact record which showed highly variable long term microparticle impact flux rates on the West, Space and Earth sides of the LDEF which could not be ascribed to astronomical variability of micrometeorite density. The IDE record also showed episodic bursts of microparticle impacts on the East, North, and South sides of the satellite, denoting passage through orbital debris clouds or rings.

Simon, Charles G.↗
DOE OSTI2026

Interfacial Chemistry Involved in Selective Separation of NMC/LMO and LCO/LMO Binary Cathode Materials by Froth Flotation Using Oleic Acid

The variability in cathode compositions within recycled lithium-ion battery (LIB) feedstocks poses a significant challenge to efficient downstream refining processes. This study demonstrates the feasibility of using froth flotation with oleic acid as a collector to selectively separate lithium nickel-manganese-cobalt oxide (NMC) and lithium cobalt oxide (LCO) from lithium manganese oxide (LMO) materials. Laboratory-scale flotation tests achieved an 80% separation efficiency in a single stage, producing a froth product with >90% purity of NMC/LCO at approximately 90% yield. Concurrently, the LMO materials were enriched in the sink product with ∼90% purity and ∼90% yield. This approach was further validated using recycled cathode materials, confirming its applicability to realistic feedstocks. The underlying mechanism governing the selective separation of NMC/LCO from LMO was investigated using ζ-potential measurements, contact angle measurements, bubble-particle attachment experiments, and X-ray photoelectron spectroscopy (XPS) analysis. Both contact angle and bubble-particle attachment results confirmed that oleic acid adsorption rendered NMC and LCO surfaces hydrophobic, thereby enhancing flotation recovery. At pH 5, oleic acid adsorbed preferentially onto NMC and LCO surfaces via electrostatic interactions, while exhibiting minimal adsorption on LMO surfaces. However, separation efficiency deteriorated at higher pH, which was attributed to the co-flotation of LMO materials caused by oleate chemisorption on MnOH + species. This work establishes froth flotation as a viable cathode/cathode separation strategy, providing a low-cost, scalable pathway to preconcentrate and enrich nickel-rich and cobalt-rich cathode active materials from incompatible cathode chemistries for direct recycling or hydrometallurgical processing. Furthermore, this study reveals, for the first time, the mechanism of oleate adsorption on the surface of different cathode materials.

PH↗
NASA NTRSDate not supplied

Considerations on Electrolytic Conductivity Measurement for Monitoring of Ionic Silver Biocide Dosing

NASA interest in ionic silver (Ag+) as a biocide for spacecraft potable water systems motivates the development of Ag+ concentration sensors to ensure nominal dosing. The electrolytic conductivity change of highly-purified potable water is linearly related to the concentration of chemically-dosed Ag+ and could serve as a useful proxy measurement, while the conductivity change during electrolytic dosing may be less so, depending on the influent water chemistry and electrolytic efficiency. Understanding and mitigating the potentially deleterious effects of Ag+ interaction with conductivity measurement systems requires investigation. Issues associated with traditional conductivity cells, which rely on wetted(typically metal or graphite) electrodes, and capacitively-coupled contactless conductivity detection (C4D) for this application are considered. Traditional conductivity cells may potentially be subject to significant excitation-induced or auto-galvanic reduction of Ag+. These may result in Ag+ depletion or electrode fouling and associated measurement error. Proper selection of electrode material, excitation parameters, and cell geometry may limit such effects. C4D uses electrodes placed outside an inert, insulating material, with dielectric polarization enabling the production of an electric field and resultant current across the analyte solution. This approach could potentially mitigate problems with Ag+ depletion and fouling by eliminating the possibility of auto-galvanic deposition and reducing the Faradaic current density. However, it is necessary to confirm C4D performance at very low conductivity levels and to determine if long-term operation produces conductive deposits, which could result in measurement error. A commercial C4D system with 1/16” (1.59 mm)outer diameter flow tubing and claimed performance in the conductivity range appropriate for this application was identified, and its sensitivity in the upper parts of this range was confirmed in a preliminary experiment. A concept for a C4D detector that could allow for full rate flow-through using planar electrodes and thin-film dielectric layers is discussed.

silver↗
DOE OSTI2023

Electrolyte Reactivity on the MgV 2 O 4 Cathode Surface

Predictive understanding of the solvation-dependent reactivity and molecular interaction of electrolyte ions and solvent molecules on reactive electrodes has been a major challenge but is essential for addressing instabilities and surface passivation that occur at electrode-electrolyte interface (EEI) of multivalent Mg batteries. In this work, the isolated intrinsic reactivities of prominent chemical species present in magnesium bis(trifluoromethanesulfonimide) (Mg(TFSI) 2 ) in diglyme (G2) electrolytes, including ionic (TFSI - , [Mg(TFSI)] + , [Mg(TFSI):G2] + , [Mg(TFSI):2G2] + ) as well as neutral molecules (G2) on magnesium vanadate cathode (MgV 2 O 4 ) surface has been studied using a combination of first-principles calculations and multimodal analysis of well-defined cathode electrolyte interphase (CEI) layers. Here, our calculations show that non-solvated [Mg(TFSI)] + is the strongest adsorbing species on the MgV 2 O 4 surface compared to all other ions while fully solvated [Mg(TFSI):2G2] + are least favorable to decomposition. The cleavage of C-S bonds in TFSI - to form CF 3 - is predicted to be most desired pathway for all ionic species, which is followed by the cleavage of C-O bonds of G2 to yield CH 3 + or OCH 3 - species. The strong stabilization and electron transfer between ionic electrolyte species and MgV 2 O 4 is found to significantly favor these decomposition reactions on the surface compared to intrinsic gas phase dissociation. Experimentally, we used state-of-the-art ion soft landing to selectively deposit mass-selected TFSI - , [Mg(TFSI):G2] + and [Mg(TFSI):2G2] + on MgV 2 O 4 thin film to form well-defined electrolyte-MgV 2 O 4 interface. Analysis of soft-landed interphase using X-ray photoelectron, X-ray absorption near edge structure, electron energy-loss spectroscopies as well as transmission electron microscopy confirmed the presence of decomposition species (e.g., MgFx, carbonates) formed in the interfacial region and the higher amount of MgFx with [Mg(TFSI):G2] + , which corroborates the theoretical observation. Overall, we established the mechanistic pathway for the electrolyte-induced formation of passivating fluorides on MgV 2 O 4 cathode facilitated by the surface adsorption and charge transfer, which provided essential knowledge for rational design of stable electrolytes for multivalent cathodes.

Cathode-electrolyte interphase formation↗
NASA NTRS1994

The NASA-JPL advanced propulsion program

The NASA Advanced Propulsion Concepts (APC) program at the Jet Propulsion Laboratory (JPL) consists of two main areas: The first involves cooperative modeling and research activities between JPL and various universities and industry; the second involves research at universities and industry that is directly supported by JPL. The cooperative research program consists of mission studies, research and development of ion engine technology using C-60 (Buckminsterfullerene) propellant, and research and development of lithium-propellant Lorentz-force accelerator (LFA) engine technology. The university/industry- supported research includes research (modeling and proof-of-concept experiments) in advanced, long-life electric propulsion, and in fusion propulsion. These propulsion concepts were selected primarily to cover a range of applications from near-term to far-term missions. For example, the long-lived pulsed-xenon thruster research that JPL is supporting at Princeton University addresses the near-term need for efficient, long-life attitude control and station-keeping propulsion for Earth-orbiting spacecraft. The C-60-propellant ion engine has the potential for good efficiency in a relatively low specific impulse (Isp) range (10,000 - 30,000 m/s) that is optimum for relatively fast (less than 100 day) cis-lunar (LEO/GEO/Lunar) missions employing near-term, high-specific mass electric propulsion vehicles. Research and modeling on the C-60-ion engine are currently being performed by JPL (engine demonstration), Caltech (C-60 properties), MIT (plume modeling), and USC (diagnostics). The Li-propellant LFA engine also has good efficiency in the modest Isp range (40,000 - 50,000 m/s) that is optimum for near-to-mid-term megawatt-class solar- and nuclear-electric propulsion vehicles used for Mars missions transporting cargo (in support of a piloted mission). Research and modeling on the Li-LFA engine are currently being performed by JPL (cathode development), Moscow Aviation Institute (engine testing), Thermacore (electrode development), as well as at MIT (plume modeling), and USC (diagnostics). Also, the mission performance of a nuclear-electric propulsion (NEP) Li-LFA Mars cargo vehicle is being modeled by JPL (mission analysis; thruster and power processor modeling) and the Rocketdyne Energy Technology and Engineering Center (ETEC) (power system modeling). Finally, the fusion propulsion research activities that JPL is supporting at Pennsylvania State University (PSU) and at Lawrenceville Plasma Physics (LPP) are aimed at far-term fast (less than 100 day round trip) piloted Mars missions and, in the very far term, interstellar missions.

Frisbee, Robert H.↗
DOE OSTI2023

Bipolar Membrane Capacitive Deionization for pH-Assisted Ionic Separations

Selective ionic separations represent an increasingly important technical area for the strategic interests of the U.S. economy–for example, securing critical minerals and materials and circular economy aspirations that include recovering organic acids from processed biomass. This work disseminates bipolar membrane (BPM) capacitive deionization for selective ionic separations from multicomponent, ionic species mixtures. The selective separations are guided by the Pourbaix diagram and acid–base equilibria principles. BPM capacitive deionization was demonstrated to generate alkaline or acidic process streams depending upon the location of the BPM in the electrochemical cell. The role of system operating parameters, such as the cell voltage, residence time, and feed concentration on effluent stream pH was studied. It was observed that the pH adjustment in BPM-CDI/MCDI (MCDI, membrane capacitive deionization) was more sensitive to the cell voltage when compared to the process stream residence time and salt feed concentration. The BPM-MCDI gave over 6 times higher percentage of copper(II) removal when compared to sodium ion removal from brine mixtures. Lastly, BPM-MCDI demonstrated over 40% greater removal for copper ions from brine mixtures and fivefold higher removal for itaconic acid from brine mixtures when benchmarked against a traditional flow-by-MCDI setup.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

Redox reactions of uranium (U) in aqueous environments have important impacts on the mobility and isotopic fractionation of U in the geosphere. Pentavalent U as the cationic uranyl ion, UO 2 +, is rarely observed in naturally occurring samples because of its limited lifetime, but it may be an important intermediate state controlling the redox kinetics between hexavalent and tetravalent U. Increasing evidence has indicated that U(V) can be stabilized under laboratory conditions. Here, we showed that U(V) is the dominant species on the magnetite (Fe 3 O 4 ) surface under reducing conditions controlled by electrochemical methods. Cyclic voltammetry reveals coupled redox peaks corresponding to the U(VI)O 2 2+ /U(V)O 2+ one-electron redox reaction. Magnetite electrodes polarized at a series of potentials to reduce U(VI)O 2 2+ were characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and Auger electron mapping. Overall, the results showed that up to twice the amount of U(V) to U(VI) was present on the magnetite surface. U(V) adopted a typical uranyl-type structure, and the U coverage on the magnetite surface increased with decreasing potentials. The formation of mixed-valence U(V)/U(VI) species on the surface of magnetite may hinder the U(V) disproportionation reaction, thereby eliminating the presence of tetravalent U. These results show that U(V) can exist over short time scales as the dominant U species on mineral surfaces under selected reducing conditions by the controlled polarization of a mineral electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Entropy-Stabilized Multication Fluorides as a Conversion-Type Cathode for Li-Ion Batteries–Impact of Element Selection

Metal fluorides (e.g., FeF 2 and FeF 3 ) have received attention as conversion-type cathode materials for Li-ion batteries due to their higher theoretical capacity compared to that of common intercalation materials. However, their practical use has been hindered by low round-trip efficiency, voltage hysteresis, and capacity fading. Cation substitution has been proposed to address these challenges, and recent advancements in battery performance involve the introduction of entropy stabilization in an attempt to facilitate reversible conversion reactions by increasing configurational entropy. Building on this concept, high entropy fluorides with five cations were synthesized by using a simple mechanochemical route. In order to examine the impact of element selection, Co 0.2 Cu 0.2 Ni 0.2 Zn 0.2 Fe 0.2 F 2 (HEF-Fe) was compared with Co 0.2 Cu 0.2 Ni 0.2 Zn 0.2 Mg 0.2 F 2 (HEF-Mg), replacing electrochemically inactive Mg with Fe as an active participant in the conversion reaction. Combining electrochemical measurements with first-principles calculations, high-resolution electron microscopy, and synchrotron X-ray analysis, HEFs’ battery performances and conversion reaction mechanisms were investigated in detail. The results highlighted that replacement of Mg with Fe was beneficial, with enhanced capacity, rate capability, and surface stability. In addition, it was found that HEF-Fe showed similar cycle stability without an electrochemically inactive element. In conclusion, these findings provide valuable insights for the design of high entropy multielement fluorides for improved Li-ion battery performance.

25 ENERGY STORAGE↗
DOE OSTI2023

Enhancing the Electrode Gravimetric Capacity of Li 1.2 Mn 0.4 Ti 0.4 O 2 Cathode Using Interfacial Carbon Deposition and Carbon Nanotube-Mediated Electrical Percolation

Mn-based cation disordered rocksalt oxides (Mn-DRX) are emerging as promising cathode materials for next-generation Li-ion batteries due to their high specific capacities and cobalt and nickel free characteristic. However, to reach the theoretical capacity, solid-state method synthesized Mn-DRX materials require activation via post-synthetic ball milling, typically incorporating more than 20 wt.% conductive carbon that adversely reduces the electrode level gravimetric capacity. To solve this issue, we firstly deposit amorphous carbon on the surface of the Li 1.2 Mn 0.4 Ti 0.4 O 2 (LMTO) particles to increase the electrical conductivity by a five order of magnitude. Although the cathode material gravimetric first charge capacity reaches 180 mAh/g, its highly irreversible behavior leads to a 70 mAh/g first discharge capacity. Subsequently, to ensure a good electrical percolation network, the LMTO material is ball milled with multi-wall carbon nanotube (CNT) to obtain a 78.7 wt.% LMTO active material loading in the cathode electrode (LMTO-CNT). As a result, a 210 mAh/g cathode electrode gravimetric first charge and 165 mAh/g first discharge capacity are obtained, compared to the respective capacity values of 222 mAh/g and 155 mAh/g for the LMTO ball milled with 20 wt.% SuperP C65 electrode (LMTO-SP). After 50 cycles, the LMTO-CNT delivers a 121 mAh/g electrode gravimetric discharge capacity, largely outperforming the 44 mAh/g value of the LMTO-SP. In conclusion, our study demonstrates that while ball milling is necessary to achieve the theoretical capacity of LMTO, a careful selection of the additive, such as CNT, effectively reduces the required carbon quantity to achieve a higher electrode gravimetric discharge capacity.

25 ENERGY STORAGE↗
DOE OSTI2024

A Comparative Study of Degradation Behaviors of LiFePO 4 , LiMn 2 O 4 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 in Different Aqueous Electrolytes

Aqueous Li-ion batteries (ALIBs) are an important class of battery chemistries owing to the intrinsic non-flammability of aqueous electrolytes. However, water is detrimental to most cathode materials and could result in rapid cell failure. Identifying the degradation mechanisms and evaluating the pros and cons of different cathode materials are crucial to guide the materials selection and maximize their electrochemical performance in ALIBs. Here, in this study, we investigate the stability of LiFePO 4 (LFP), LiMn 2 O 4 (LMO) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC) cathodes, without protective coating, in three different aqueous electrolytes, i.e., salt-in-water, water-in-salt, and molecular crowding electrolytes. The latter two are the widely reported "water-deficient electrolytes." LFP cycled in the molecular crowding electrolyte exhibits the best cycle life in both symmetric and full cells owing to the stable crystal structure. Mn dissolution and surface reduction accelerate the capacity decay of LMO in water-rich electrolyte. On the other hand, the bulk structural collapse leads to the degradation of NMC cathodes. LMO demonstrates better full-cell performance than NMC in water-deficient aqueous electrolytes. LFP is shown to be more promising than LMO and NMC for long-cycle-life ALIB full cells, especially in the molecular crowding electrolyte. However, none of the aqueous electrolytes studied here provide enough battery performance that can compete with conventional non-aqueous electrolytes. This work reveals the degradation mechanisms of olivine, spinel, and layered cathodes in different aqueous electrolytes and yields insights into improving electrode materials and electrolytes for ALIBs.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu 3-a Sb 1+b S 4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g -1 obtained at a scan rate of 5 mV s -1 . Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Redox-Active Crown Ether Copolymer for Selective Lithium Recovery from Spent Lithium-Ion Batteries

The increasing demand for lithium, alongside concerns over resource scarcity and supply chain risks, has driven the need for alternative lithium sources, particularly from spent lithium-ion batteries (LIBs). Here, in this work, we introduce a redox-active crown ether copolymer designed for highly selective and electrochemically reversible lithium recovery from organic LIB leachates. A lithium-selective moiety, (12-crown-4)methyl methacrylate (12C4MA), is combined with a redox-active moiety, ferrocenylpropyl methacrylamide (FPMAm), into a redox copolymer electrosorbent to replace acid-based regeneration with electrostatic repulsion. The redox response enhances lithium ingress into the polymer, doubling lithium uptake (0.58 mol Li /mol CrE ) and enabling electrochemical regeneration upon the FPMAm oxidation. Our system exhibits exclusive lithium uptake, even in complex leachates containing competing metals (e.g., iron, nickel, and cobalt) and organic degradants. Techno-economic analysis highlights high energy efficiency and competitive lithium pricing to the market value (∼$12.7 per kg Li ). Overall, our work demonstrates a scalable, electrified adsorbent platform for sustainable and chemical-free critical metal recovery.

adsorption↗
DOE OSTI2026

Lattice-Oxygen-Driven Selective Oxidation Strategy for Stable Argyrodite Solid-State Lithium Metal Batteries

All-solid-state lithium metal batteries (ASSLMBs) with Li6PS5Cl argyrodite electrolytes and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes offer high energy density but suffer from rapid capacity fading due to the layered-to-rock-salt transition of NMC811 and structural degradation of Li6PS5Cl from parasitic interfacial reactions. Here, we demonstrate a catholyte engineering strategy using a Li2S scavenging additive to suppress interfacial reactivity and preserve the structural and electrochemical stability of both NMC811 and Li6PS5Cl. Incorporating 0.10 wt.% Li2S enables exceptional cycling stability, achieving 76% capacity retention after 550 cycles at C/10 and 88% retention after 800 cycles at C/3 at 60 degrees C, compared with rapid failure in pristine cells. Spectroscopic, electrochemical, and morphological analyses confirm that Li2S maintains electrode integrity by sustaining particle contact and suppressing phase decomposition. This work elucidates interfacial degradation pathways in NMC811/argyrodite systems and introduces a low-cost, scalable strategy to stabilize nickel-rich oxide cathodes in ASSLMBs, advancing their practical viability.

25 ENERGY STORAGE↗
DOE OSTI2025

Enabling Solar Water Oxidation by BiVO 4 in Strongly Acidic Solutions

The oxygen evolution reaction (OER) is paired with various electrochemical and photoelectrochemical reduction reactions used for fuel and chemical production. As there is a strong interest in performing many of these reduction reactions in strongly acidic solutions to increase the reaction rate, efficiency, or selectivity, there is also a great interest in enabling efficient and stable OER in strongly acidic solutions. In this study, we report stable photoelectrochemical OER (POER) of a BiVO 4 photoanode in 0.1 M HNO 3 (pH 1). This was achieved by using Nb 2 O 5 as a protection layer. While Nb 2 O 5 was rarely used as a protection layer for photoelectrodes in the past, we show its excellent capability to suppress both the chemical and photoelectrochemical dissolution of BiVO 4 at pH 1. After stabilizing BiVO 4 with a Nb 2 O 5 protection layer, we added Co 2+ ions to the electrolyte as an OER catalyst to enhance the POER. We found that Co (aq) 2+ can serve as a homogeneous OER catalyst without being deposited as a CoO x solid catalyst on Nb 2 O 5 . When we performed the POER using unprotected BiVO 4 with Co (aq) 2+ under the same condition, although POER was enhanced, the enhancement could not be sustained due to the chemical dissolution of BiVO 4 . After the POER, we found that a Co 3+ -containing OER catalyst was deposited on the bare BiVO 4 surface. This result suggested that the use of Co 2+ ions as a homogeneous catalyst was possible due to the inertness of the Nb 2 O 5 surface toward the adsorption or deposition of Co ions. This study enabling stable POER of BiVO 4 in 0.1 M HNO 3 using the combination of a Nb 2 O 5 protection layer and Co (aq) 2+ as a homogeneous OER catalyst provides promising possibilities for acidic POER and OER.

Catalysts↗