Molecular modeling of electrolyte and polysulfide ions for lithium-sulfur batteries

The operation of a lithium-sulfur (Li-S) battery involves the transport of Li+ ions and soluble sulfides mostly in the form of solvated ions. Key challenges in the development of Li-S battery technology are the diffusion of Li+ in micropores filled with sulfur and eliminating the “shuttling” of polysulfides. Ion dimensions in solvated and desolvated forms are key parameters determining the diffusion coefficient and the rate of transport of such ions, while constrictivity effects due to the effect of pore size compared to ion size control both transport and filling of the pores. We present molecular simulations to determine the solvation parameters of electrolyte ions and sulfides S22−, S42−, S62−, and S82− in two different electrolyte systems: LiTFSI in DOL/DME and LiPF6 in EC/DMC. The calculated parameters include the coordination number and the geometrically optimized model and dimensions, using the van der Waals surface approach, of the solvated and desolvated ions. The desolvation energy of the electrolyte ions is also calculated. Such data is useful for the modeling and design of the pore sizes of cathode host materials to be able to accommodate the different sulfides while minimizing their “shuttling” between cathode and anode.

Towards Electrochemical Water Desalination Techniques: A Review on Capacitive Deionization, Membrane Capacitive Deionization and Flow Capacitive Deionization

Electrochemical water desalination has been a major research area since the 1960s with the development of capacitive deionization technique. For the latter, its modus operandi lies in temporary salt ion adsorption when a simple potential difference (1.0–1.4 V) of about 1.2 V is supplied to the system to temporarily create an electric field that drives the ions to their different polarized poles and subsequently desorb these solvated ions when potential is switched off. Capacitive deionization targets/extracts the solutes instead of the solvent and thus consumes less energy and is highly effective for brackish water. This paper reviews Capacitive Deionization (mechanism of operation, sustainability, optimization processes, and shortcomings) with extension to its counterparts (Membrane Capacitive Deionization and Flow Capacitive Deionization).

Towards Wireless Characterization of Solvated Ions with Uncoated Resonant Sensors

<p></p><p>Uncoated resonant sensors are presented here for wireless monitoring of solvated ions, with progress made toward monitoring nitrates in agricultural runoff. The sensor, an open-circuit Archimedean coil, is wirelessly interrogated by a portable vector network analyzer (VNA) that monitors the scattering parameter response to varying ionic concentrations. The sensor response is defined in terms of the resonant frequency and the peak-to-peak amplitude of the transmission scattering parameter profile (|S₂₁|). Potassium chloride (KCl) solutions with concentrations in the range of 100 nM – 4.58 M were tested on nine resonators having different length and pitch sizes to study the effect of sensor geometry on its response to ion concentration. The resonant sensors demonstrated an ion-specific response, caused by the variations in the relative permittivity of the solution, which was also a function of the resonator geometry. A lumped circuit model, which fit the experimental data well, confirms signal transduction via change in solution permittivity. Also, a ternary ionic mixture (composed of potassium nitrate (KNO₃), ammonium nitrate (NH₄NO₃), and ammonium phosphate (NH₄H₂PO₄)) response surface was constructed by testing 21 mixture variations on three different sensor geometries and the phase and magnitude of scattering parameters were monitored. It was determined that the orthogonal responses presented by resonant sensor arrays can be used for quantifying levels of target ions in ternary mixtures. Applications of these arrays include measuring the concentration of key ions in bioreactors, human sweat, and agricultural waters. Preliminary results are shown for calibration standards and real waterway samples in Iowa, USA.</p><br><p></p>

Towards Wireless Characterization of Solvated Ions with Uncoated Resonant Sensors

<p></p><p>Uncoated resonant sensors are presented here for wireless monitoring of solvated ions, with progress made toward monitoring nitrates in agricultural runoff. The sensor, an open-circuit Archimedean coil, is wirelessly interrogated by a portable vector network analyzer (VNA) that monitors the scattering parameter response to varying ionic concentrations. The sensor response is defined in terms of the resonant frequency and the peak-to-peak amplitude of the transmission scattering parameter profile (|S₂₁|). Potassium chloride (KCl) solutions with concentrations in the range of 100 nM – 4.58 M were tested on nine resonators having different length and pitch sizes to study the effect of sensor geometry on its response to ion concentration. The resonant sensors demonstrated an ion-specific response, caused by the variations in the relative permittivity of the solution, which was also a function of the resonator geometry. A lumped circuit model, which fit the experimental data well, confirms signal transduction via change in solution permittivity. Also, a ternary ionic mixture (composed of potassium nitrate (KNO₃), ammonium nitrate (NH₄NO₃), and ammonium phosphate (NH₄H₂PO₄)) response surface was constructed by testing 21 mixture variations on three different sensor geometries and the phase and magnitude of scattering parameters were monitored. It was determined that the orthogonal responses presented by resonant sensor arrays can be used for quantifying levels of target ions in ternary mixtures. Applications of these arrays include measuring the concentration of key ions in bioreactors, human sweat, and agricultural waters. Preliminary results are shown for calibration standards and real waterway samples in Iowa, USA.</p><br><p></p>

Energetic Performance of Pure Silica Zeolites under High-Pressure Intrusion of LiCl Aqueous Solutions: An Overview

An overview of all the studies on high-pressure intrusion—extrusion of LiCl aqueous solutions in hydrophobic pure silica zeolites (zeosils) for absorption and storage of mechanical energy is presented. Operational principles of heterogeneous lyophobic systems and their possible applications in the domains of mechanical energy storage, absorption, and generation are described. The intrusion of LiCl aqueous solutions instead of water allows to considerably increase energetic performance of zeosil-based systems by a strong rise of intrusion pressure. The intrusion pressure increases with the salt concentration and depends considerably on zeosil framework. In the case of channel-type zeosils, it rises with the decrease of pore opening diameter, whereas for cage-type ones, no clear trend is observed. A relative increase of intrusion pressure in comparison with water is particularly strong for the zeosils with narrow pore openings. The use of highly concentrated LiCl aqueous solutions instead of water can lead to a change of system behavior. This effect seems to be related to a lower formation of silanol defects under intrusion of solvated ions and a weaker interaction of the ions with silanol groups of zeosil framework. The influence of zeosil nanostructure on LiCl aqueous solutions intrusion–extrusion is also discussed.

Glow Discharge Plasma as a Cause of Changes in Aqueous Solutions: The Mass Spectrometry Study of Solvation Processes of Ions

A new apparatus for inducing changes in the properties of water in closed dielectric vessel by subjecting it to pulsed direct current glow discharge plasma is designed and constructed. It has been hypothesized that the action of plasma on the structure of water consists in resonance excitation of water aggregates. As a result of resonance excitation, aggregates of high molar masses are broken down into low molecular mass aggregates. Analysis of the ESI MS spectra revealed that in all tested aqueous solutions after exposure to plasma, the concentration of low-molecular solvated ions [M(H2O)]+ and [M(H2O)2]+ significantly increased, while the concentration of the ions of high molecular masses [M(H2O)6-10]+ solvated by water aggregates decreased, relative to their concentrations in the water solutions not subjected to plasma irradiation. According to our measurements also a significant change in pH occurs. The presented results clearly show that it is possible to process a liquid that changes its structure without involving high processing energy and, unexpectedly, the obtained change of parameters is significant and stable over time.

Frontiers in molecular simulation of solvated ions, molecules and interfaces

This themed collection is a collection of articles on frontiers in molecular simulation of solvated ions, molecules and interfaces.

Specific ion effects at graphitic interfaces

Improved understanding of aqueous solutions at graphitic interfaces is critical for energy storage and water desalination. However, many mechanistic details remain unclear, including how interfacial structure and response are dictated by intrinsic properties of solvated ions under applied voltage. In this work, we combine hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and within graphene slit-pores. We confirm that adsorption energy increases with ionic radius, while being highly dependent on the pore size. In addition, in contrast with conventional electrochemical models, we find that interfacial charge transfer contributes non-negligibly to this interaction and can be further enhanced by confinement. We conclude that the measured interfacial capacitance trends result from a complex interplay between voltage, confinement, and specific ion effects-including ion hydration and charge transfer.

Water and Metal Cations in Solution

Water has an exceptional ability to dissolve minerals. It is safe and chemically stable, and it remains liquid over a wide temperature range. Thus, it is the best solvent and reaction medium for both laboratory and industrial purposes. Water is able to dissolve ionic and ionocovalent solids because of the high polarity of the molecule (dipole moment μ = 1.84 Debye) as well as the high dielectric constant of the liquid (ε = 78.5 at 25°C). This high polarity allows water to exhibit a strong solvating power: that is, the ability to fix onto ions as a result of electrical dipolar interactions. Water is also an ionizing liquid able to polarize an ionocovalent molecule. For example, the solvolysis phenomenon increases the polarization of the HCl molecule in aqueous solution. Finally, owing to the high dielectric constant of the liquid, water is a dissociating solvent that can decrease the electrostatic forces between solvated cations and anions, allowing their dispersion as H+solvated and Cl−solvated through the liquid. (The attractive force F between charges q and q′ separated by the distance r is given by Coulomb’s law, F = qq′/εr2.) These characteristics are rarely found together in common liquids. The dipole moment of the ethanol molecule (μ = 1.69 Debye) is close to that of water, but the dielectric constant of ethanol is much lower (ε = 24.3). Ethanol is a good solvating liquid, but a poor dissociating one; consequently, it is considered a bad solvent of ionic compounds. Dissolution in water of an ionic solid such as sodium chloride is limited to dipolar interactions with Na+ and Cl− ions and their dispersion in the liquid as solvated ions, regardless of the pH of the solution. Cations with higher charge, especially cations of transition metals, retain a fixed number of water molecules, thereby forming a true coordination complex [M(OH2)N]z+ with a well-defined geometry. In addition to the dipolar interactions, water molecules behave as true ligands because they are Lewis bases exerting an electron σ-donor effect on the empty orbitals of the cation.