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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Purification of U from U-10Mo scrap generated during the fabrication of high performance research reactor fuel

A low enriched U-Mo alloy fuel is under development to replace highly enriched U fuels currently used in United States high performance research reactors. The alloy casting and fuel fabrication processes will generate scrap streams containing low enriched U (LEU) which must be recovered. Solvent extraction processes were designed using the Argonne Model for Universal Solvent Extraction (AMUSE) to purify solutions containing 20 and 50 g/L U. The feed for the solvent extraction processes was prepared from solutions generated from the dissolution of U-10Mo-Zr foils and U-10Mo-Zr-Al mini-plates. The U purification processes were demonstrated using two, 16-stage banks of miniature mixer-settlers. The solvent extraction experiments demonstrated that all design objectives for the U purification processes could be met. The U recovery in the product stream for each flowsheet was ≥99.9%. The flowsheet demonstrations also showed that the purity of the U Product will meet the requirements of the ASTM International C1462-21 specification for LEU metal enriched to less than 20% 235 U. In conclusion, the AMUSE modeling for both flowsheet demonstrations was validated by comparing predicted and measured concentrations of U, Mo, and Zr in the exit streams and stage samples at steady-state conditions in the mixer-settlers.

modified PUREX process↗
DOE OSTI2026

Compatibility of Type 304H Stainless Steel in Static Molten FLiBe for Inertial Confinement Fusion Reactors: Role of Impurities and Redox Control

Molten fluoride salts, such as FLiBe (LiF-BeF2), are promising candidates for tritium breeding and heat transfer in fusion reactors, but corrosion of structural materials remains a major challenge. This study investigates the corrosion behavior of austenitic stainless steel 304H in purified and NiF2-containing FLiBe at 500°C and 600°C, focusing on the effects of impurities and redox control. Exposure to purified FLiBe resulted in the concurrent depletion of Cr, Mn, and Fe, with corrosion at 500 °C dominated by the combined oxide formation and elemental dissolution, while at 600°C elemental depletion was predominant. The addition of a controlled NiF2 impurity significantly accelerated corrosion at both temperatures, demonstrating the sensitivity of 304H to the salt redox state. Beryllium additions were effective in mitigating corrosion for both baseline and NiF2-containing FLiBe; minimal depletion of Cr, Mn, and Fe occurred with Be additions as low as 2.5 mg (147 wppm), and no NiBe intermetallics formed at 5 mg (294 wppm), indicating that small Be inventories can provide substantial protection without deleterious phase formation. Thermodynamic equilibrium and coupled thermodynamic-kinetic analyses at the salt-alloy interface suggested low corrosion rates in systems with limited hydrogen fluoride (HF) generation, highlighting the importance of salt redox control. Estimates for a Be addition rate were calculated for the HYLIFE-II fusion reactor that can mitigate corrosion-induced degradation, assuming complete conversion of tritium to tritium fluoride (TF). Overall, 304H shows reasonable compatibility with FLiBe under optimized redox conditions. These results provide quantitative guidance for material selection and salt management in fusion blanket and heat exchanger systems and motivate validation under flowing, nonisothermal, and irradiated conditions.

Pillai, Rishi [ORNL] (ORCID:0000000243688197)↗
DOE OSTI2024

Soil management practices can contribute to net carbon neutrality in California

Stabilizing climate requires reducing greenhouse gas (GHG) emissions and storing atmospheric carbon dioxide (CO 2 ) in land or ocean systems. Soil management practices can reduce GHG emissions or sequester atmospheric CO 2 into inorganic and organic forms. However, whether soil carbon strategies represent a viable and impactful climate mitigation pathway is uncertain. A specific question concerns the role that land-management practices and soil amendments can play in realizing California's ambition for carbon neutrality by 2045. Here we examine the carbon flux impacts of soil conservation (i.e., compost, reduced tillage, cover crop) and enhanced silicate rock weathering (EW) practices at different areal extents of implementation in cropland, grassland, and savanna in California under two climate change cases. We show that with implementation areas of 15% or 50% of private cultivated land, grassland, and savanna in California, soil conservation practices alone can contribute $1.4^{2.1}_{0.7}$% ($-1.8^{-2.7}_{ -0.9}$ Mt CO 2 eq y -1 ) and $4.6^{6.9}_{2.3}$% ($-6.0^{-8.9}_{-3.0}$ Mt CO 2 eq y -1 ) of the additional emissions reduction needed (beyond previous targets) to meet the 2045 net neutrality goal (-129.3 Mt CO 2 eq y -1 ), respectively, on an average annual basis, including climate uncertainty. Including EW in these scenarios increases the total contributions of management practices to $4.1^{5.6}_{2.5}$% ($-5.2^{-7.3}_{-3.2}$ Mt CO 2 eq y -1 ) and $13.5^{18.6}_{8.2}$% ($-17.5^{-24.2}_{-10.7}$ Mt CO 2 eq y -1 ), respectively, of this reduction. This highlights that the extent of implementation area is a major factor in determining benefits and that EW has the potential to make a real contribution to net reduction targets. Results are similar across climate cases, indicating that contemporary field data can be used to make future projections. With EW there remains mechanistic uncertainties, however, such as rock dissolution rate and environmental controls on weathering products, which require additional field research to improve understanding of the technological efficacy of this approach for California's 2045 carbon neutrality goal.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Time-resolved cryogenic electron tomography for the study of transient cellular processes

Cryogenic electron tomography (cryo-ET) is the highest resolution imaging technique applicable to the life sciences, enabling sub-nanometer visualization of specimens preserved in their near native states. The rapid plunge freezing process used to prepare samples lends itself to time-resolved studies, which researchers have pursued for in vitro samples for decades. Here, we focus on developing a freezing apparatus for time-resolved studies in situ. The device mixes cellular samples with solution-phase stimulants before spraying them directly onto an electron microscopy grid that is transiting into cryogenic liquid ethane. By varying the flow rates of cell and stimulant solutions within the device, we can control the reaction time from tens of milliseconds to over a second prior to freezing. In a proof-of-principle demonstration, the freezing method is applied to a model bacterium, Caulobacter crescentus, mixed with an acidic buffer. Through cryo-ET we resolved structural changes throughout the cell, including surface-layer protein dissolution, outer membrane deformation, and cytosolic rearrangement, all within 1.5 seconds of reaction time. This new approach, Time-Resolved cryo-ET (TR-cryo-ET), enhances the capabilities of cryo-ET by incorporating a sub-second temporal axis and enables the visualization of induced structural changes at the molecular, organelle, or cellular level.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Molecular-Resolution Electron Imaging of Defects and Dynamics at the Ice-Water Interface

Water crystallization into hexagonal ice (type I h ) is one of the most critical processes relevant to the Earth’s environment and human activities. However, despite recent breakthroughs in imaging non-equilibrium condensed ice structures, the ice-water interface has never been imaged at a molecular resolution. This is primarily due to the low stability of the hydrogen bonds in ice under high-resolution microscopy conditions and a lack of methods to prepare compatible samples. Here, this presentation describes the first molecular-resolution imaging of ice crystallized from liquid water and the ice-water interface using high-resolution transmission electron microscopy (HRTEM). By encapsulating deionized (DI) water between two amorphous carbon (a-C) TEM grids and subsequently freezing it with liquid N 2 on a cryo sample stage, we generated two types of ice: non-equilibrium, condensed ice from the atmosphere and encapsulated ice from the DI water (Fig. 1A). Condensed ice usually shows irregular, spherulitic shapes (Fig. 1B). Selected area electron diffraction (SAED) shows that they are a mixture of cubic and hexagonal crystals (Fig. 1C). On the contrary, encapsulated ice forms thin films that contain large-area single-crystalline regions of hexagonal ice oriented along the [0001] zone axis (Fig. 1D). Differential electron energy-loss spectroscopy (EELS) confirmed the high purity of the encapsulated ice free from organic contaminations that are common in other encapsulation methods for HRTEM such as graphene liquid cells. These single-crystalline areas are robust under the electron beam up to ~100 e/Å 2 s. Aberration-corrected HRTEM imaging in these areas achieved a line resolution of ~1.3 Å (Fig. 1E and F). This platform allows us to study near-equilibrium ice structures and dynamics at an unprecedented spatial resolution (Fig. 2). For example, we discovered subdomain-rich regions near the defective crystal edges despite the structure appearing single-crystalline according to diffraction criteria. These subdomains connect via low-angle grain boundaries with flat energy landscapes as a function of tilt angles (according to simulations), showing the high tolerance of ice to defect structures. When we tuned the sample temperature and electron flux rate, we observed radiolysis-controlled bubble generation and dissolution in ice single crystals near a steady state of bubble dynamics. Furthermore, rich beam-induced melting and recrystallization dynamics were observed at the ice-water interface with lattice resolution. These data represent the first observation of the ice-water phase transformation at the sub-nanometer level. In summary, the methods developed in this work enabled molecular-resolution observations of ice and the ice-water interface and shed light on the microstructures and phase transformation pathways. Finer control on the temperature, electron irradiation profile, and imaging detector could eventually lead to real-time observation of ice nucleation in water and address long-standing questions in the nucleation pathways.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

New Roadmap for Microelectronics: Charting the Semiconductor Industry's Path Over the Next 5, 10, and 20 Years

In the past, the role of strategic planning for semiconductor industry was met by the International Technology Roadmap for Semiconductors (ITRS), serving as a guiding light that provided manufacturers, designers, equipment suppliers, and researchers with direction years in advance. By providing a common framework for coordination across semiconductor industry stakeholders, technology development efforts were efficient and aligned. However, the dissolution of the ITRS in 2015 left a void, leading to years of disjointed efforts. Recognizing the need for unified guidance, the industry rallied for the creation of a new strategic plan, the Microelectronics and Advanced Packaging Technologies (MAPT) Roadmap (2023) was developed, through the efforts of hundreds of industry, academic and government experts, to provide detailed strategies for achieving these goals. This comprehensive plan outlines ambitious goals for the industry's future.

HPC, Roadmap, AI, Liquid Cooling, Power, Silicon, ↗
DOE OSTI2024

Structure–property relations of sodium iron phosphate nuclear waste glasses: Effects of iron redox ratio and glass composition

Iron phosphate glasses, known for their exceptional chemical durability and potential applicability in nuclear waste management, have gained significant attention over the years. The structures of these glasses are complicated by the coexistence of Fe 3+ and Fe 2+ , which plays a crucial role in determining their structures and properties. Here, this work uses molecular dynamics simulations to study the structural changes in Na 2 O–Fe 2 O 3 –P 2 O 5 glasses with varying glass composition and Fe 2+ /Fe 3+ redox ratio. It was found that the redox ratio and modifier contents significantly affected the short-range and medium-range orders in the glasses. Significant changes in the local environments around P 5+ and Fe 3+ were observed, as reflected by the bond distances and coordination numbers. Na + cations are found to preferentially associate with Fe 3+ (rather than Fe 2+ ), whereas Fe 2+ has stronger association with P 5+ than Na + , confirming the structural role of Fe 2+ as a glass modifier. The disruptions in P–O–P linkages upon increasing FeO suggest that FeO causes glass depolymerization. These glasses achieved higher connectivity with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, conerting phosphorous Q 2 to Q 3 units and iron Q 5 units to Q 4 units. The decrease of nonbridging oxygen fractions with increasing Fe 3+ / (Fe 3+ + Fe 2+ ) ratios, through creating P–O–Fe linkages, is the main reason of enhanced network connectivity. Quantitative structure–property relationship analyses with different structural descriptors were used to correlate with measured properties. The analyses provided valuable insights into structure–property relationships, emphasizing the importance of choosing relevant energy parameters and defining glass network connectivity, particularly in F net descriptors. It was found the Fe–O–P linkage density exhibits strong correlations to measured dissolution rates, supporting the importance of these linkages in improving the chemical durability in iron phosphate glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Stabilizing Cathode–Electrolyte Interphase of Nickel-Rich Single-Crystal Cathodes for Lithium-Ion Batteries

Nickel-rich single-crystal (SC) layered oxides are promising cathode candidates for next-generation lithium-ion batteries (LIBs) owing to their high energy density and structural robustness against intergranular cracking. However, their intrinsic surface reactivity with liquid electrolytes accelerates parasitic reactions at the cathode–electrolyte interphase (CEI), leading to transition-metal dissolution, gas generation, and impedance buildup. In this work, we synthesized SC-Li x Ni 0.9 Mn 0.05 Co 0.05 O 2 (NMC9055, 1 ≤ x ≤ 1.2) using a eutectic-assisted method and investigated interface stabilization strategies. A nickel-deficient Li x Ni 0.6 Mn 0.2 Co 0.2 O 2 (NMC622, 1 ≤ x ≤ 1.2) coating was applied via evaporation-based deposition to suppress CEI degradation pathways. Structural and compositional analyses confirmed uniform shell formation and preserved particle integrity. Half-cell electrochemical testing against lithium metal revealed ∼10% higher capacity retention and improved reversibility compared with pristine SC NMC9055, particularly under high-voltage operation. In conclusion, these results highlight the critical role of controlled surface chemistry in mitigating CEI instability in nickel-rich SC cathodes, offering a pathway toward enabling durable high-energy LIBs.

Coating processes↗
DOE OSTI2025

Tantalum-stabilized ruthenium oxide electrocatalysts for industrial water electrolysis

The iridium oxide (IrO 2 ) catalyst for the oxygen evolution reaction used industrially (in proton exchange membrane water electrolyzers) is scarce and costly. Although ruthenium oxide (RuO 2 ) is a promising alternative, its poor stability has hindered practical application. Here, we used well-defined extended surface models to identify that RuO 2 undergoes structure-dependent corrosion that causes Ru dissolution. Tantalum (Ta) doping effectively stabilized RuO 2 against such corrosion and enhanced the intrinsic activity of RuO 2 . In an industrial demonstration, Ta-RuO 2 electrocatalyst exhibited stability near that of IrO 2 and had a performance decay rate of ~14 microvolts per hour in a 2800-hour test. At current densities of 1 ampere per square centimeter, it had an overpotential 330 millivolts less than that of IrO 2 .

Zhang, Jiahao [Sichuan Univ., Chengdu (China); Uni↗
DOE OSTI2025

Overexpression of sulfide:quinone reductase (SQR) in Acidithiobacillus ferrooxidans enhances sulfur, pyrite, and pyrrhotite oxidation

ABSTRACT Hydrogen sulfide is produced during the dissolution of some sulfidic minerals and during the microbial metabolism of reduced sulfur compounds. The sulfide:quinone reductase (SQR) enzyme is able to oxidize H 2 S, and the bioleaching cells Acidithiobacillus ferrooxidans have two SQR genes, only one of which has been characterized. We cloned and overexpressed the two SQR genes in A. ferrooxidans and show that they both have SQR activity. Both AFE_0267 and AFE_1792 are active under anaerobic conditions, but only AFE_1792 is active under aerobic conditions. The effect of the SQR overexpression and the expression of related genes on sulfur metabolism was investigated. The overexpression of SQR improved cell growth and sulfur oxidation, suggesting enhanced SQR activity led to a reduction in H 2 S toxicity as well as providing additional energy through H 2 S oxidation. Additionally, the impact on the oxidation of pyrite and pyrrhotite was investigated. The rate of oxidation of pyrite by the engineered cells was enhanced, and, furthermore, the rate of pyrrhotite oxidation was more than doubled. IMPORTANCE H 2 S is a toxic sulfur intermediate, and the SQR enzyme has evolved to oxidize H 2 S in A. ferrooxidans . In addition to detoxification, H 2 S oxidation provides energy, and overexpression of SQR enhanced aerobic and anaerobic growth on sulfur. The SQR overexpression also enhanced pyrite and pyrrhotite oxidation, which may facilitate the pyrometallurgical processing of a number of critical materials including copper, nickel, and the platinum group metals.

Jung, Heejung↗
DOE OSTI2024

Physics-Based Continuum Modeling for an Aqueous Rechargeable Zn/MnO 2 Battery

This study introduces a framework for modeling the aqueous Zn/MnO 2 rechargeable battery. A reaction system and a physics-based continuum model are proposed based on two reaction types, one involving insertion and the second related to dissolution and deposition of a solid reaction product. The model, fitted to empirical data, predicts voltage behavior and capacity limitations during cycling, identifying electrolytic zinc depletion as a limiting mechanism, depending on the original cell construction. The research suggests the need for further material characterization and reaction analysis, which will advance our understanding and facilitate the development of grid-scale energy storage solutions.

Electrochemistry↗
DOE OSTI2024

Understanding the Interactions of Multiple Pits Under Freely Corroding Conditions

The interactions of two propagating pits on a single cathode surface were evaluated across variations in chloride concentration, water layer (WL), pit sizes, separation distance (x 2 ), and cathode size (L Cath ) under freely corroding conditions using Finite Element Methods (FEM). Calculated FEM current was utilized to predict stability based on the Galvele pit stability product. FEM predictions were utilized to train a neural network machine learning model for rapid stability predictions. Pit one is in the center of a circular cathode while pit two moves radially from the center pit. With two pits, the overall current in each pit is decreased with respect to a single pit, however, the total current is increased. Increasing WL and L Cath generally increased overall current in each pit and increased predicted maximum pit sizes. Increasing x 2 decreased current in pit two due to less cathode being available to support dissolution in proximity to pit two. Increasing chloride concentration from 0.6 to 3 M NaCl increased current, while increasing from 3 to 5.3 M NaCl decreased current. An overall increase in predicted pit size with increase in chloride concentration is predicted. A machine learning model was created to predict current and maximum pit size and captured underlying physics and predicted stability across the multidimensional parameter space.

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

Impact of Silicon Impurity on the Hydrometallurgical Recovery of NCM622 Cathode

Hydrometallurgy is one of the best approaches to date for recycling LIBs due to its high efficiency, low energy usage, and industrial scalability. However, impurities have always been a thorny issue because they could have unintended impacts on the recovered cathode materials. This research marks the first systematic investigation into the influence of silicon impurity on the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode obtained from hydrometallurgical recycling. Here we find that silicon nanoparticles will be nucleated at the center of the precursor particles during co-precipitation synthesis, and the silicon core will slowly dissolve in the surrounding ammonia, creating a special hollow structure in the particle. More importantly, the dissolution of silicon impurity will eventually lead to the deposition of silicates in the cathode material, which is an unfavorable result. Test data indicate that NCM622 cathode with 5 at% silicon has a capacity of 148.8 mAh g −1 after 100 cycles at 1/3 C, approximately 10 mAh g −1 lower than the virgin. Despite being relatively mild, the adverse influence of silicon impurity in hydrometallurgical recycling still requires attention.

25 ENERGY STORAGE↗
DOE OSTI2025

On the Source of Conductivity in Alkaline Zn Anodes: Zn Percolation and ZnO Bridging

Alkaline Zn anodes are fundamental to commercial Zn-MnO 2 batteries as well as emerging rechargeable designs. In these electrodes, Zn particles are both the active material and source of electronic conduction. However, there are known cases in which electronic connectivity between Zn particles or the current collecting pin is lost even though the battery continues to function. Here we use X-ray computed tomography (CT) of AA batteries to demonstrate several examples of Zn particle-to-particle connectivity breakdown, which is observed even in cases at relatively high discharge rate. This indicates maintenance of the electronic network through the less-conductive ZnO discharge product. We introduce a new equation for electronic conductivity maintained through bridges of ZnO formed between percolating Zn particles. This necessitates discarding the Bruggeman correlation and instead redefining effective electronic conductivity using percolation theory. We demonstrate that such a model for conduction enables prediction of an inverted reaction zone, which is an experimentally observed case in which significant Zn dissolution and ZnO formation occurs heavily near the current collecting pin. Current computational Zn-MnO 2 models never predict an inverted reaction zone, and thus the updated conductivity enables models to accurately explain a wider range of experimental conditions.

Guida, Dominick P. [Northeastern Univ., Boston, MA↗
DOE OSTI2025

Role of Pb/PbSO 4 Morphologies in Dynamic Charge Acceptance of Lead Acid Batteries

The dynamic charge acceptance (DCA) of negative pastes in lead acid batteries is studied using a continuum level model that is validated against in situ X-ray diffraction experiments. The model matches the current transient during a ten-minute, 2.4 V charge at 80% state of charge (SOC) using a distribution of PbSO 4 particles. <2% by volume of small, reactive particles is shown to provide ∼50% of the capacity during the first ten seconds. Increases in DCA with increasing carbon content are captured with increasing lead surface area. The increase in DCA when the 2.4 V charge is done after discharging to 80% SOC (vs charging to 80%) is captured by reducing the PbSO 4 particle sizes. It is hypothesized that the lower DCA after charging is caused by the absence of smaller particles that were consumed during the initial charge to 80% SOC, which is confirmed from X-ray measurements. Finally, two-particle case studies show that reducing the PbSO 4 particle size is more effective for increasing DCA than increasing the PbSO 4 dissolution rate alone. For a given lead surface area, the optimal DCA occurs when the particle sizes are large enough to avoid blocking the surface but small enough to provide dissolution/diffusion improvements.

Knehr, Kevin W. [Argonne National Laboratory (ANL)↗
DOE OSTI2025

Ab Initio Insights to Metal Passivation: Diffusion and Defect Formation in Amorphous Zirconia and Alumina

Metal passivation refers to the formation of protective oxide films on metals, which shield them from further corrosion and oxidation, playing a crucial role in maintaining their stability. The mesoscopic Point Defect Model has successfully predicted passivity as a steady state process where oxide growth from oxygen vacancies at the metal/film interface competes with oxide dissolution at the film/environment interface. In this work, informed by the Point Defect Model parameters, we use first-principles calculations to calculate defect formation and atomic diffusion in amorphous materials and correlate these descriptors with the behavior and growth of the oxide film. Focusing on amorphous zirconia and alumina, we demonstrate that defect formation energies exhibit significant variability in amorphous systems. In alumina, vacancies dominate, with cation and anion vacancies occurring at comparable concentrations. Diffusion calculations for stoichiometric amorphous alumina and zirconia, as well as oxygen-deficient zirconia, reveal faster diffusion in the oxygen-deficient case, highlighting the impact of defects on transport. Comparison of calculated self-diffusion coefficients for the dominant defect species with experimentally measured oxide thicknesses shows a clear correlation, suggesting that first-principles-derived diffusivity information can serve as a key descriptor for surface passivation film growth.

Farnell, Mackinzie S. [University of California, B↗
DOE OSTI2025

Elucidating Sodium-Sulfur Battery Chemistry using Operando Transmission X-ray Microscopy and X-ray Absorption Spectroscopy

Room-temperature sodium-sulfur (Na-S) batteries offer a beneficial and cost-effective solution for powering modern electric grids and devices. However, Na-S batteries suffer from performance decay during battery cycling due to the sluggish kinetics and polysulfide shuttling. Revealing the conversion mechanism of the Na-S chemistry is critical to designing high-capacity and stable Na-S batteries. In this study, we employed operando X-ray microscopy and operando X-ray absorption spectroscopy to elucidate the sulfur conversion in a carbon host using an ether-based electrolyte. We reveal the structural and chemical evolution of the sulfur cathode during cycling, which results in volume expansion and the dissolution of active material, ultimately affecting the battery performance. Our work provides fundamental insight into the sulfur reaction scheme, addressing the lingering challenges before establishing inexpensive Na-S batteries for broad applications, including portable electronics and large-scale energy storage.

Jagadeesan, Sathya Narayanan [SLAC National Accele↗
DOE OSTI2025

Cycling Performance and Structure Evolution of Co-Free Lithium- and Manganese-Rich Layered Oxides in Lithium-Ion Batteries

Lithium- and manganese-rich (LMR) layered oxides are high-capacity cathode materials that are being considered for electric vehicle (EV) lithium-ion batteries (LIBs). Here, we investigate the electrochemical cycling behavior of cells containing a cobalt-free LMR oxide, 0.3Li 2 MnO 3 ·0.7LiMn 0.5 Ni 0.5 O 2 , paired with either Li or graphite anodes. Two- and three-electrode cells are cycled under varying conditions to examine the effects of oxide activation, upper cutoff voltage, separator type, and electrolyte composition. Post-cycling characterization of harvested electrodes, with electrochemical, X-ray absorption spectroscopy, and solid-state 6 Li nuclear magnetic resonance spectroscopy techniques, are used to correlate cell performance changes with redox state evolution in the oxide and Li inventory shifts in the cell. Our results show that capacity fade and impedance rise primarily originate at the graphite anode and LMR cathode, respectively. Notably, while Ni undergoes reversible redox, Mn shows no evidence of bulk redox activity even in highly-aged electrodes: only relithiated LMR electrodes show some reduction of Mn. Graphite electrodes degrade due to particle isolation and SEI growth, exacerbated by Mn dissolution and deposition on graphite anodes. These findings highlight the coupled structural and electrochemical degradation mechanisms in LMR/graphite cells and underscore lithium inventory retention and electrode interfacial stability as critical factors for enhancing long-term performance.

Badami, Pavan P. [Argonne National Laboratory (ANL↗