Solvent Self-diffusion Coefficients Research Articles

Molecular Dynamics Simulations of High-Concentration Li[TFSA] Sulfone Solution: Effect of Easy Conformation Change of Sulfolane on Fast Diffusion of Li Ion.

The parameters of the polarizable force field used for molecular dynamics simulations of Li diffusion in high-concentration lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) sulfone (sulfolane, dimethylsulfone, ethylmethylsulfone, and ethyl-i-propylsulfone) solutions were refined. The densities of the solutions obtained by molecular dynamics simulations reproduced well the experimental values. The calculated concentration, temperature, and solvent dependencies of self-diffusion coefficients of ions and solvents in the mixtures well reproduce the experimentally observed dependencies. Ab initio calculations show that the intermolecular interactions between Li ions and four sulfones are not largely different. Conformational analyses show that sulfolane can change the conformation more easily owing to lower barrier height for pseudorotation compared to the rotational barrier heights of diethylsulfone and ethylmethylsulfone. Molecular dynamics simulations indicate that the easy conformation change of solvent affects the rotational relaxation of the solvent and the diffusion of Li ion in the mixture. The easy conformation change of sulfolane is one of the causes of faster diffusion of Li ion in the mixture of Li[TFSA] and sulfolane compared to the mixtures of smaller dimethylsulfone and ethylmethylsulfone.

Diffusional Motion of Solvated Ions in Super-Concentrated Electrolytes

The evolution of solvation structure and dynamics of aqueous LiTFSI based electrolytes with varying salt concentration and competing divalent (Zn2+, Mg2+ and Ca2+) and ammonium based (Me3EtN+) cations were studied using 7Li, 19F and 1H nuclear magnetic resonance (NMR) spectroscopy and pulsed-field gradient (PFG) NMR methods. The NMR peak intensity analysis (Figure 1(a)), reveals that more than half of Li+, TFSI- and H2O molecules are invisible in liquid NMR spectra, likely due to the loss of mobility (broader NMR line width) associated with formation of bigger solvate clusters at higher salt concentrations. The 7Li, 19F and 1H chemical shift values (Figure 1(b)), were shifted to the higher field (more negative chemical shift values) with salt concentration, indicating the interaction between Li+ cations and TFSI- anions became stronger, while the hydrogen bonding network between H2O molecules became weaker resulting from the localization of water clusters in the solutions. The mobility of the remaining species were analyzed through the PFG-NMR based diffusion measurements (Figure 1(c)). It showed that Li+ cation diffuses relatively faster than TFSI- anion (D H2O>D Li>D TFSI) for these aqueous electrolytes, and differ from non-aqueous electrolyte solutions which traditionally register higher anion diffusion rates (D anion > D Li) [1-4]. The D H2O/D TFSI diffusion ratio showed that the relative mobility of water molecules increases with LiTFSI concentration and by addition of multivalent (Zn2+, Mg2+ and Ca2+) cation salt. The D Li/D TFSI diffusion ratio reaches the maximum value of ~3.4 for the 20 m LiTFSI/H2O solution, and the addition of competing cations tends to minimally affect the lithium diffusion. The different behavior between D H2O/D TFSI and D Li/D TFSI values suggest that the localized water molecules diffuse freely in the higher concentration electrolytes, while the diffusion motions of Li+ cation and TFSI- anion depend strongly on the total composition of the competing ions in the solution. The structural and diffusional properties of high concentration electrolytes will be discussed based on diffusion and chemical shift analysis. References Frömling, T., et al., Enhanced Lithium Transference Numbers in Ionic Liquid Electrolytes. J. Phys. Chem. B, 2008. 112(41): p. 12985-12990.Hayamizu, K., Temperature Dependence of Self-Diffusion Coefficients of Ions and Solvents in Ethylene Carbonate, Propylene Carbonate, and Diethyl Carbonate Single Solutions and Ethylene Carbonate + Diethyl Carbonate Binary Solutions of LiPF6 Studied by NMR. J. Chem. Eng. Data, 2012. 57(7): p. 2012-2017.Hayamizu, K., et al., Pulse-Gradient Spin-Echo 1H, 7Li, and 19F NMR Diffusion and Ionic Conductivity Measurements of 14 Organic Electrolytes Containing LiN(SO2CF3)2. J. Phys. Chem. B, 1999. 103(3): p. 519-524.Wu, T.-Y., et al., Influence of LiTFSI Addition on Conductivity, Diffusion Coefficient, Spin–Lattice Relaxation Times, and Chemical Shift of One-Dimensional NMR Spectroscopy in LiTFSI-Doped Dual-Functionalized Imidazolium-Based Ionic Liquids. J. Chem. Eng. Data, 2015. 60(3): p. 471-483. Figure 1

Solvent self-diffusion dependence on the swelling degree of a hydrogel.

This article describes high-field nuclear magnetic resonance experiments using pulsed gradient spin echo methods to investigate water mobility inside homogeneously swollen polyacrylamide hydrogel beads. The NMR data permitted determining the solvent self-diffusion coefficient dependence on either the swelling time or the polymer volume fraction. The sensitivity to the structure of the hydrogel network could be tuned to a certain extent via controlling the diffusion probing time. Relaxation measurements have helped substantiate a theoretical description for these self-diffusion dependencies based upon a fast-exchange two-site model. A tortuosity-porosity dependence is extracted from the model and then compared to other known tortuosity regimes. The diffusion dependence on the degree of swelling obtained here corroborates the existence of a gel swelling-front observed during inhomogeneous solvent imbibition experiments. Finally, we stress that the NMR experimental results reported here are of great value on performing theoretical modeling of gel swelling via solvent imbibition.

Combining Freezing Point Depression and Self-Diffusion Data for Characterizing Aggregation.

The colligative property freezing point depression is evaluated as a means for estimating the extent of aggregation for solutions of poly(ethylene oxide) alcohol (C10E6) nonionic surfactant in cyclohexane. Combined with additional measurements of self-diffusion coefficients, it is shown that both unaggregated C10E6 as well as reverse micelles are significantly present for the entire range of measured C10E6 concentration (0.048-2.35 mol kg-1). A change in speciation near 0.2 mol kg-1 is indicated by the results from both freezing point depression and self-diffusion coefficient measurements. It is shown that average reverse micelle radii and aggregation numbers obtained from the ratio of solvent and C10E6 self-diffusion coefficients are consistent with prior reported results. However, unreasonably small radii for the reverse micelles as well as for the cyclohexane were obtained from analysis of the results by the Stokes-Einstein equation using additional measured solution viscosities. The concentration of reverse micelles and unaggregated C10E6 was calculated from the freezing point depression results using the aggregation numbers obtained from ratio of self-diffusion coefficients. These concentrations indicate that the reverse micelles become smaller in average size and increase in number with increasing temperature without an increase in unaggregated C10E6.

NMR Transport Study of LiPF6 and NaPF6 in Glymes for Use in Supercapacitors

Electric double-layer capacitors (EDLC) store ionic charge electrostatically at the interface of high surface area electrodes such as carbon in a liquid electrolyte. Despite significant improvements in electrode and materials design, virtually all state-of-the-art nonaqueous electrochemical capacitors use the same electrolyte: tetraethylammonium tetrafluoroborate (TEABF4) in acetonitrile (ACN). This electrolyte has an exceptionally high conductivity which minimizes resistive losses and enables capacitors to operate at very high power. However, this electrolyte has a practical voltage window around only 2.7 V, beyond which the capacitor lifetime is significantly shortened. Since the energy stored in a capacitor increases quadratically with voltage, extending this electrochemical window could significantly improve the energy density. In this study we report on electrolytes consisting of LiPF6 or NaPF6 in tetraethylene glycol dimethyl ether (TEGDME or tetraglyme or G4), bis(2-methoxyethyl) ether (diglyme, or G2) and dimethoxyethane (DME or G1) which clearly show a 4 V electrochemical window. The extended voltage window doubles the energy density that can be achieved with any given capacitor electrode. Electrolyte conductivities range from 1-10 mS/cm, which are comparable to ionic liquids and adequate for moderate power applications. Futhermore, glyme-based electrolytes have good chemical stability and low flammability. Importantly, all salts and solvents are commercially available, which should enable these electrolytes to be as cost-effective and scalable as the current generation of commercial supercapacitor electrolytes. NMR experiments were performed on 0.1m LiPF6 and 0.1m/0.8m NaPF6, each dissolved in G1, G2, and G4. Using Pulsed Field Gradient (PFG) NMR, the solvent and ionic self-diffusion coefficients, D, of 1H, 7Li, 19F, and 23Na were measured, at both 25°C and 60°C. As NMR does not distinguish between the movement of single ions and ion pairs, it can be difficult to accurately determine the true conductivity of the material. However, the diffusion measurements were used to find the limiting conductivity, σNMR , of each material via the Nernst-Einstein equation: σNMR = F2[C]/(RT)*(Dcation+Danion) Direct comparison with conductivity values obtained by electrochemical impedance spectroscopy measurements yields the degree of ion association, α: α = 1 - (σdirect/σNMR) Both diffusion and conductivity decrease with increasing solvent size, primarily attributed to viscosity effects. However the degree of ion association is significant, determined to be 85% for both 0.1m LiPF6 and 0.1m NaPF6 in G2. In glyme solvents, ion association tends to decrease with increasing solvent molecular mass, and increase with increasing temperature. These results will be discussed in the context of practical use of glyme-based electrolytes for electrochemical capacitors.

An empirical relation between the limiting ionic molar conductivities and self-diffusion coefficients of pure solvents

The limiting ionic molar conductivity (λ∞) of an electrolyte solution depends on the self-diffusion coefficient (Ds) of the pure solvent when the temperature (T) changes. To study the Ds-dependence of λ∞, we proposed a new empirical relation λ∞∝(Ds/T)t, with a parameter t. The relation is applied to the λ∞ and Ds of alkali, tetra-alkyl ammonium, and halogen ions in water or methanol. All ions except for tetra-alkyl ammonium ions in water exhibit excellent linear relationships in their λ∞∝(Ds/T)tplots, with t in the range from 0.88 to 1.26. This is the first report showing an affirmative linear correlation between λ∞ and Ds.

Computational and Spectroscopic Analysis of Ion Interactions in Sodium and Lithium Ion Battery Electrolytes

Rising interests in sodium ion batteries as low-cost alternatives to lithium ion batteries necessitates a closer look at the interactions between the sodium ion and its anion in electrolyte solution. As demonstrated in lithium ion batteries, solvent and anion species involved in solvation of the lithium ion contribute to the nucleation and growth of the solid electrolyte interphase of the anode. The same is true of sodium ion batteries, which parallel lithium ion batteries in their use of carbonate-based organic solvents and the hexafluorophosphate (PF6 -) anion. Infrared spectroscopy (FTIR) was used to probe the interaction between PF6 - and sodium in various carbonate-based solvent, and these measurements were interpreted using predictions made by density functional theory (DFT) calculations on the model LiPF6 and NaPF6-based solvates. In addition, molecular dynamics (MD) simulations were performed on the EC:DMC/LiPF6 and EC:DMC/NaPF6 electrolytes. A revised many-body polarizable APPLE&P force field was used in MD simulations. Solvate structures extracted from MD simulations were found in good agreement with interpretations of FTIR spectra. Specifically, initial MD results supported our previous finding indicating that the Li+ and Na+ solvation numbers from Raman measurements are found are similar in linear carbonates. Moreover, MD simulations predicted that the PF6 - anion coordination to Li+ and Na+ are quite different. Mono-dentate LiPF6 binding prevailing in LiPF6-DMC, and a combination of bi- and tri-dentate binding dominating in NaPF6-DMC in agreement with the free energies of solvates estimated from DFT cluster – continuum calculations. MD simulations also predicted solvent, anion, Li and Na self-diffusion coefficients in excellent agreement with pfg-NMR measurements.

Hydrated Micellar Structure of Ethoxylated Nonyl Phenols from PGSE NMR

Abstract Solvent self-diffusion coefficients $D_{w}^{*}$ and Dw are respectively determined by PGSE NMR in the bulk solvent and in suitably prepared aqueous micellar solutions of a series of commercial ethoxylated nonyl phenols (ENPs) at 298 and 317 K. The capability of ENP micelles for obstructing the free diffusion of solvent molecules is characterized by the obstruction ratio $K = D_{w}/D_{w}^{*}$, which turns out to depend merely on the volume fraction of EO units present—regardless of significant changes in solute concentration, distribution of EO chain length, micellar aggregation number and temperature. The experiments are interpreted in terms of a renewed analytical model of ENP micellar structure, based on Tanford’s concept of hydrodynamic particle. The results from model fitting return the characteristic sizes of ENP monomers, support the ellipsoid shape of the micelles, indicate a stable EO shell, follow the trend in the variation of hydration number vs. the chain length predicted by thermal analysis in PEO solutions.

Self diffusion coefficients of organic solvents and their binary mixtures with CO2 in silica alcogels at pressures up to 6 MPa derived by NMR pulsed gradient spin echo

Self diffusion coefficients were determined using NMR (nuclear magnetic resonance) pulsed gradient spin echo (PGSE) in combination with a special high pressure autoclave. The goal was to determine the self diffusion coefficients for different CO2/methanol and CO2/ethanol mixtures within the pore phase of silica alcogels at pressures up to 6MPa. These values are required as input data for the modeling of process steps preceding the supercritical drying of these gels.The self diffusion coefficients derived with the set-up at 15°C for unconfined CO2/methanol and CO2/ethanol mixtures as a function of concentration of the organic solvent as well as of fluid pressure are in line with results from previous publications thus proofing the approach to provide reliable data.Measurements of self diffusion coefficients of methanol at different pressures and methanol/CO2 ratios were performed in tetramethoxysilane based silica alcogels with target densities ranging from 80 to 200kg/m3; the results reveal tortuosities of up to 2.5 depending on the silica fraction in the gel as well as its structure. The experimental self diffusion coefficients are in good agreement with the transport diffusion coefficient determined from time resolved NMR imaging of a fluid exchange within a alcogel of methanol for CO2 at 5.8MPa.

Three-dimensional phase-field simulations of membrane porous structure formation by thermally induced phase separation in polymer solutions

We present a three-dimensional phase-field simulation of membrane porous structure formation via spinodal decomposition by the thermally induced phase separation (TIPS) method. The free energy of the polymer solution system was described based on the Flory–Huggins theory, and the mobility was calculated from the solvent self-diffusion coefficients estimated by the free-volume theory of Vrentas and Duta. We explored the effects of initial polymer concentration, quench temperature, and gradient energy parameter on the membrane morphology evolution. The initial domain size increased with the decreasing driving force for the spinodal decomposition and the increasing contribution of the gradient energy to the total energy. The morphology evolution during the intermediate and late stage of spinodal decomposition also depended on the membrane morphology formed at the initial stage, such as bicontinuous or droplet structures. We also simulated the membrane formation under the influence of a polymer concentration gradient in the TIPS process. The polymer concentration gradient led to the formation of membranes with anisotropic pore structures.

Diffusional motion of redox centers in carbonate electrolytes.

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self-diffusion coefficients (D) of solutes and solvents were measured by (1)H and (19)F pulsed field gradient nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC), and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0-50 °C and for various concentrations (0.25-1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increased in all solvents. Since TFSI(-) has fluoromethyl groups (CF3), D(TFSI) could be measured separately and the values found are larger than those for D(Fc1N112) in all samples measured. The EC, PC, and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC, and EMC. A difference in D (D(PC) < D(EC) < D(EMC)), and both a higher E(a) for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112(+), which is a relatively stronger interaction than that between Fc1N112(+) and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that D(PC) = D(EC) = D(EMC) and Fc1N112(+) and all components of the EC/PC/EMC solution have the same E(a) for translational motion, while the ratio D(EC/PC/EMC)/D(Fc1N112) is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112(+) transference numbers lie around 0.4 and increase slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.

Temperature Dependence of Self-Diffusion Coefficients of Ions and Solvents in Ethylene Carbonate, Propylene Carbonate, and Diethyl Carbonate Single Solutions and Ethylene Carbonate + Diethyl Carbonate Binary Solutions of LiPF6 Studied by NMR

The self-diffusion coefficients, D, of lithium, anions, and solvents in four binary-solution electrolytes of ethylene carbonate (EC)–diethyl carbonate (DEC) and three single-solution electrolytes of EC, DEC, and propylene carbonate (PC) including 1 M LiPF6 were measured by 1H, 7Li, and 19F NMR spectroscopy from (353 to 243) K or above freezing for seven solution electrolytes. In the single DEC electrolyte, DLi and DPF6 had almost the same values at every temperature, whereas DLi was smaller than DPF6 in the EC and PC solutions. In the binary EC–DEC electrolytes, as the ratio of EC increased, DLi gradually became smaller, while DPF6 remained almost unchanged in the temperature range studied. At 303 K, the degree of ion dissociation α was evaluated from the ionic conductivity, DLi and DPF6. The α value increased from 0.17 to 0.71 as the EC ratio increased from (0 to 100) %.

Self-diffusion in supercritical water and benzene in high-temperature high-pressure conditions studied by NMR and dynamic solvation-shell model

The self-diffusion coefficients of water and organic solvents in the high-temperature high-pressure conditions are studied by using high-temperature NMR and MD simulation methods. The experimental results are analyzed using a scheme based on the solvation shell relaxation time obtained by MD simulation. The dynamic effect of hydrogen bonding is discussed through the comparison between water and a nonpolar organic solvent, benzene, over a wide range of density and temperature. The hydrogen-bonding effects are as follows: (1) the self-diffusion coefficient of water depends on density more weakly than that of benzene, (2) the self-diffusion coefficient of water at the ambient density depends on temperature more strongly than that of benzene at the density, (3) the turnover from the mobile-shell type to the in-shell type with increasing density does not occur in supercritical water up to the ambient density, whereas such turnover is observed in benzene. These contrasts are reflecting the dynamic effect of the anisotropic attractive interactions.

Self-diffusion of small molecules into rubbery polymers: A lattice free-volume theory

In the framework of the free-volume (FV) theory, a new equation was derived for the evaluation of self-diffusion coefficients of small molecules in polymers above the mixture glass transition temperature. The derivation of the equation turned out to be straightforward once the equivalence between the free volume and the unoccupied volume given by thermodynamic lattice theories is assumed. A parameter evaluation scheme is proposed, which is substantially simpler compared with the conventional Vrentas–Duda approach, even without losing generality. The key assumption is discussed, and its consistency is verified from a numerical viewpoint. A comparison with experimental solvent self-diffusion coefficients for several solvent/polymer binary systems confirmed that the proposed theory presents good correlative ability over wide temperature and composition ranges. Moreover, the introduced thermodynamic foundation allows one to easily include the pressure effect too. In the frame of the proposed lattice free volume theory, the sizes of the polymer jumping units decrease with temperature and increase with pressure. Such behavior converges with theoretical expectations and opens the way for a predictive FV theory. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 529–540, 2010

Steady state analysis of water vapor transport in ionomers

Diffusion coefficients for water in high permeability ionomers are determined from steady state permeation measurements, corrected for boundary layer resistance and change in vapor concentration along sample length, to circumvent problems due to heat of condensation and structural relaxation. Values for water in the perfluoroionomer, Nafion, converted to solvent self-diffusion coefficients, D 1, are consistent with the NMR based free volume (fv) relation for Nafion at high concentrations. At low concentrations D 1 decreases more rapidly than fv values, an effect attributed to ion hydration involving up to 6 water molecules per sulfonate group. The reduction in D 1 due to concentration averaging in permeation, estimated using the fv relation, is about 23%. Water vapor sorption isotherms and steady state values of D 1, for two different types of styrene hydrogenated butadiene triblock ionomers and Nafion can be superimposed using morphology dependent vertical scaling factors. The simple correspondence between results for the hydrocarbon ionomers and Nafion, is attributed to a common transport mechanism based on the restriction of water to ionic pathways. There are a number of claims in the literature that water uptake by highly permeability polymers is greater from the liquid phase than from saturated vapor at unit activity. This paper demonstrates that the disparity, known as Schroeder's paradox, does not occur in sorption under equilibrium conditions or in permeability measurements, if proper corrections for boundary layer resistance and vapor concentration profile are applied.

Heat- and mass-transport in aqueous silica nanofluids

Using the transient hot wire and pulsed field gradient nuclear magnetic resonance methods we determined the thermal conductivity and the solvent self-diffusion coefficient (SDC) in aqueous suspensions of quasi-monodisperse spherical silica nanoparticles. The thermal conductivity was found to increase at higher volume fraction of nanoparticles in accordance with the effective medium theory albeit with a smaller slope. On the other hand, the SDC was found to decrease with nanoparticle volume fraction faster than predicted by the effective medium theory. These deviations can be explained by the presence of an interfacial heat-transfer resistance and water retention by the nanoparticles, respectively. We found no evidence for anomalous enhancement in the transport properties of nanofluids reported earlier by other groups.

Self-diffusion coefficients of organic solvents in linear and branched high density polyethylene particles measured by PFG NMR

Pulsed field gradient nuclear magnetic resonance (PFG NMR) has been performed to study the diffusion of organic solvents into semicrystalline polyethylene particles. Self-diffusion coefficients in different domains of the sample can be extracted through a bi-exponential fit to the echo intensity attenuation, which allows the precise determination of the tortuosity of the polyethylene particles. Further exploration comes from the measurements with branched polyethylene particles and it was found that the diffusion in polymer phase contributed significantly to the slow component of the exponential decay curve.

A Group Contribution-Based Model to Predict Organic Solvent Diffusivities in Amorphous Rubbery Polymers

A modified free-volume model was developed to predict solvent diffusion coefficients in amorphous rubbery polymers, with the introduction of the Sanchez-Lacombe equation-of-state (EOS) into the free-volume theory. The characteristic parameters of the EOS are the only introduced parameters, and they can be determined with the knowledge of polymer structural units. Since all of the parameters with respect to the polymer can be determined by the group contribution method, this model provides feasibility to correlate the solvent diffusivities with polymer structures, without the knowledge of any diffusion or viscoelastic data. The calculations of infinite dilution diffusion coefficients and solvent self-diffusion coefficients for seven kinds of organic solvents in seven kinds of polymers were generally consistent with the published experimental results.

Correlation between thermal diffusion and solvent self-diffusion in semidilute and concentrated polymer solutions

We have performed measurements of thermal diffusion coefficients DT and solvent self-diffusion coefficients Dss in semidilute to concentrated polymer solutions. Solutes of different glass transition temperatures and solvents of different solvent qualities have been used. The investigated systems are in detail: poly(dimethyl-siloxane) in toluene, tristyrene in toluene, polystyrene in toluene, polystyrene in tetrahydrofuran, polystyrene in benzene, and polystyrene in cyclohexane. The thermal diffusion data are compared to our data and literature data for solvent self-diffusion coefficients. In all systems the concentration dependence of DT closely parallels the one of Dss which may be viewed as a local probe for friction on a length scale of the size of one polymer segment. This identifies local friction as the dominating parameter determining the concentration dependence of DT. Solvent quality, in contrast, has no influence on DT.

Development of Many−Body Polarizable Force Fields for Li-Battery Applications: 2. LiTFSI-Doped Oligoether, Polyether, and Carbonate-Based Electrolytes

A quantum chemistry study of Li(+) interactions with ethers, carbonates, alkanes, and a trifluoromethanesulfonylimide anion (TFSI(-)) was performed at the MP2, B3LYP, and HF levels using the aug-cc-pvDz basis set for solvents and TFSI(-) anion, and [8s4p3d/5s3p2d]-type basis set for Li. A classical many-polarizable force field was developed for the LiTFSI salt interacting with ethylene carbonate (EC), gamma-butyrolactone (GBL), dimethyl carbonate (DMC), acetone, oligoethers, n-alkanes, and perfluoroalkanes. Molecular dynamics (MD) simulations were performed for EC/LiTFSI, PC/LiTFSI, GBL/LiTFSI, DMC/LiTFSI, 1,2-dimethoxyethane/LiTFSI, pentaglyme/LiTFSI, and poly(ethylene oxide) (MW = 2380)/LiTFSI electrolytes at temperatures from 298 to 423 K and salt concentrations from 0.3 to 5 M. The ion and solvent self-diffusion coefficients, electrolyte conductivity, electrolyte density, LiTFSI apparent molar volumes, and structure of the Li(+) cation environment predicted by MD simulations were found in good agreement with experimental data.