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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Examining Graphite Degradation in Molten Salt Environments: A Chemical, Physical, and Material Analysis

Molten-salt reactors (MSRs) are Generation IV nuclear reactors that use liquid salt as a coolant and/or fuel. In several MSR designs, graphite serves as a moderator and/or reflector. However, due to limited experimental data and operational experience, our understanding of graphite behavior in molten salt environments remains incomplete. This report aims to identify the degradation mechanisms of nuclear graphite in MSRs, detail the mechanisms of each factor, and provide an initial assessment of their impact on the structural integrity of graphite components. This assessment is based on an extensive literature review and insights from subject matter experts. Furthermore, given the limited data, a modeling strategy using existing Grizzly software is proposed for a more thorough analysis where appropriate. Additionally, it presents mitigation strategies where applicable. The report covers physical degradation mechanisms such as infiltration, erosion, and abrasion, as well as chemical degradation mechanisms including fluorination, intercalation, corrosion, and oxidation. Molten salt can infiltrate the porous structure of graphite, leading to several detrimental effects. Entrapment of fissile products within the graphite pores can cause radiation damage and could pose challenges in the handling and disposal of contaminated components. The differential thermal expansion between the infiltrated salt and graphite, along with internal stress from pressurized molten salt and volumetric heating, can compromise the structural integrity of graphite. To mitigate these effects, employing ultra-fine graphite grades and applying sealants and coatings are effective strategies. A computational model based on coupled solid mechanics and heat transfer phenomena could be used to predict the internal stresses using Grizzly software. In pebble-bed MSRs, graphite fuel pebbles can cause abrasion against reactor components due to friction and wear. The severity of wear is influenced by various factors such as temperature, environment, and the presence of lubricants. Tribological studies reveal that higher temperatures and molten salt environments, such as FLiBe, significantly reduce wear rates compared to dry conditions. Additionally, the chemical composition of the salt can further optimize graphite's tribological performance. Long-term wear effects can be modeled by incorporating surface defects into the geometry and predict stresses under thermal and radiation effects using Grizzly software. Chemical degradation of graphite in a molten salt environment can occur through fluorination and intercalation. Fluorination can occur via replacement of hydrogen or oxygen atoms, or at the active sites, but does not cause structural degradation. Intercalation, on the other hand, can lead to exfoliation, where layers of graphite separate and peel away, damaging the graphite. Protective coatings can enhance graphite's resistance to intercalation. Graphite generally exhibits good chemical stability in molten salt environments, though it can corrode under specific conditions, particularly in the presence of impurities or oxidants. Studies have shown that protective coatings, such as plasma-sprayed partially stabilized zirconia (PSZ), can effectively prevent such degradation. Corrosion behavior varies significantly with different graphite grades and coating applications, underscoring the need for detailed studies on uncoated and coated graphite to understand and mitigate corrosion mechanisms in MSRs. Research indicates that the presence of oxidants and impurities can accelerate graphite degradation in molten salts, making it essential to explore acceptable impurity limits. Oxidation is another critical degradation mechanism, leading to weight loss and structural damage due to the formation of CO and CO 2 from the reaction of carbon atoms with oxygen. This process creates new porosity and compromises graphite's integrity. While extensive research on graphite oxidation has been conducted for gas-cooled reactors, studies specific to MSRs are limited. Findings from the coal industry suggest that molten alkali metal salts can significantly accelerate graphite oxidation, a hypothesis worth exploring for fluoride salts in MSRs. Understanding oxidation behavior in MSRs is vital for developing protective measures. The analysis of post-irradiated graphite from the MSRE experiment demonstrated exceptional chemical compatibility with molten fluoride salt, suggesting that the extent of chemical attack on graphite largely depends on the salt's infiltration capability. Therefore, the use of ultra-fine grade graphite could help mitigate chemical degradation effects. Existing oxidation modeling capabilities in Grizzly, which use reaction-diffusion equations to model graphite-air interactions, could be adapted to simulate the chemical degradation effects of graphite in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2026

Mitigation of polysulfide shuttle effect in Li-S batteries through catalytic disproportionation reaction

Polysulfides are poorly retained within porous cathodes and readily diffuse into the electrolyte over time, leading to the well-known shuttle effect that undermines the reversibility of Li-S batteries. Here, in this study, we demonstrate that catalytic disproportionation of polysulfides provides an effective pathway to suppress this process by rapidly converting dissolved species into solid sulfur and sulfides, thereby preventing their migration into the electrolyte. Fundamentally, the sluggish kinetics of sulfur redox reactions are responsible for the accumulation and redistribution of soluble polysulfides in the bulk electrolyte. By accelerating these kinetics, catalyzed disproportionation not only confines sulfur within the conductive cathode matrix but also promotes the homogeneous precipitation of Li₂S₂/Li₂S, which enhances electrochemical reversibility and cycling stability. Using nitrogen-doped carbon (NC800) as a model catalyst, we reveal its ability to drive a pseudo-16-electron reduction pathway, leading to a single dominant Li₂S product and uniform deposition within the porous framework. In contrast, a non-catalytic carbon (KB) yields multiple polysulfide intermediates and heterogeneous deposition. The mechanistic insights provided here highlight the pivotal role of catalytic disproportionation in reshaping sulfur redox pathways and offer a rational strategy for mitigating polysulfide shuttling in practical Li-S pouch cells.

25 ENERGY STORAGE↗
DOE OSTI2025

Modeling diffusion and depletion in high-aspect-ratio atomic layer deposition processes: Process parameters and manufacturing impacts

Atomic layer deposition (ALD) is a powerful technique for modifying the surface chemistry and properties of substrates with complex and nonplanar topologies. However, achieving uniform and conformal deposition on ultrahigh-aspect-ratio substrates remains challenging, typically requiring large quantities of precursors and long exposure times. Furthermore, process optimization is often performed empirically and involves substantial trial and error. In this work, we perform a combined experimental and computational study of ALD Al 2 O 3 infiltration into silica aerogel monoliths (aspect ratio >10 5 ). A reaction-diffusion model is used to explore the effects of key processing parameters, namely, exposure time per dose, precursor source temperature, number of aerogels in the reactor, and reactor volume. The model is based on quasi-static mode ALD, where the dosed precursor is held in the chamber for a fixed period of time before purging. We analyze the trade-offs between process throughput and precursor utilization for each of these parameters. Furthermore, we investigate the co-optimization and interactions between multiple process parameters, demonstrating the potential for further improvements. Furthermore, this physics-based model can be used to identify a set of process parameters for high-aspect-ratio ALD that meet specific manufacturing objective functions, including throughput, cost, and sustainability.

Aerogel↗
DOE OSTI2026

Effects of temperature and dose rate on ion-irradiated γ-LiAlO 2 pellets

Defect accumulation and microstructural evolution during ion irradiation at elevated temperatures are governed by competing processes of defect production, driven by the dose rate, and defect recovery, controlled by diffusion, interaction, and annihilation. Here, this study investigates the effects of irradiation temperature and the dose rate on microstructural evolution, deuterium retention, and lithium volatilization in γ-LiAlO 2 pellets subjected to sequential He + and D + ion irradiation. Experiments were performed to a total fluence of 3 × 10 17 (He + + D + )/cm 2 at 623, 673, 723, and 773 K with an average He + dose rate of 7.7 × 10 −4 dpa/s, and to 2 × 10 17 (He + + D + )/cm 2 at 773 K with dose rates of 6.8 × 10 −5 , 2.9 × 10 −4 , and 7.3 × 10 −4 dpa/s. At 623 K, the microstructure was dominated by cavities and fractures with no observable precipitate formation, while small precipitates emerged at 673 K. Increasing the irradiation temperature to 723–773 K promoted the formation of larger, faceted LiAl 5 O 8 precipitates, and surface amorphization, accompanied by pronounced lithium depletion and H–D isotopic exchange. At 773 K, medium and high dose rates produced an amorphized surface layer over a crystalline subsurface containing LiAl 5 O 8 precipitates and blisters at the crystalline–amorphous interface, whereas low-dose-rate irradiation preserved surface crystallinity with cavities distributed in the matrix, around precipitates, and along grain boundaries. Precipitate morphology was anisotropic with limited size dependence on the dose rate. These results elucidate the coupled effects of temperature and the dose rate and demonstrate that sequential He + and D 2 + irradiation at 773 K reproduces key microstructural features and H isotope behavior observed in neutron-irradiated γ-LiAlO 2 at 573 K.

dose rate effects↗
DOE OSTI2024

Tailoring Ion Transport in Li 3‐3y Ho 1+y Cl 6‐x Br x via Transition‐Metal Free Structural Planes and Charge Carrier Distribution

Abstract Localized atomistic disorder in halide‐based solid electrolytes (SEs) can be leveraged to boost Li + mobility. In this study, Li + transport in structurally modified Li 3 HoCl 6 , via Br − introduction and Li + deficiency, is explored. The optimized Li 3‐3 y Ho 1+ y Cl 6‐ x Br x achieves an ionic conductivity of 3.8 mS cm −1 at 25 °C, the highest reported for holmium halide materials. 6,7 Li nuclear magnetic resonance and relaxometry investigations unveil enhanced ion dynamics with bromination, attaining a Li + motional rate neighboring 116 MHz. X‐ray diffraction analyses reveal mixed‐anion‐induced phase transitions with disproportionate octahedral expansions and distortions, creating Ho‐free planes with favorable energetics for Li + migration. Bond valence site energy analysis highlights preferred Li + transport pathways, particularly in structural planes devoid of Ho 3+ blocking effects. Molecular dynamics simulations corroborate enhanced Li + diffusion with Br − introduction into Li 3 HoCl 6 . Li‐Ho electrostatic repulsions in the (001) plane presumably drive Li + diffusion into the Ho‐free (002) layer, enabling rapid intraplanar Li + motion and exchange between the 2d and 4h sites. Li 3‐3 y Ho 1+ y Cl 6‐ x Br x also demonstrates good battery cycling stability. These findings offer valuable insights into the intricate correlations between structure and ion transport and will help guide the design of high‐performance fast ion conductors for all‐solid‐state batteries.

Chemistry↗
DOE OSTI2024

Effects of Ligand Chemistry on Ion Transport in 2D Hybrid Organic–Inorganic Perovskites

2D hybrid organic–inorganic perovskites are potentially promising materials as passivation layers that can enhance the efficiency and stability of perovskite photovoltaics. The ability to suppress ion transport is proposed as a stabilization mechanism, yet an effective characterization of relevant modes of halide diffusion in 2D perovskites is nascent. In light of this knowledge gap, molecular dynamics simulations with enhanced sampling and experimental validation to systematically characterize how ligand chemistry in seven (R-NH 3 ) 2 PbI 4 systems impacts halide diffusion, particularly in the out-of-plane direction is combined. It is found that increasing stiffness and length of ligands generally inhibits ion transport, while increasing ligand polarization generally enhances it. Structural and energetic analyses of the migration pathways provide quantitative explanations for these trends, which reflect aspects of the disorder of the organic layer. Overall, this mechanistic analysis greatly enhances the current understanding of halide migration in 2D hybrid organic–inorganic perovskites and yields insights that can inform the design of future passivation materials.

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

Selective atomic sieving across metal/oxide interface for super-oxidation resistance

Abstract Surface passivation, a desirable natural consequence during initial oxidation of alloys, is the foundation for functioning of corrosion and oxidation resistant alloys ranging from industrial stainless steel to kitchen utensils. This initial oxidation has been long perceived to vary with crystal facet, however, the underlying mechanism remains elusive. Here, using in situ environmental transmission electron microscopy, we gain atomic details on crystal facet dependent initial oxidation behavior in a model Ni-5Cr alloy. We find the (001) surface shows higher initial oxidation resistance as compared to the (111) surface. We reveal the crystal facet dependent oxidation is related to an interfacial atomic sieving effect, wherein the oxide/metal interface selectively promotes diffusion of certain atomic species. Density functional theory calculations rationalize the oxygen diffusion across Ni(111)/NiO(111) interface, as contrasted with Ni(001)/NiO(111), is enhanced. We unveil that crystal facet with initial fast oxidation rate could conversely switch to a slow steady state oxidation.

(S)TEM, oxidizing metals↗
DOE OSTI2024

Development of APCVD BSG and POCl 3 Codiffusion Process for Double-Side TOPCon Solar Cell Precursor Fabrication

This paper presents a commercially viable process for fabricating a high-quality double-side tunnel oxide passivating contact (DS-TOPCon) cell precursor using APCVD-deposited boron silicate glass and ex-situ POCl 3 diffusion in a single high-temperature step, eliminating the need for additional masking and diffusion processes. A two-tier temperature profile was developed, involving a pre-annealing at above 900°C in nitrogen (N2) ambient followed by POCl 3 diffusion at 840°C. We investigated the effect of varying pre-annealing temperatures, ranging from 875°C to 950°C, on the passivation quality and metal-Si contact properties of both n-TOPCon and p-TOPCon layers. The resultant DS-TOPCon cell precursor after silicon nitride (SiNX) passivation exhibited an excellent iV OC of close to 730 mV. In addition, a rapid asymmetric poly-Si thinning technique, developed in this work, enabled adjustment of the front n + poly-Si thickness while maintaining the rear p + poly-Si thickness. Two types of DS-TOPCon cell architectures can be fabricated: i) full-area thin (≈40nm) n-TOPCon layer on the front and ii) selective-area thick (≈200nm) n-TOPCon fingers underneath the metal grid. Device simulations suggest that full-area DS-TOPCon cell with 40 nm n + poly-Si and selective-area DS-TOPCon cell with 200 nm n + poly fingers on the front, fabricated from our current DS-TOPCon cell precursor, can achieve cell efficiencies of 22.1 and 23.5%, respectively. Detailed power loss analysis and device simulation reveal that further improvements in material and device parameters have potential to push the cell efficiencies of DS-TOPCon cell structure beyond 25%, making it a promising alternative to fabricate a high-efficiency next-generation solar cells at low cost.

14 SOLAR ENERGY↗
DOE OSTI2025

Computational Modeling of Molten Salt Infiltration and Oxidation in Nuclear Graphite

Graphite is utilized as a moderator and reflector in advanced nuclear reactor designs due to its high thermal conductivity, neutron moderation properties, and resistance to radiation damage. However, its longterm performance and reliability are challenged by degradation mechanisms such as molten salt infiltration in molten salt reactors (MSRs) and oxidation in gas-cooled reactors (GCRs). These mechanisms can compromise the structural integrity and operational lifetime of graphite components, necessitating a more detailed assessment of their physical behavior. This report focuses on the development of computational models for molten salt infiltration and oxidation of graphite to aid the design and performance analysis of graphite components. For molten salt infiltration, a computational framework is developed that couples incompressible Navier-Stokes and phase-field model to simulate the penetration of molten salt into graphite?s interconnected pore structure. Initial model verification is performed using two-phase flows in two dimensions, demonstrating the models ability to capture fundamental physical behavior and agree with analytical solution. This framework is then applied to a realistic IG110 nuclear graphite , where a computed tomography extracted pore geometry is used to analyse the infiltration behavior of FLiNaK molten salt. This model provides insights into how the microstructure and other relevant parameters influence the transport pathways of molten salt into graphite, potentially offering a means to rapidly evaluate a graphite grade?s resistance to infiltration. For oxidation, the report details pore-scale mass and heat transport models, describing the diffusion of gases, reaction kinetics, and thermal effects. Additionally, this report highlights inconsistencies in the existing volume-averaged macroscopic model, particularly in upscaling of reaction kinetics and flux terms, and surface to volume transformations. These inconsistencies suggest that current formulations may not accurately capture the experimentally observed graphite oxidation process, highlighting the need for improved model development. This work advances the development of physics-based computational models for graphite degradation, contributing to improved predictive models for next-generation nuclear reactor designs. Future efforts will focus on refining the infiltration model to address non-physical behaviors and enhance its robustness. Additionally, for oxidation, further studies will employ the principles of volume averaging to rigorously derive the upscaled equations, potentially in collaboration with subject matter experts.

Computational Modeling of Molten Salt Infiltration↗
DOE OSTI2025

Probing the Impact of Vacancy Diffusion on Void Dynamics at the Lithium Metal–Solid Electrolyte Interface

Lithium (Li) metal-based solid-state batteries (SSBs) are considered promising candidates for next-generation energy storage due to their superior energy density and enhanced safety compared to conventional Li-ion systems. However, their practical application is limited by challenges such as void formation at the Li-solid electrolyte (SE) interface, which disrupts ion transport and accelerates interfacial degradation. This work investigates how the coupled effects of electro-dissolution kinetics and surface diffusion at the Li metal surface govern the evolution of interfacial morphology during stripping. This work examines the influence of three distinct surface diffusion modes, which are terrace diffusion, step diffusion, and interlayer diffusion, on maintaining interfacial stability. In addition, how the dominant surface diffusion mechanism can overcome the contact loss due to high reaction kinetics is explored. Furthermore, the roughness of the Li metal anode surface is quantified, and the influence of different diffusion mechanisms on the evolution of the dynamic solid–solid interface is examined. The critical role of temperature in enhancing Li surface diffusivity and expanding the regime of stable contact is highlighted. By identifying distinct regimes of interface stability, this study analyzes how non-uniform electrochemical dynamics dictate void morphology evolution and interfacial contact. These insights offer guiding principles for engineering robust Li–SE interfaces in SSBs.

lithium metal anode↗
DOE OSTI2026

Integrated Strategies for Overcoming Resolution Limits in Electron Beam Lithography of Chemically Amplified Resists

Electron beam lithography (EBL) of chemically amplified resists (CARs) faces fundamental challenges, including stochastic electron scattering and acid diffusion, that limit resolution and reproducibility. Using SU-8 as a model CAR, this study systematically investigated complementary strategies to address these challenges, combining multipass exposure, proximity effect correction (PEC) with midrange correction factors, base quencher incorporation, and post-exposure bake (PEB) suppression. Monte Carlo simulations and calibrated PEC modeling revealed that extending the point spread function to include a midrange scattering component significantly improved critical dimension (CD) control across varying pattern densities, correcting deviations that conventional two-term PEC failed to capture. Multipass exposure, particularly 4-pass writing with a 25% offset, redistributed the dose to average stochastic beam and scattering fluctuations, reducing line-width roughness by more than 50% and yielding more uniform nanoscale features. Photoacid confinement was investigated by adding urea as a base quencher, which successfully reduced acid diffusion but introduced substantial sensitivity penalties without improving ultimate resolution or Z-factor performance, underscoring the trade-offs of chemical versus physical confinement. Suppressing PEB most directly minimized acid diffusion, resulting in improved Z-factors and reproducible 30 nm half-pitch dense line/space patterns. Overall, these results demonstrated that PEC with midrange correction, multipass strategies, quencher additives, and PEB-free processing addresses different aspects of the EBL process window and that their integration provides a comprehensive framework for managing stochastic scattering, diffusion, and chemical amplification effects. This framework advances dense nanoscale patterning in CARs and establishes guiding principles for optimizing resist design and process strategies in high-resolution EBL and potentially other advanced lithographies, such as extreme ultraviolet (EUV) lithography.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Interfaces enhanced plasma irradiation resistance in CrMoTaWV/W multilayer films through blocking He diffusion

The performance of plasma-facing materials (PFMs) is one of the key factors that significantly impact the stability of operation in fusion reactors. Herein, a new CrMoTaWV/W (high entropy alloy (HEA)/W) multilayer structure is designed as PFM to investigate its resistance to He plasma irradiation. It was observed that the introduction of the interfaces effectively absorbed plenty of He atoms, preventing them from diffusing into the material and delaying the formation of fuzz incubation zone, therefore, enhancing the resistance to plasma irradiation. The thickness transformed to fuzz in the HEA/W multilayer films was observed to be about two-thirds of those in the CrMoTaWV (HEA) film. Additionally, the fuzz growth rates in HEA/W multilayer films are lower than the average growth rate of bulk W and HEA films combined. These findings highlight a promising new avenue for the exploration of high-performance PFMs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Insights into Rotational and Translational Dynamics in Mixtures of Ethylene Glycol and Choline Chloride Using Nuclear Magnetic Resonance Techniques

This work examines molecular dynamics and interactions in ethylene glycol–choline chloride (EG–ChCl) mixtures across 0–33 mol % ChCl, spanning the true eutectic region near 17–20 mol % and the commonly used 1:2 formulation. We combine pulsed-field-gradient (PFG) diffusion, fast-field-cycling (FFC) relaxometry, temperature-dependent 13 C T 1 , and nuclear Overhauser effect spectroscopy (NOESY) to disentangle local from macroscopic dynamics. PFG and FFC show that both translational and average rotational motions largely track the strong increase in viscosity with ChCl content, with ethylene glycol consistently diffusing faster than the choline cation and no global dynamical anomaly at the eutectic composition. More subtle, site-specific composition effects nevertheless emerge. The ratio of the diffusion coefficient of the hydroxyl group of choline to the diffusion coefficient of the methyl group of choline displays a shallow minimum in the 17–25 mol % region, indicating a modest change in how the hydroxyl-bearing end of choline samples the underlying translational motion relative to the methyl groups. 13 C T 1 analysis shows that rotational correlation times at 25 °C generally increase with ChCl, reflecting viscosity-coupled slowing, while the CH 2 –N α site exhibits a small but reproducible deviation from this monotonic trend near the eutectic. NOESY spectra at similar compositions reveal enhanced cross-relaxation between EG and choline protons, consistent with increased headgroup–solvent contact density rather than a wholesale structural rearrangement. Overall, our multitechnique study demonstrates that EG–ChCl dynamics are predominantly viscosity-dominated, with the eutectic region acting as a subtle dynamical crossover where specific choline segments become maximally coupled to the hydrogen-bond network. These insights refine the structure–dynamics picture of choline-chloride DESs and provide practical guidance for tuning composition in electrochemical, separation, and catalytic applications.

diffusion↗
DOE OSTI2025

Doping in Efficient Polycrystalline CdSeTe Solar Cells via AsCl 3 Vapor Annealing

Doping in cadmium telluride (CdTe) thin-film solar cells is a critical step in producing highly efficient CdTe solar modules. To date, copper (Cu) ex-situ diffusion doping and group V in situ doping (such as arsenic, As) have been effectively used in manufacturing CdTe solar modules. However, Cu doping is prone to rapid degradation, whereas the low activation ratio of the dopants constrains group V in situ doping. Recently, ex-situ group V doping has been developed, showing an improved doping activation ratio through a solution process. Here, in this study, we developed a vapor-based AsCl 3 doping method for diffusion doping of polycrystalline CdSeTe devices. AsCl 3 vapor annealing can promote the diffusion of As into the bulk CdSeTe through a surface chemical reaction between CdTe and AsCl 3 . This approach has led to a long carrier lifetime of over 72 ns, V oc of 850 mV, and power conversion efficiency of ~18% with Au metal electrodes. The vapor-based ex situ group V doping approach offers an effective means to perform group V diffusion doping into the CdSeTe device.

14 SOLAR ENERGY↗
DOE OSTI2024

Self-diffusion of liquid deuterium hydride and liquid tritium

Here, we present a quasi-elastic neutron scattering study of liquid deuterium hydride carried out using the Disk Chopper Spectrometer at the National Institute of Standards and Technology. Under saturated vapor pressure, the self-diffusion constant of deuterium hydride obeys an Arrhenius law D = D 0 exp(-E A /k B T), where the prefactor D 0 is given by D 0 = 9.5 ± 1.2 Å 2 /ps and the activation energy is given by E A = 58 ± 2 K. We apply the quantum law of corresponding states to the known diffusion constants of the hydrogen isotopologues. From this application, we estimate that D 0 ≈ 9.1 Å 2 /ps and E A ≈ 75 K in liquid tritium. Young’s theory of quantum-mechanical effects in van der Waals fluids is shown to apply to the diffusion constants of the liquid hydrogens. Our results underscore the importance of nuclear quantum effects in shaping the properties and behavior of the hydrogen isotopologues.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Structural origin of disorder-induced ion conduction in NaFePO 4 cathode materials

Diffusion in NaFePO 4 can be enhanced through amorphization. Based on computations using DFT and machine learning potentials, we ascribe this phenomenon to the formation of less constrained Na-ion environments upon disordering. Most modern battery technologies depend on solid-state crystalline cathode materials. However, some of these materials are constrained by the low ionic conductivity of their most stable phases. An example of this is maricite (NaFePO 4 ). Interestingly, experiments have shown that maricite can improve its rate capability through disordering (amorphization). However, experimental characterization of amorphous cathode materials remains a major challenge, hindering a clear understanding of the structural origin of the disorder-induced improvement in sodium-ion mobility. To address this, we here employ molecular dynamics simulations by first training a machine learning potential for NaFePO 4 based on the atomic cluster expansion approach and a batch active learning potential parameterization scheme. This potential is then applied to explore the structural and dynamical properties of NaFePO 4 glasses as cathode materials. Specifically, we investigate the effect of glass structure on sodium-ion diffusion, revealing the relative influences of short-range and medium-range order features. We find significant heterogeneity in sodium-ion diffusivity in the glass, with fast-conducting ions residing in less constrained atomic environments with fewer P and Fe neighbors. These more mobile ions are also surrounded by larger ring-type structures. Overall, the results and developed approach present promising avenues for developing high-performance glassy cathodes for next-generation batteries.

Christensen, Rasmus↗
DOE OSTI2024

Phase-space entropy cascade and irreversibility of stochastic heating in nearly collisionless plasma turbulence

We consider a nearly collisionless plasma consisting of a species of “test particles” in one spatial and one velocity dimension, stirred by an externally imposed stochastic electric field—a kinetic analog of the Kraichnan model of passive advection. The mean effect on the particle distribution function is turbulent diffusion in velocity space—known as stochastic heating. Accompanying this heating is the generation of fine-scale structure in the distribution function, which we characterize with the collisionless (Casimir) invariant C 2 ∝ ∫ ∫ d x d v 〈 f 2 〉 —a quantity that here plays the role of (negative) entropy of the distribution function. We find that C 2 is transferred from large scales to small scales in both position and velocity space via a phase-space cascade enabled by both particle streaming and nonlinear interactions between particles and the stochastic electric field. We compute the steady-state fluxes and spectrum of C 2 in Fourier space, with k and s denoting spatial and velocity wave numbers, respectively. In our model, the nonlinearity in the evolution equation for the spectrum turns into a fractional Laplacian operator in k space, leading to anomalous diffusion. Whereas even the linear phase mixing alone would lead to a constant flux of C 2 to high s (towards the collisional dissipation range) at every k , the nonlinearity accelerates this cascade by intertwining velocity and position space so that the flux of C 2 is to both high k and high s simultaneously. Integrating over velocity (spatial) wave numbers, the k -space ( s -space) flux of C 2 is constant down to a dissipation length (velocity) scale that tends to zero as the collision frequency does, even though the rate of collisional dissipation remains finite. The resulting spectrum in the inertial range is a self-similar function in the ( k , s ) plane, with power-law asymptotics at large k and s . Our model is fully analytically solvable, but the asymptotic scalings of the spectrum can also be found via a simple phenomenological theory whose key assumption is that the cascade is governed by a “critical balance” in phase space between the linear and nonlinear timescales. We argue that stochastic heating is made irreversible by this entropy cascade and that, while collisional dissipation accessed via phase mixing occurs only at small spatial scales rather than at every scale as it would in a linear system, the cascade makes phase mixing even more effective overall in the nonlinear regime than in the linear one. Published by the American Physical Society 2024

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗