Publications

Individual lanthanide elements have physical/electronic/magnetic properties that make each useful for specific applications. Several of the lanthanides cations (Ln3+) naturally occur together in the same ores. They are notoriously difficult to separate from each other due to their chemical similarity. Predicting the Ln3+ differential binding energies (ΔΔE) or free energies (ΔΔG) at different binding sites, which are key figures of merit for separation applications, will help design of materials with lanthanide selectivity. We apply ab initio molecular dynamics (AIMD) simulations and density functional theory (DFT) to calculate ΔΔG for Ln3+ coordinated to ligands in water and embedded in metal-organic frameworks (MOFs), and ΔΔE for Ln3+ bonded to functionalized silica surfaces, thus circumventing the need for the computational costly absolute binding (free) energies ΔG and ΔE. Perturbative AIMD simulations of water-inundated simulation cells are applied to examine the selectivity of ligands towards adjacent Ln3+ in the periodic table. Static DFT calculations with a full Ln3+ first coordination shell, while less rigorous, show that all ligands examined with net negative charges are more selective towards the heavier lanthanides than a charge-neutral coordination shell made up of water molecules. Amine groups are predicted to be poor ligands for lanthanide-binding. We also address cooperative ion binding, i.e., using different ligands in concert to enhance lanthanide selectivity.

High-nickel-content layered oxides are among the most promising electric vehicle battery cathode materials. However, their interfacial reactivity with electrolytes and tendency toward oxygen release (possibly yielding reactive 1O2) remain degradation concerns. Elucidating the most relevant (i.e., fastest) interfacial degradation mechanism will facilitate future mitigation strategies. We apply screened hybrid density functional (HSE06) calculations to compare the reaction kinetics of LixNiO2 surfaces with ethylene carbonate (EC) with those of O2 release. On both the (001) and (104) facets, EC oxidative decomposition exhibits lower activation energies than O2 release. Our calculations, coupled with previously computed liquid-phase reaction rates of 1O2 with EC, strongly question the role of “reactive 1O2” species in electrolyte oxidative degradation. The possible role of other oxygen species is discussed. To deal with the challenges of modeling LixNiO2 surface reactivity, we emphasize a “local structure” approach instead of pursuing the global energy minimum.

Recent studies of power flow and particle transport in multi-MA pulsed-power accelerators demonstrate that electrode plasmas may reduce accelerator efficiency by shunting current upstream from the load. The detailed generation and evolution of these electrode plasmas are examined here using fully relativistic, Monte Carlo particle-in-cell (PIC) and magnetohydrodynamic (MHD) simulations over a range of peak currents (8–48 MA). The PIC calculations, informed by vacuum science, describe the electrode surface breakdown and particle transport prior to electrode melt. The MHD calculations show the bulk electrode evolution during melt. The physical description provided by this combined study begins with the rising local magnetic field that increases the local electrode surface temperature. This initiates the thermal desorption of contaminants from the electrode surface, with contributions from atoms outgassing from the bulk metal. The contaminants rapidly ionize forming a 10¹⁵-10¹⁸ cm^-3 plasma that is effectively resistive while weakly collisional because it is created within, and rapidly penetrated by, a strong magnetic field (> 30 T). Prior to melting, the density of this surface plasma is limited by the concentration of absorbed contaminants in the bulk (~10¹⁹ cm^-3 for hydrogen), its diffusion, and ionization. Eventually, the melting electrodes form a conducting plasma (10²¹-10²³ cm^-3) that experiences j × B compression and a typical decaying magnetic diffusion profile. This physical sequence ignores the transport of collisional plasmas of 10¹⁹ cm^-3 which may arise from electrode defects and associated instabilities. Nonetheless, this picture of plasma formation and melt may be extrapolated to higher-energy pulsed-power systems.

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precursors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode-electrolyte interphase (CEI) film formation, transition-metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply density functional theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen-terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition-metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition-metal ions. The structure-degradation relation complexity underscores the challenge of understanding the function of the CEI but also offers a guide to future degradation-mitigation strategies including facet engineering. Our predictions and models help establish a framework for future studies relevant to high-voltage conditions.

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Understanding the adsorption of isolated metal cations from water on to mineral surfaces is critical for toxic waste retention and cleanup in the environment. Heterogeneous nucleation of metal oxyhydroxides and other minerals on material surfaces is key to crystal growth and dissolution. The link connecting these two areas, namely cation dimerization and polymerization, is far less understood. In this work we apply ab initio molecular dynamics calculations to examine the coordination structure of hydroxide-bridged Cu(II) dimers, and the free energy changes associated with Cu(II) dimerization on silica surfaces. The dimer dissociation pathway involves sequential breaking of two Cu2+-OH− bonds, yielding three local minima in the free energy profiles associated with 0-2 OH− bridges between the metal cations, and requires the design of a (to our knowledge) novel reaction coordinate for the simulations. Cu(II) adsorbed on silica surfaces are found to exhibit stronger tendency towards dimerization than when residing in water. Cluster-plus-implicit-solvent methods yield incorrect trends if OH− hydration is not correctly depicted. The predicted free energy landscapes are consistent with fast equilibrium times (seconds) among adsorbed structures, and favor Cu2+ dimer formation on silica surfaces over monomer adsorption.

Artificial solid electrolyte interphases have provided a path to improved cycle life for high energy density, next-generation anodes like lithium metal. Although long cycle life is necessary for widespread implementation, understanding and mitigating the effects of aging and self-discharge are also required. Here, we investigate several coating materials and their role in calendar life aging of lithium. We find that the oxide coatings are electronically passivating whereas the LiF coating slows charge transfer kinetics. Furthermore, the Coulombic loss during self-discharge measurements improves with the oxide layers and worsens with the LiF layer. It is found that none of the coatings create a continuous conformal, electronically passivating layer on top of the deposited lithium nor are they likely to distribute evenly through a porous deposit, suggesting that none of the materials are acting as an artificial solid electrolyte interphase. Instead, they likely alter performance through modulating lithium nucleation and growth.

The surfaces of most metals immersed in aqueous electrolytes have a several-nanometer-thick oxide/hydroxide surface layer. This gives rise to the existence of both metal∣oxide and oxide∣liquid electrotlyte interfaces, and makes it challenging to correlate atomic length-scale structures with electrochemical properties such the potential-of-zero-charge (PZC). The PZC has been shown to be correlated the onset potential for pitting corrosion. In this work, we conduct large-scale Density Functional Theory and ab initio molecular dynamics to calculate the PZC of a Al(111)∣γ-Al2O3(110)∣ water double-interface model within the context of aluminum corrosion. By partitioning the multiple interfaces involved into binary components with additive contributions to the overall work function and voltage, we predict the PZC to be −1.53 V vs SHE for this model. We also calculate the orbital energy levels of defects like oxygen vacancies in the oxide, which are critical parameters in theories associated with pitting corrosion. We predict that the Fermi level at the PZC lies above the impurity defect levels of the oxygen vacancies, which are therefore uncharged at the PZC. From the PZC estimate, we predict the voltage needed to create oxygen vacancies with net postive charges within a flatband approximation.

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Lithium/fluorinated graphite (Li/CF _x ) primary batteries show great promise for applications in a wide range of energy storage systems due to their high energy density (>2100 Wh kg ^–1 ) and low self‐discharge rate (<0.5% per year at 25 °C). While the electrochemical performance of the CF _x cathode is indeed promising, the discharge reaction mechanism is not thoroughly understood to date. In this article, a multiscale investigation of the CF _x discharge mechanism is performed using a novel cathode structure to minimize the carbon and fluorine additives for precise cathode characterizations. Titration gas chromatography, X‐ray diffraction, Raman spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, cross‐sectional focused ion beam, high‐resolution transmission electron microscopy, and scanning transmission electron microscopy with electron energy loss spectroscopy are utilized to investigate this system. Results show no metallic lithium deposition or intercalation during the discharge reaction. Crystalline lithium fluoride particles uniformly distributed with <10 nm sizes into the CF _x layers, and carbon with lower sp ² content similar to the hard‐carbon structure are the products during discharge. This work deepens the understanding of CF _x as a high energy density cathode material and highlights the need for future investigations on primary battery materials to advance performance.

In “Interfacial structures and acidity constants (pKa) of goethite from first principles molecular dynamics simulations,” authors Y. Zhang, X. Lui, J. Cheng, and X. Lu apply First Principles molecular dynamics (FPMD, also called Density Functional Theory MD, DFT/MD, or ab initio MD, AIMD), to evaluable the complete set of acidity constants (pK_a) of the hydroxyl groups on the most prominent goethite crystal facets. The pK_a of these OH and OH$^+_2$ groups are compared with available data from the multisite complexation (MUSIC) model traditionally used to estimate pK_a on mineral surfaces. The authors have presented eloquent rationale for the importance and implications of understanding goethite acidity constants in room temperature geochemistry settings. In this paper, I focus on the computational aspects, the strengths of FPMD, and its possibilities.

The treatment of emissions from natural gas engines is an important area of research since methane is a potent greenhouse gas. The benchmark catalysts, based on Pd, still face challenges such as water poisoning and long-term stability. Here we report an approach for catalyst synthesis that relies on the trapping of metal single atoms on the support surface, in thermally stable form, to modify the nature of further deposited metal/metal oxide. By anchoring Pt ions on a catalyst support we can tailor the morphology of the deposited phase. In particular, two-dimensional (2D) rafts of PdOx are formed, resulting in higher reaction rates and improved water tolerance during methane oxidation. The results show that modifying the support by trapping single atoms could provide an important addition to the toolkit of catalyst designers for controlling the nucleation and growth of metal and metal oxide clusters in heterogeneous catalysts. [Figure not available: see fulltext.].

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Lanthanide elements have well-documented similarities in their chemical behavior, which make the valuable trivalent lanthanide cations (Ln3+) particularly difficult to separate from each other in water. In this work, we applyab initiomolecular dynamics simulations to compare the free energies (ΔGads) associated with the adsorption of lanthanide cations to silica surfaces at a pH condition where SiO−groups are present. The predicted ΔGadsfor lutetium (Lu3+) and europium (Eu3+) are similar within statistical uncertainties; this is in qualitative agreement with our batch adsorption measurements on silica. This finding is remarkable because the two cations exhibit hydration free energies (ΔGhyd) that differ by >2 eV, different hydration numbers, and different hydrolysis behavior far from silica surfaces. We observe that the similarity in Lu3+and Eu3+ΔGadsis the result of a delicate cancellation between the difference in Eu3+and Lu3+hydration (ΔGhyd), and their difference in binding energies to silica. We propose that disrupting this cancellation at the two end points, either for adsorbed or completely desorbed lanthanides (e.g.,viananoconfinment or mixed solvents), will lead to effective Ln3+separation.

Graphite fluoride (CFx) cathodes coupled with lithium anodes yield one of the highest theoretical specific capacities (>860 mAh/g) among primary batteries. In practice, the observed discharge voltage (∼2.5 V) is significantly lower than thermodynamic limits (>4.5 V), the discharge rate is low, and so far Li/CFx has only been used in primary batteries. Understanding the discharge mechanism at atomic length scales will improve practical CFx energy density, rate capability, and rechargeability. So far, purely experimental techniques have not identified the correct discharge mechanism or explained the discharge voltage. We apply density functional theory calculations to demonstrate that a CFx-edge propagation discharge mechanism based on lithium insertion at the CF/C boundary in partially discharged CFx exhibits a voltage range of 2.5 to 2.9 V - depending on whether solvent molecules are involved. The voltages and solvent dependence agree with our discharge and galvanostatic intermittent titration technique measurements. The predicted discharge kinetics are consistent with CFx operations. Finally, we predict some Li/CFx rechargeability under the application of high potentials, along a charging pathway different from that of discharge. Our work represents a general, quasi-kinetic framework to understand the discharge of conversion cathodes, circumventing the widely used phase diagram approach which most likely does not apply to Li/CFx because equilibrium conditions are not attained in this system.

Elucidating the mechanisms responsible for sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for understanding pulsed power behavior. Ionization of desorbed impurities in the vacuum regions causes power or current loss; devising methods to limit such desorption during the short time scale of pulsed power is needed to improve corresponding applications. Previous molecular modeling studies have strongly suggested that, under high vacuum conditions, the amount of water impurity desorbing from oxide surfaces on metal electrodes is at a sub-monolayer level at room temperature, which appears insufficient to explain observed pulsed power energy losses at high current densities. In this work, we apply Density Functional Theory (DFT) techniques to show that hydrogen trapped inside iron metal can diffuse into hematite (α-Fe₂O₃) on the metal surface, ultimately reacting with the oxide to form Fe(II) and H₂O. The latter desorbs at elevated temperature and may explain the anomalous amount of desorbed impurity inferred from pulsed-power experiments. We also apply a suite of characterization techniques to demonstrate that when iron metal is heated to 650 °C, the dominant surface oxide component becomes α-Fe₂O₃. The oxide facets exposed are found to be a mixture of (0001), (10-10), and others, in agreement with the DFT models used.

This report describes the high-level accomplishments from the Plasma Science and Engineering Grand Challenge LDRD at Sandia National Laboratories. The Laboratory has a need to demonstrate predictive capabilities to model plasma phenomena in order to rapidly accelerate engineering development in several mission areas. The purpose of this Grand Challenge LDRD was to advance the fundamental models, methods, and algorithms along with supporting electrode science foundation to enable a revolutionary shift towards predictive plasma engineering design principles. This project integrated the SNL knowledge base in computer science, plasma physics, materials science, applied mathematics, and relevant application engineering to establish new cross-laboratory collaborations on these topics. As an initial exemplar, this project focused efforts on improving multi-scale modeling capabilities that are utilized to predict the electrical power delivery on large-scale pulsed power accelerators. Specifically, this LDRD was structured into three primary research thrusts that, when integrated, enable complex simulations of these devices: (1) the exploration of multi-scale models describing the desorption of contaminants from pulsed power electrodes, (2) the development of improved algorithms and code technologies to treat the multi-physics phenomena required to predict device performance, and (3) the creation of a rigorous verification and validation infrastructure to evaluate the codes and models across a range of challenge problems. These components were integrated into initial demonstrations of the largest simulations of multi-level vacuum power flow completed to-date, executed on the leading HPC computing machines available in the NNSA complex today. These preliminary studies indicate relevant pulsed power engineering design simulations can now be completed in (of order) several days, a significant improvement over pre-LDRD levels of performance.

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Controlling sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for pulsed power applications. Despite the short time scales involved, quasi-equilibrium ideas based on transition state theory (TST) and Arrhenius temperature dependence have been widely applied to fit desorption activation free energies. In this work, we apply molecular dynamics (MD) simulations in conjunction with equilibrium potential-of-mean-force (PMF) techniques to directly compute the activation free energies (ΔG∗) associated with desorption of intact water molecules from Fe2O3 and Cr2O3 (0001) surfaces. The desorption free energy profiles are diffuse, without maxima, and have substantial dependences on temperature and surface water coverage. Incorporating the predicted ΔG∗ into an analytical form gives rate equations that are in reasonable agreement with non-equilibrium molecular dynamics desorption simulations. We also show that different ΔG∗ analytical functional forms which give similar predictions at a particular heating rate can yield desorption times that differ by up to a factor of four or more when the ramp rate is extrapolated by 8 orders of magnitude. This highlights the importance of constructing a physically-motivated ΔG∗ functional form to predict fast desorption kinetics.

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