Diffusion and structure of propylene carbonate-metal salt electrolyte solutions for post-lithium-ion batteries: From experiment to simulation.

The diffusion of cations in organic solvent solutions is important for the performance of metal-ion batteries. In this article, pulsed field gradient nuclear magnetic resonance experiments and fully atomistic molecular dynamic simulations were employed to study the temperature-dependent diffusive behavior of various liquid electrolytes representing 1M propylene carbonate solutions of metal salts with bis(trifluoromethylsulfonyl)imide (TFSI-) or hexafluorophosphate (PF6-) anions commonly used in lithium-ion batteries and beyond. The experimental studies revealed the temperature dependence of the diffusion coefficients for the propylene carbonate (PC) solvent and for the anions following an Arrhenius type of behavior. It was observed that the PC molecules are the faster species. For the monovalent cations (Li+, Na+, K+), the PC solvent diffusion was enhanced as the cation size increased, while for the divalent cations (Mg2+, Ca2+, Sr2+, Ba2+), the opposite trend was observed, i.e., the diffusion coefficients decreased as the cation size increased. The anion diffusion in LiTFSI and NaTFSI solutions was found to be similar, while in electrolytes with divalent cations, a decrease in anion diffusion with increasing cation size was observed. It was shown that non-polarizable charge-scaled force fields could correspond perfectly to the experimental values of the anion and PC solvent diffusion coefficients in salt solutions of both monovalent (Li+, Na+, K+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations at a range of operational temperatures. Finally, after calculating the radial distribution functions between cations, anions, and solvent molecules, the increase in the PC diffusion coefficient established with the increase in cation size for monovalent cations was clearly explained by the large hydration shell of small Li+ cations, due to their strong interaction with the PC solvent. In solutions with larger monovalent cations, such as Na+, and with a smaller solvation shell of PC, the PC diffusion is faster due to more liberated solvent molecules. In the salt solutions with divalent cations, both the anion and the PC diffusion coefficients decreased as the cation size increased due to an enhanced cation-anion coordination, which was accompanied by an increase in the amount of PC in the cation solvation shell due to the presence of anions.

Ionic poly(dimethylsiloxane)-silica nanocomposites: Dispersion and self-healing.

Abstract: Poly(dimethylsiloxane) (PDMS)-based nanocomposites have attracted increasing attention due to their inherent outstanding properties. Nevertheless, the realization of high levels of dispersion of nanosilicas in PDMS represents a challenge arising from the poor compatibility between the two components. Herein, we explore the use of ionic interactions located at the interface between silica and a PDMS matrix by combining anionic sulfonate-functionalized silica and cationic ammonium-functionalized PDMS. A library of ionic PDMS nanocomposites was synthesized and characterized to highlight the impact of charge location, density, and molecular weight of ionic PDMS polymers on the dispersion of nanosilicas and the resulting mechanical reinforcement. The use of reversible ionic interactions at the interface of nanoparticles-polymer matrix enables the healing of scratches applied to the surface of the nanocomposites. Molecular dynamics simulations were used to estimate the survival probability of ionic cross-links between nanoparticles and the polymer matrix, revealing a dependence on polymer charge density. Impact statement: Poly(dimethylsiloxane) (PDMS) has been widely used in diverse applications due to its inherent attractive and multifunctional properties including optical transparency, high flexibility, and biocompatibility. The combination of such properties in a single polymer matrix has paved the way toward a wide range of applications in sensors, electronics, and biomedical devices. As a liquid at room temperature, the cross-linking of the PDMS turns the system into a mechanically stable elastomer for several applications. Nanofillers have served as a reinforcing agent to design PDMS nanocomposites. However, due to significant incompatibility between silica and the PDMS matrix, the dispersion of nanosilica fillers has been challenging. One of the existing strategies to improve nanoparticle dispersion consists of grafting oppositely charged ionic functional groups to the nanoparticle surface and the polymer matrix, respectively, creating nanoparticle ionic materials. Here, this approach has been explored further to improve the dispersion of nanosilicas in a PDMS matrix. The designed ionic PDMS nanocomposites exhibit self-healing properties due to the reversible nature of ionic interactions. The developed synthetic approach can be transferred to other kinds of inorganic nanoparticles dispersed in a PDMS matrix, where dispersion at the nanometer scale is a prerequisite for specific applications such as encapsulants for light-emitting diodes (LEDs). Supplementary information: The online version contains supplementary material available at 10.1557/s43577-022-00346-x.

Insights from modeling into structure, entanglements, and dynamics in attractive polymer nanocomposites.

Conformations, entanglements and dynamics in attractive polymer nanocomposites are investigated in this work by means of coarse-grained molecular dynamics simulation, for both weak and strong confinements, in the presence of nanoparticles (NPs) at NP volume fractions φ up to 60%. We show that the behavior of the apparent tube diameter dapp in such nanocomposites can be greatly different from nanocomposites with nonattractive interactions. We find that this effect originates, based on a mean field argument, from the geometric confinement length dgeo at strong confinement (large φ) and not from the bound polymer layer on NPs (interparticle distance ID <2Rg) as proposed recently based on experimental measurements. Close to the NP surface, the entangled polymer mobility is reduced in attractive nanocomposites but still faster than the NP mobility for volume fractions beyond 20%. Furthermore, entangled polymer dynamics is hindered dramatically by the strong confinement created by NPs. For the first time using simulations, we show that the entangled polymer conformation, characterized by the polymer radius of gyration Rg and form factor, remains basically unperturbed by the presence of NPs up to the highest volume fractions studied, in agreement with various experiments on attractive nanocomposites. As a side-result we demonstrate that the loose concept of ID can be made a microscopically well defined quantity using the mean pore size of the NP arrangement.

The effect of different organic solvents on sodium ion storage in carbon nanopores.

In this study fully atomistic grand canonical Monte Carlo (GCMC) simulations have been employed to study the behaviour of an electrolyte salt (NaPF6) and different non-aqueous (organic) solvents in carbon nanopores, to reveal the structure and storage mechanism. Organic solutions of Na+ and PF6- ions at 1 M concentration were considered, based on the conditions in operational sodium ion batteries and supercapacitors. Three organic solvents with different properties were selected: ethylene carbonate (EC), propylene carbonate (PC), and ethyl methyl carbonate (EMC). The effects of solvents, pore size and surface charge were quantified by calculating the radial distribution functions and ionic density profiles. It is shown that the organic solvent properties and nanopore confinement can affect the structure of the organic electrolyte solution. For the pore size range (1-5 nm) investigated in this paper, the surface charge used in this study can alter the sodium ions but not the solvent structure inside the pore.

Polymer and spherical nanoparticle diffusion in nanocomposites.

Nanoparticle and polymer dynamics in nanocomposites containing spherical nanoparticles were investigated by means of molecular dynamics simulations. We show that the polymer diffusivity decreases with nanoparticle loading due to an increase of the interfacial area created by nanoparticles, in the polymer matrix. We show that small sized nanoparticles can diffuse much faster than that predicted from the Stokes-Einstein relation in the dilute regime. We show that the nanoparticle diffusivity decreases at higher nanoparticle loading due to nanoparticle-polymer interface. Increase of the nanoparticle radius slows the nanoparticle diffusion.

Entanglements in polymer nanocomposites containing spherical nanoparticles.

We investigate the polymer packing around nanoparticles and polymer/nanoparticle topological constraints (entanglements) in nanocomposites containing spherical nanoparticles in comparison to pure polymer melts using molecular dynamics (MD) simulations. The polymer-nanoparticle attraction leads to good dispersion of nanoparticles. We observe an increase in the number of topological constraints (decrease of total entanglement length Ne with nanoparticle loading in the polymer matrix) in nanocomposites due to nanoparticles, as evidenced by larger contour lengths of the primitive paths. An increase of the nanoparticle radius reduces the polymer-particle entanglements. These studies demonstrate that the interaction between polymers and nanoparticles does not affect the total entanglement length because in nanocomposites with small nanoparticles, the polymer-nanoparticles topological constraints dominate.

Effects of pore size and surface charge on Na ion storage in carbon nanopores.

Na ion batteries (NIBs) are considered as a promising low cost and sustainable energy storage technology. To better design nanoporous carbons as anode materials for NIBs, molecular dynamics simulations have been employed to study the behavior of Na+ ions (as well as PF6- ions) confined within carbon nanopores, in the presence of non-aqueous (organic) solvent. The effects of pore size and surface charge density were quantified by calculating ionic density profiles and concentration within the pores. Carbon slit pores of widths 0.72-10 nm were considered. The carbon surfaces were charged with densities of 0 (neutral pores), -0.8e nm-2, -1.2e nm-2, and -2e nm-2. Organic solutions of Na+ and PF6- at 1 M concentrations were considered under operating conditions of sodium ion batteries. As the surface charge density increases, more Na+ ions enter the pores. In all pores, when the surface is highly charged the Na+ ions move toward the negatively charged graphene surfaces because of counterion condensation effects. In some instances, our results reveal the formation of multiple layers of adsorbed Na+ inside the pores. Both the nanopore width and surface charge alter the density profiles of ions and solvent inside the pores.

Polymer conformations in polymer nanocomposites containing spherical nanoparticles.

We investigate the effect of various spherical nanoparticles on chain dimensions in polymer melts for high nanoparticle loading which is larger than the percolation threshold, using molecular dynamics simulations. We show that polymer chains are unperturbed by the presence of repulsive nanoparticles. In contrast polymer chains can be perturbed by the presence of attractive nanoparticles when the polymer radius of gyration is larger than the nanoparticle radius. At high nanoparticle loading, chains can be stretched and flattened by the nanoparticles, even oligomers can expand under the presence of attractive nanoparticles of very small size.

Molecular Simulation of Covalent Adaptable Networks and Vitrimers: A Review.

Covalent adaptable networks and vitrimers are novel polymers with dynamic reversible bond exchange reactions for crosslinks, enabling them to modulate their properties between those of thermoplastics and thermosets. They have been gathering interest as materials for their recycling and self-healing properties. In this review, we discuss different molecular simulation efforts that have been used over the last decade to investigate and understand the nanoscale and molecular behaviors of covalent adaptable networks and vitrimers. In particular, molecular dynamics, Monte Carlo, and a hybrid of molecular dynamics and Monte Carlo approaches have been used to model the dynamic bond exchange reaction, which is the main mechanism of interest since it controls both the mechanical and rheological behaviors. The molecular simulation techniques presented yield sufficient results to investigate the structure and dynamics as well as the mechanical and rheological responses of such dynamic networks. The benefits of each method have been highlighted. The use of other tools such as theoretical models and machine learning has been included. We noticed, amongst the most prominent results, that stress relaxes as the bond exchange reaction happens, and that at temperatures higher than the glass transition temperature, the self-healing properties are better since more bond BERs are observed. The lifetime of dynamic covalent crosslinks follows, at moderate to high temperatures, an Arrhenius-like temperature dependence. We note the modeling of certain properties like the melt viscosity with glass transition temperature and the topology freezing transition temperature according to a behavior ruled by either the Williams-Landel-Ferry equation or the Arrhenius equation. Discrepancies between the behavior in dissociative and associative covalent adaptable networks are discussed. We conclude by stating which material parameters and atomistic factors, at the nanoscale, have not yet been taken into account and are lacking in the current literature.

Structure and Diffusion of Ionic PDMS Melts.

Ionic polymers exhibit mechanical properties that can be widely tuned upon selectively charging them. However, the correlated structural and dynamical properties underlying the microscopic mechanism remain largely unexplored. Here, we investigate, for the first time, the structure and diffusion of randomly and end-functionalized ionic poly(dimethylsiloxane) (PDMS) melts with negatively charged bromide counterions, by means of atomistic molecular dynamics using a united atom model. In particular, we find that the density of the ionic PDMS melts exceeds the one of their neutral counterpart and increases as the charge density increases. The counterions are condensed to the cationic part of end-functionalized cationic PDMS chains, especially for the higher molecular weights, leading to a slow diffusion inside the melt; the counterions are also correlated more strongly to each other for the end-functionalized PDMS. Temperature has a weak effect on the counterion structure and leads to an Arrhenius type of behavior for the counterion diffusion coefficient. In addition, the charge density of PDMS chains enhances the diffusion of counterions especially at higher temperatures, but hinders PDMS chain dynamics. Neutral PDMS chains are shown to exhibit faster dynamics (diffusion) than ionic PDMS chains. These findings contribute to the theoretical description of the correlations between structure and dynamical properties of ion-containing polymers.

From Ionic Nanoparticle Organic Hybrids to Ionic Nanocomposites: Structure, Dynamics, and Properties: A Review.

Ionic nanoparticle organic hybrids have been the focus of research for almost 20 years, however the substitution of ionic canopy by an ionic-entangled polymer matrix was implemented only recently, and can lead to the formulation of ionic nanocomposites. The functionalization of nanoparticle surface by covalently grafting a charged ligand (corona) interacting electrostatically with the oppositely charged canopy (polymer matrix) can promote the dispersion state and stability which are prerequisites for property "tuning", polymer reinforcement, and fabrication of high-performance nanocomposites. Different types of nanoparticle, shape (spherical or anisotropic), loading, graft corona, polymer matrix type, charge density, molecular weight, can influence the nanoparticle dispersion state, and can alter the rheological, mechanical, electrical, self-healing, and shape-memory behavior of ionic nanocomposites. Such ionic nanocomposites can offer new properties and design possibilities in comparison to traditional polymer nanocomposites. However, to achieve a technological breakthrough by designing and developing such ionic nanomaterials, a synergy between experiments and simulation methods is necessary in order to obtain a fundamental understanding of the underlying physics and chemistry. Although there are a few coarse-grained simulation efforts to disclose the underlying physics, atomistic models and simulations that could shed light on the interphase, effect of polymer and nanoparticle chemistry on behavior, are completely absent.

Ionic Polymer Nanocomposites Subjected to Uniaxial Extension: A Nonequilibrium Molecular Dynamics Study.

We explore the behavior of coarse-grained ionic polymer nanocomposites (IPNCs) under uniaxial extension up to 800% strain by means of nonequilibrium molecular dynamics simulations. We observe a simultaneous increase of stiffness and toughness of the IPNCs upon increasing the engineering strain rate, in agreement with experimental observations. We reveal that the excellent toughness of the IPNCs originates from the electrostatic interaction between polymers and nanoparticles, and that it is not due to the mobility of the nanoparticles or the presence of polymer-polymer entanglements. During the extension, and depending on the nanoparticle volume fraction, polymer-nanoparticle ionic crosslinks are suppressed with the increase of strain rate and electrostatic strength, while the mean pore radius increases with strain rate and is altered by the nanoparticle volume fraction and electrostatic strength. At relatively low strain rates, IPNCs containing an entangled matrix exhibit self-strengthening behavior. We provide microscopic insight into the structural, conformational properties and crosslinks of IPNCs, also referred to as polymer nanocomposite electrolytes, accompanying their unusual mechanical behavior.

Polymer Conformations, Entanglements and Dynamics in Ionic Nanocomposites: A Molecular Dynamics Study.

We investigate nanoparticle (NP) dispersion, polymer conformations, entanglements and dynamics in ionic nanocomposites. To this end, we study nanocomposite systems with various spherical NP loadings, three different molecular weights, two different Bjerrum lengths, and two types of charge-sequenced polymers by means of molecular dynamics simulations. NP dispersion can be achieved in either oligomeric or entangled polymeric matrices due to the presence of electrostatic interactions. We show that the overall conformations of ionic oligomer chains, as characterized by their radii of gyration, are affected by the presence and the amount of charged NPs, while the dimensions of charged entangled polymers remain unperturbed. Both the dynamical behavior of polymers and NPs, and the lifetime and amount of temporary crosslinks, are found to depend on the ratio between the Bjerrum length and characteristic distance between charged monomers. Polymer-polymer entanglements start to decrease beyond a certain NP loading. The dynamics of ionic NPs and polymers is very different compared with their non-ionic counterparts. Specifically, ionic NP dynamics is getting enhanced in entangled matrices and also accelerates with the increase of NP loading.

Modeling of Entangled Polymer Diffusion in Melts and Nanocomposites: A Review.

This review concerns modeling studies of the fundamental problem of entangled (reptational) homopolymer diffusion in melts and nanocomposite materials in comparison to experiments. In polymer melts, the developed united atom and multibead spring models predict an exponent of the molecular weight dependence to the polymer diffusion very similar to experiments and the tube reptation model. There are rather unexplored parameters that can influence polymer diffusion such as polymer semiflexibility or polydispersity, leading to a different exponent. Models with soft potentials or slip-springs can estimate accurately the tube model predictions in polymer melts enabling us to reach larger length scales and simulate well entangled polymers. However, in polymer nanocomposites, reptational polymer diffusion is more complicated due to nanoparticle fillers size, loading, geometry and polymer-nanoparticle interactions.

Miscibility and Nanoparticle Diffusion in Ionic Nanocomposites.

We investigate the effect of various spherical nanoparticles in a polymer matrix on dispersion, chain dimensions and entanglements for ionic nanocomposites at dilute and high nanoparticle loading by means of molecular dynamics simulations. The nanoparticle dispersion can be achieved in oligomer matrices due to the presence of electrostatic interactions. We show that the overall configuration of ionic oligomer chains, as characterized by their radii of gyration, can be perturbed at dilute nanoparticle loading by the presence of charged nanoparticles. In addition, the nanoparticle's diffusivity is reduced due to the electrostatic interactions, in comparison to conventional nanocomposites where the electrostatic interaction is absent. The charged nanoparticles are found to move by a hopping mechanism.

One-component plasma of point charges and of charged rods.

An approximate theory is developed to describe the properties of mobile particles with extended charge distributions in the presence of a neutralizing fixed background charge. Long-wavelength fluctuations of the electric potential are handled within a variational perturbation approximation, and the short-wavelength fluctuations are handled within a cumulant (fugacity) expansion. The distinct treatment of these two contributions to the free energy enables the theory to provide quantitative predictions for the properties of these systems from the weak- to the strong-coupling regimes. With this theory, we study three different variations in the classical one-component plasma model: a plasma of point charges, a plasma of particles consisting of 8 linearly bonded point charges (8-mer), and a plasma of line charges. The theory was found to agree well with the available computer simulation data for the electrostatic interaction energy of these systems for all values of the plasma coupling parameter examined ( Gamma=0 to 400). In addition, we find that both the 8-mer rod and the line charge systems form a strongly ordered nematic phase, which is entirely driven by electrostatic interactions. The nematic phase only exists within a finite range of lengths of the charged particles. If the particles are too short or too long, the nematic phase does not appear. Finally, we find that the nematic phase is stable over a broader range of conditions for the line charge system than for the 8-mer rod system; consequently, the phase behavior of the one-component plasma is sensitive to the manner in which the charge is distributed on the particles.