Investigations of clustering of ions and diffusivity in concentrated aqueous solutions of lithium chloride by molecular dynamic simulations

Singh, Meena B.; Dalvi, Vishwanath H.; Gaikar, Vilas G.

doi:10.1039/c4ra15124k

Cited by 41 publications

(84 citation statements)

References 59 publications

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“…Using highly concentrated electrolytes, the water molecules largely bond to Li + ions, leading to a decreased activity of water molecules. 3,49,50 As a result, these side reactions involving free water molecules near the electrode surface become more sluggish, leading to slow self-discharge rates and a shi of the self-discharge process from the activation-controlled to diffusion-controlled faradaic mechanism. It should be noted that the increased electrolyte concentration may also impede electron transfer between redox molecules and the electrode surface.…”

Section: Resultsmentioning

confidence: 99%

Hydrogels with highly concentrated salt solution as electrolytes for solid-state supercapacitors with a suppressed self-discharge rate

et al. 2022

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Section: Resultsmentioning

confidence: 99%

Hydrogels with highly concentrated salt solution as electrolytes for solid-state supercapacitors with a suppressed self-discharge rate

et al. 2022

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“…The advantageous effects of using reduced charges (which originates from the electronic continuum model [89]) are examined in several papers (see e.g. [65,90]  Singh-Dalvi-Gaikar parameter sets (SDG-S, SDG-T) [91]. These models are combinations, in which the Li + ion parameters are obtained from the DS FF, and the Clion parameters are equal to the JJ Clparameters.…”

Section: Interatomic Potentialsmentioning

confidence: 99%

The structure of aqueous lithium chloride solutions at high concentrations as revealed by a comparison of classical interatomic potential models

Pethes

2018

Journal of Molecular Liquids

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Highly concentrated aqueous lithium chloride solutions were investigated by classical molecular dynamics (MD) and reverse Monte Carlo (RMC) simulations. At first MD calculations were carried out applying twenty-nine combinations of ion-water interaction models at four salt concentrations. The structural predictions of the different models were compared, the contributions of different structural motifs to the partial pair correlation functions (PPCF) were determined. Particle configurations obtained from MD simulations were further refined using the RMC method to get better agreement with experimental X-ray and neutron diffraction data. The PPCFs calculated from MD simulations were fitted together with the experimental structure factors to construct structural models that are as consistent as possible with both the experimental results and the results of the MD simulations. The MD models were validated according to the quality of the fits. Although none of the tested MD models can describe the structure perfectly at the highest investigated concentration, their comparison made it possible to determine the main structural properties of that solution as well. It was found that four nearest neighbors (oxygen atoms and chloride ions together) are around a lithium ion at each concentration, while in the surroundings of the chloride ion hydrogen atom pairs are replaced by one lithium ion as the concentration increases. While in pure liquid water four water molecules can be found around a central water molecule, near the solubility limit nearly all water molecules are connected to two chloride ions (via their hydrogen atoms) and one lithium ion (by their oxygen atoms).Ion-water potential model; Structure nowadays. Unfortunately, for highly concentrated LiCl solutions they are almost absent, and the comparison with experimental data sets (e.g. XRD or ND data) is completely missing.Several interaction models (force fields, FF) have been developed and used for MD simulations in the context of electrolyte solutions. However, for concentrated aqueous LiCl solutions their applicability is very limited, as was shown recently [65]. In that work 29 different models were investigated; it turns out that their predictions about density, dielectric constant and self-diffusion constants scatter widely. Neutron and X-ray weighted structure factors were also calculated and compared with experimental data: it was found that the agreement between the experimental and simulation curves was poor, especially for the highest investigated concentration (19.55 mol/kg, near the solubility limit).The reverse Monte Carlo method [66] is a useful tool to find three dimensional configurations consistent with experimental data sets. However the number of experimental data sets (mostly one or two structure factors from neutron and/or X-ray diffraction measurements) is low compared to the number of the independent partial pair correlation functions (10). This lack of information results in a highly underdetermined system (see the 'pure' RMC results in R...

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“…In the following years, a variety of studies have followed suit, combining the JC TIP4P/Ewoptimized ion parameters (JCTIP4PEw) or other ion parameters with the TIP4P/2005 water model. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] Following the increased use of TIP4P/2005 and demand of ion parameters specifically optimized for TIP4P/2005, the Vega group started working on obtaining parameters for NaCl in terms of solubility. 41,42 The final parameters are presented in the study of Benavides et al 43 Recently, additional ion parameters were published, 44 for Li + , Na + , K + , Mg 2+ , Ca 2+ , Cl − , and SO 2− 4 .…”

Section: Introductionmentioning

confidence: 99%

On the transferability of ion parameters to the TIP4P/2005 water model using molecular dynamics simulations

Döpke

Moultos

Hartkamp

2020

The Journal of Chemical Physics

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Investigations of clustering of ions and diffusivity in concentrated aqueous solutions of lithium chloride by molecular dynamic simulations

Abstract: The diffusion coefficient of Li+ ions decreases with increase in LiCl concentration which depends on the size of coordination structure of ions formed in solutions.

Cited by 41 publications

References 59 publications

Hydrogels with highly concentrated salt solution as electrolytes for solid-state supercapacitors with a suppressed self-discharge rate

Hydrogels with highly concentrated salt solution as electrolytes for solid-state supercapacitors with a suppressed self-discharge rate

The structure of aqueous lithium chloride solutions at high concentrations as revealed by a comparison of classical interatomic potential models

On the transferability of ion parameters to the TIP4P/2005 water model using molecular dynamics simulations

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