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All sources NASA NTRS DOE OSTI

DOE OSTI2019

Localized High Concentration Electrolyte Behavior near a Lithium-Metal Anode Surface

Wide-scale practical application of rechargeable lithium-metal batteries remains a significant challenge due to dendrite growth. To overcome this challenge, electrolytes must be designed to allow for the formation of protective solid electrolyte interphase (SEI) layers on the highly reactive lithium-metal anode (LMA) surfaces. Recently, novel localized high-concentration electrolytes (LHCEs) were introduced as a potential solution to enable dendrite-free cycling of LMAs, by using an inert solvent to “dilute” the high concentration electrolytes. Ideally, the diluent itself does not dissolve the salt but is miscible with the solvent to form a localized high concentrated salt/solvent cluster surrounded by the diluent. However, detailed structure and potential surface reactions that may take place in LHCE environment are not yet clear. In this work, we investigated the reactivity of a 1M lithium bis(fluorosulfonyl)imide (LiFSI) in a mixture of dimethoxyethane (DME)/Tris(2,2,2-trifluoroethyl)orthoformate (TFEO) (1:3 by mol) electrolyte near a Li metal surface based on density functional theory and ab-initio molecular dynamics (MD) simulations. Selected liquid interfacial configurations were obtained from classical MD simulasults indicate that when salt and TFEO molecules are close to each other and to the surface, fluorine anions resulting from the fast salt anion decomposition can trigger a cascade of reactions that lead to the decomposition of TFEO. However, if the Li cation is initially solvated by DME and the anion forming a complex, the stability of the anion increases significantly. The Li solvated structure is implied in the LHCE concept; however statistically the larger amount of TFEO molecules suggest also the first scenario leading to TFEO decomposition. Therefore, the broader implication of our simulations is that the defluorination of TFEO may contribute, together with the anion decomposition, to the observed rapid formation of a stable SEI on the surface of the lithium metal; consequently, favorably affecting the stability of LMAs during battery operation.

Zheng, Yu↗

DOE OSTI2024

Elucidating and contrasting the mechanisms for Mg and Ca sulfate ion-pair formation with multi-level embedded quantum mechanics/molecular dynamics simulations

Here, solutions and minerals containing sulfate (SO 4 2- ), and Ca 2+ and Mg 2+ cations, are ubiquitous throughout the lithosphere and are significant components of seawater, thus presenting a prototypical system for the study of strong electrolytes and crystal nucleation mechanisms. However, despite their relative abundance, key questions remain unanswered about the most fundamental atomic-level steps of their mineralization pathways and aqueous dynamics. Here, we carry out enhanced sampling multi-level molecular dynamics (MD) embedded correlated wavefunction theory simulations to elucidate ion-pairing mechanisms for Mg–SO 4 and Ca–SO 4 in concentrated aqueous solution, accurately capturing effects arising from both structural dynamics and electron exchange–correlation. We predict contact-ion-pair formation to be barrierless and highly exoergic for Ca–SO 4 , in agreement with its minimal solubility, whereas for Mg–SO 4 , solvent-shared and contact ion pairs have similar free energies, qualitatively consistent with its higher solubility. Finally, we demonstrate that brief high-temperature pre-equilibration may be utilized to accelerate convergence of free energies in blue-moon-ensemble enhanced-sampling MD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

On the mechanisms of ion adsorption to aqueous interfaces: air-water vs. oil-water

The adsorption of ions to water-hydrophobe interfaces influences a wide range of phenomena, including chemical reaction rates, ion transport across biological membranes, and electrochemical and many catalytic processes; hence, developing a detailed understanding of the behavior of ions at water-hydrophobe interfaces is of central interest. Here, we characterize the adsorption of the chaotropic thiocyanate anion (SCN − ) to two prototypical liquid hydrophobic surfaces, water-toluene and water-decane, by surface-sensitive nonlinear spectroscopy and compare the results against our previous studies of SCN − adsorption to the air-water interface. For these systems, we observe no spectral shift in the charge transfer to solvent spectrum of SCN − , and the Gibb’s free energies of adsorption for these three different interfaces all agree within error. We employed molecular dynamics simulations to develop a molecular-level understanding of the adsorption mechanism and found that the adsorption for SCN − to both water-toluene and water-decane interfaces is driven by an increase in entropy, with very little enthalpic contribution. This is a qualitatively different mechanism than reported for SCN − adsorption to the air-water and graphene-water interfaces, wherein a favorable enthalpy change was the main driving force, against an unfavorable entropy change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Results of Hg Speciation Testing on 2Q15 Tank 50 WAC and Cs-Decontaminated Tank 21 Waste Samples

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The fourth shipment of samples was designated to include 2Q15 Tank 50 WAC material (HTF-50-15-39) collected on April 7, 2015, and Tank 21 material (HTF-21-15-32, HTF-21-15-36, and HTF-21-15-37) the first collected on March 9 and the second two collected on April 6, 2015. The combined samples were subjected to Cs-decontamination through the use of MCU solvent. Samples were collected with the minimum possible free headspace and refrigerated prior to final dilution.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2015

Results of Hg Speciation Testing on 2Q15 Tank 50 WAC and Cs-Decontaminated Tank 21 Waste Samples (Rev.1)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

NASA NTRS1978

Configurations of base-pair complexes in solutions

A theoretical search for the most stable conformations (i.e., stacked or hydrogen bonded) of the base pairs A-U and G-C in water, CCl4, and CHCl3 solutions is presented. The calculations of free energies indicate a significant role of the solvent in determining the conformations of the base-pair complexes. The application of the continuum method yields preferred conformations in good agreement with experiment. Results of the calculations with this method emphasize the importance of both the electrostatic interactions between the two bases in a complex, and the dipolar interaction of the complex with the entire medium. In calculations with the solvation shell method, the last term, i.e., dipolar interaction of the complex with the entire medium, was added. With this modification the prediction of the solvation shell model agrees both with the continuum model and with experiment, i.e., in water the stacked conformation of the bases is preferred.

Egan, J. T.↗

NASA NTRS1981

Physical aging of linear and network epoxy resins

Network and linear epoxy resins principally based on the diglycidyl ether of bisphenol-A and its oligomers are prepared and studied using diamine and anhydride crosslinking agents. Rubber modified epoxies and a carbon fiber reinforced composite are also investigated. All materials display time-dependent changes when stored at temperatures below the glass transition temperature after quenching (sub-T/g/ annealing). Solvent sorption experiments initiated after different sub-T(g) annealing times demonstrate that the rate of solvent uptake can be indirectly related to the free volume of the epoxy resins. Residual thermal stresses and water are found to have little effect on the physical aging process, which affects the sub-T(g) properties of uniaxial carbon fiber reinforced epoxy material. Finally, the importance of the recovery phenomenon which affects the durability of epoxy glasses is considered.

Kong, E. S.-W.↗

DOE OSTI2023

Direct recycling of lithium-ion battery scraps for manufacturing a new anode

An improved method of recycling lithium-ion battery anode scraps is provided. The method involves isolating an anode scrap including a graphite anode film adhered to a current collector foil with a polyvinylidene fluoride binder. The anode scrap is combined with deionized water to form a first mixture. The graphite anode film is delaminated from the current collector foil to form a second mixture comprising a free collector foil and a free graphite anode film. The free graphite anode film is filtered and dried from the second mixture to recover the free graphite anode film. The free graphite anode film is combined with a solvent comprising N-methyl-2-pyrrolidone (NMP) to form an anode formation slurry. The slurry is coated onto a copper current collector to produce a new anode.

Bai, Yaocai↗

DOE OSTI2019

String Method for Protein–Protein Binding Free-Energy Calculations

A powerful computational strategy to determine the equilibrium association constant of two macromolecules with explicit-solvent molecular dynamics (MD) simulations is the "geometric route", which considers the reversible physical separation of the bound complex in solution. Nonetheless, multiple challenges remain to render this type of methodology reliable and computationally efficient in practice. In particular, in one, formulation of the geometric route relies on the potential of mean force (PMF) for physically separating the two binding partners restrained along a straight axis, which must be selected prior to the calculation. However, practical applications indicate that the calculation of the separation PMF along the predefined rectilinear pathway may be suboptimal and slowly convergent. Recognizing that a rectilinear straight separation pathway is generally not representative of how the protein complex physically separates in solution, we put forth a novel theoretical framework for binding free-energy calculations, leaning on the optimal curvilinear minimum free-energy path (MFEP) determined from the string method. The proposed formalism is validated by comparing the results obtained using both rectilinear and curvilinear pathways for a prototypical host-guest complex formed by cucurbit[7]uril (CB[7]) binding benzene, and for the barnase-barstar protein complex. On the basis of multi-microsecond MD calculations, we find that the calculations following the traditional rectilinear pathway and the string-based curvilinear pathway agree quantitatively, but convergence is faster with the latter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1989

Contamination removal using various solvents and methodologies

Critical and non-critical bonding surfaces must be kept free of contamination that may cause potential unbonds. For example, an aft-dome section of a redesigned solid rocket motor that had been contaminated with hydraulic oil did not appear to be sufficiently cleaned when inspected by the optically stimulated electron emission process (Con Scan) after it had been cleaned using a hand double wipe cleaning method. As a result, current and new cleaning methodologies as well as solvent capability in removing various contaminant materials were reviewed and testing was performed. Bonding studies were also done to verify that the cleaning methods used in removing contaminants provide an acceptable bonding surface. The removal of contaminants from a metal surface and the strength of subsequent bonds were tested using the Martin Marietta and double-wipe cleaning methods. Results are reported.

Jeppsen, J. C.↗

DOE OSTI2014

Investigations of α-helix↔β-sheet transition pathways in a miniprotein using the finite-temperature string method

A parallel implementation of the finite-temperature string method is described, which takes into account the invariance of coordinates with respect to rigid-body motions. The method is applied to the complex α-helix↔β-sheet transition in a β-hairpin miniprotein in implicit solvent, which exhibits much of the complexity of conformational changes in proteins. Two transition paths are considered, one derived from a linear interpolant between the endpoint structures and the other derived from a targeted dynamics simulation. Two methods for computing the conformational free energy (FE) along the string are compared, a restrained method, and a tessellation method introduced by E. Vanden-Eijnden and M. Venturoli [J. Chem. Phys. 130, 194103 (2009)]. It is found that obtaining meaningful free energy profiles using the present atom-based coordinates requires restricting sampling to a vicinity of the converged path, where the hyperplanar approximation to the isocommittor surface is sufficiently accurate. This sampling restriction can be easily achieved using restraints or constraints. The endpoint FE differences computed from the FE profiles are validated by comparison with previous calculations using a path-independent confinement method. The FE profiles are decomposed into the enthalpic and entropic contributions, and it is shown that the entropy difference contribution can be as large as 10 kcal/mol for intermediate regions along the path, compared to 15–20 kcal/mol for the enthalpy contribution. This result demonstrates that enthalpic barriers for transitions are offset by entropic contributions arising from the existence of different paths across a barrier. The possibility of using systematically coarse-grained representations of amino acids, in the spirit of multiple interaction site residue models, is proposed as a means to avoid ad hoc sampling restrictions to narrow transition tubes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

VR-SCOSMO: A smooth conductor-like screening model with charge-dependent radii for modeling chemical reactions

To better represent the solvation effects observed along reaction pathways, and of ionic species in general, a charge-dependent variable-radii smooth conductor-like screening model (VR-SCOSMO) is developed. This model is implemented and parameterized with a third order density-functional tight binding quantum model, DFTB3/3OB-OPhyd, a quantum method which was developed for organic and biological compounds, utilizing a specific parameterization for phosphate hydrolysis reactions. Unlike most other applications with the DFTB3/3OB model, an auxiliary set of atomic multipoles is constructed from the underlying DFTB3 density matrix which is used to interact the solute with the solvent response surface. The resulting method is variational, produces smooth energies, and has analytic gradients. As a baseline, a conventional SCOSMO model with fixed radii is also parameterized. The SCOSMO and VR-SCOSMO models shown have comparable accuracy in reproducing neutral-molecule absolute solvation free energies; however, the VR-SCOSMO model is shown to reduce the mean unsigned errors (MUEs) of ionic compounds by half (about 2-3 kcal/mol). The VR-SCOSMO model presents similar accuracy as a charge-dependent Poisson-Boltzmann model introduced by Hou et al. [J. Chem. Theory Comput. 6, 2303 (2010)]. VR-SCOSMO is then used to examine the hydrolysis of trimethylphosphate and seven other phosphoryl transesterification reactions with different leaving groups. Two-dimensional energy landscapes are constructed for these reactions and calculated barriers are compared to those obtained from ab initio polarizable continuum calculations and experiment. Results of the VR-SCOSMO model are in good agreement in both cases, capturing the rate-limiting reaction barrier and the nature of the transition state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Machine Learning-Guided Approach for Studying Solvation Environments

Molecular-level understanding and characterization of solvation environments are often needed across chemistry, biology, and engineering. Toward practical modeling of local solvation effects of any solute in any solvent, in this work, we report a static and all-quantum mechanics-based cluster-continuum approach for calculating single-ion solvation free energies. This approach uses a global optimization procedure to identify low-energy molecular clusters with different numbers of explicit solvent molecules and then employs the smooth overlap for atomic positions learning kernel to quantify the similarity between different low-energy solute environments. From these data, we use sketch maps, a nonlinear dimensionality reduction algorithm, to obtain a two-dimensional visual representation of the similarity between solute environments in differently sized microsolvated clusters. After testing this approach on different ions having charges 2+, 1+, 1–, and 2–, we find that the solvation environment around each ion can be seen to usually become more similar in hand with its calculated single-ion solvation free energy. Without needing either dynamics simulations or an a priori knowledge of local solvation structure of the ions, this approach can be used to calculate solvation free energies within 5% of experimental measurements for most cases, and it should be transferable for the study of other systems where dynamics simulations are not easily carried out.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Solvent effects on extractant conformational energetics in liquid–liquid extraction: a simulation study of molecular solvents and ionic liquids

Extractant design in liquid–liquid extraction (LLE) is a research frontier of metal ion separations that typically focuses on the direct extractant–metal interactions. However, a more detailed understanding of energetic drivers of separations beyond primary metal coordination is often lacking, including the role of solvent in the extractant phase. In this work, we propose a new mechanism for enhancing metal-complexant energetics with nanostructured solvents. Using molecular dynamics simulations with umbrella sampling, we find that the organic solvent can reshape the energetics of the extractant's intramolecular conformational landscape. Here, we calculate free energy profiles of different conformations of a representative bidentate extractant, n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO), in four different solvents: dodecane, tributyl phosphate (TBP), and dry and wet ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]). By promoting reorganization of the extractant molecule into its binding conformation, our findings reveal how particular solvents can ameliorate this unfavorable step of the metal separation process. In particular, the charge alternating nanodomains formed in ILs substantially reduce the free energy penalty associated with extractant reorganization. Importantly, using alchemical free energy calculations, we find that this stabilization persists even when we explicitly include the extracted cation. These findings provide insight into the energetic drivers of metal ion separations and potentially suggest a new approach to designing effective separations using a molecular-level understanding of solvent effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Multiply Reduced Oligofluorenes: Their Nature and Pairing with THF-Solvated Sodium Ions

Conjugated oligofluorenes are chemically reduced up to five charges in tetrahydrofuran solvent and confirmed with clear spectroscopic evidence. Stimulated by these experimental results, we have conducted a comprehensive computational study of the electronic structure and the solvation structure of representative oligofluorene anions with a focus on the pairing between sodium ions and these multianions. In addition, using density functional theory (DFT) methods and a solvation model of both explicit solvent molecules and implicit polarizable continuum, we first elucidate the structure of tightly solvated free sodium ions, and then explore the pairing of sodium ions either in contact with reduced oligofluorenes or as solvent-separated ion pairs. Computed time-dependent-DFT absorption spectra are compared with experiments to assign the dominant ion pairing structure for each multianion. Computed ion pair binding energies further support our assignment. Lastly, the availability of different length and reducing level of oligofluorenes enables us to investigate the effects of total charge and charge density on the binding with sodium ions, and our results suggest both factors play important roles in ion pairing for small molecules. However, as the oligofluorene size grows, its charge density determines the binding strength with the sodium ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Solvent-Mediated Crystallization of CH 3 NH 3 SnI 3 Films for Heterojunction Depleted Perovskite Solar Cells

Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ~20%. However, the potential toxicity of lead in these systems raises environmental concerns for widespread deployment. In this work we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH 3 NH 3 SnI 3 ) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI 2 ·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO 2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm –2 . Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH 3 NH 3 SnI 3 perovskite device which are one order of magnitude larger than CH 3 NH 3 PbI 3 -based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Stabilizing Graphite Anode in Electrolytes with Nanoscale Anion Networking for High-Rate Lithium Storage

Graphite is the preferred anode material in commercial lithium-ion batteries (LIBs), but its limited compatibility with various organic molecules restricts the electrolyte solvent options. The primary challenge is solvent co-intercalation with Li ions, leading to graphite layer exfoliation. As a result, electrolyte selection often relies on ethylene carbonate (EC)-based solvents. Here, in this study, we introduce electrolytes featuring a nanoscale anion network ordering that hinders the liquid-phase exfoliation of graphite. This network, formed from concentrated long-chain lithium salts, traps free dioxolane (DOL) molecules, reducing the interactions between graphite particles and solvents during Li intercalation. Our findings reveal a mechanism that stabilizes graphite in otherwise unstable solvents with concentrated salts like LiTFSI, providing key insights for improving LIB performance by addressing electrolyte limitations on graphite anodes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2025

Correlating Solvation Free Energy to Electrolyte Properties for Lithium Metal Batteries

The electrolyte plays a critical role in lithium metal batteries. In particular, ion solvation profoundly impacts key electrolyte properties and battery performance. Here, in this study, we systematically investigate solvation-property relationships in a series of electrolytes with different solvent-diluent ratios. Through potentiometric techniques that measure the relative solvation free energies of electrolytes, we find that weaker solvation correlates with larger ion clusters, lower ionic conductivity and diffusion coefficient, and superior electrochemical stability. Weaker solvation leads to the formation of a small number of Li clusters with large hydrodynamic radii, which lowers the Li + diffusivity and ionic conductivity of the electrolyte. Concurrently, weaker solvation leads to improved electrochemical stability at both the cathode and anode interfaces. Understanding these solvation-property relationships and trade-offs is important to designing electrolytes for optimized lithium metal battery performance.

25 ENERGY STORAGE↗