Molecular Level Origin of Ion Dynamics in Highly Concentrated Electrolytes

Shigenobu, Keisuke; Tsuzuki, Seiji; Philippi, Frederik; Sudoh, Taku; Ugata, Yosuke; Dokko, Kaoru; Watanabe, Masayoshi; Ueno, Kazuhide; Shinoda, Wataru

doi:10.1021/acs.jpcb.3c05864

Cited by 5 publications

(4 citation statements)

References 81 publications

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“…This thermodynamic barrier leads to an energetic competition between the hydrated and ion-paired states, where the probability of ion pairing increases as the cation−anion interaction strength increases. 87 While the formation of ion pairs is not the only mechanism for affecting dynamics and chemical interactions, the effect of ion pairs on the solution structure must be considered to understand dynamical differences between Li + electrolyte solutions. Li + ions are generally poor at forming ion pairs with larger halide ions compared to other alkali ions.…”

Section: T H I S C O N T E N T Imentioning

confidence: 99%

“…Ion pairs can weaken the chemical interactions of two species by creating an activation energy barrier that must be overcome to solvate the ion. This thermodynamic barrier leads to an energetic competition between the hydrated and ion-paired states, where the probability of ion pairing increases as the cation–anion interaction strength increases . While the formation of ion pairs is not the only mechanism for affecting dynamics and chemical interactions, the effect of ion pairs on the solution structure must be considered to understand dynamical differences between Li + electrolyte solutions.…”

mentioning

confidence: 99%

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Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

Felsted,

Graham,

Zhao

et al. 2024

J. Phys. Chem. Lett.

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The dynamics, orientational anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO 2 ), and lithium nitrate (LiNO 3 ), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. The 2D IR, NMR, and viscosity results show that LiNO 2 exhibits longer correlation times, lower diffusivity, and nearly 4 times greater viscosity compared to those of the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water−ion network interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO 2 and LiNO 3 solutions show significantly weakened chemical interactions between the lithium cations and the methyl thiocyanate when compared with those of the lithium halide salts.

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Section: T H I S C O N T E N T Imentioning

confidence: 99%

mentioning

confidence: 99%

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

Felsted,

Graham,

Zhao

et al. 2024

J. Phys. Chem. Lett.

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“…In the present work, we focus on the common n -alkyl-methyl-imidazolium chloride ILs (with n ∈ {2, 4, 6, 8, 10, 12}) and aim at unraveling the morphology of this specific IL family. We acknowledge previous works that investigate the structure and/or related properties of different imidazolium-based ILs or IL families. − To commence this investigation, classical nonpolarizable molecular dynamics (MD) simulations of the ILs were performed. Subsequently, cluster and aggregation analyses from TRAVIS − and AGGREGATES were carried out.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Morphology of [C_nC₁Im]Cl Ionic Liquids Combining Cluster and Aggregation Analyses

Frömbgen,

Canongia Lopes,

Kirchner

et al. 2024

J. Phys. Chem. B

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A characteristic feature of ionic liquids is their nanosegregation, resulting in the formation of polar and nonpolar domains. The influence of increasing the alkyl side chain on the morphology of ionic liquids has been the subject of many studies. Typically, the polar network (charged part of the cation and anion) constitutes a continuous subphase that partially breaks to allow the formation of a nonpolar domain with the increase of the alkyl chain. As the nonpolar network expands, the number of tails per aggregate increases until the ionic liquid percolates. In this work, we demonstrate how the complementary software packages TRAVIS and AGGREGATES can be employed in conjunction to gain insights into the size and morphology of the [C n C 1 Im]Cl family, with n ∈ {2, 4, 6, 8, 10, 12}. The combination of the two approaches rounds off the picture of the intricate arrangement and structural features of the alkyl chains.

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“…The typical commercial LIB electrolyte − is fundamentally regarded as a high-concentration solution because its ionic species interact with each other and hence do not fulfill the Debye–Huckel model of a dilute solution . However, the term HCE has been used for electrolytes with salt concentrations well beyond the typical 1–1.5 M. ,,,,− Previous studies have defined HCEs differently. One of the earliest studies of HCEs using LiTFSI in acetonitrile at a 1:1.9 salt:solvent molar ratio (>4.2 M) referred to it as a superconcentrated electrolyte (SCE) .…”

Section: Introductionmentioning

confidence: 99%

Transitioning from Regular Electrolytes to Solvate Ionic Liquids to High-Concentration Electrolytes: Changes in Transport Properties and Ionic Speciation

Nachaki,

Kuroda

2024

J. Phys. Chem. C

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Glyme-based lithium-ion electrolytes have received considerable attention from the scientific community due to their improved safety, as well as electrochemical and thermal stability over carbonate-based electrolytes. However, these electrolytes suffer from major drawbacks such as high viscosities. To overcome the challenges that hinder their full potential, the molecular description of glyme-based lithium electrolytes in the highconcentration regime, particularly in the solvate ionic liquid (SIL) and high-concentration electrolyte (HCE) regimes, is needed. In this study, model glyme-based electrolytes based on a lithium thiocyanate and either tetraglyme (G4) or a mixture of monoglyme (G1) and diglyme (G2) were investigated as a function of the solvent-to-lithium ratio using linear and nonlinear IR spectroscopies, in combination with ab initio computations as well as electrochemical methods . The transport properties reveal enhanced ionicities in the HCE and SIL regimes ([O]/[Li] ≤ 5) compared to the regular electrolytes (REs, with [O]/[Li] > 5) in both pure (G4) and mixed (G1:G2) glymes. IR and ab initio computations relate these larger ionicities to the higher concentration of charged aggregates in the HCE and SIL electrolytes ([O]/[Li] ≤ 5). Moreover, it was observed that the use of mixed glymes appears to have a minimal effect on the transport properties of REs but exhibits deleterious effects on SILs. Overall, the results provide a molecular framework for describing the local structure of lithium glyme-based electrolytes and demonstrate the key role that the nature of glyme solvation plays in the molecular structure and consequently the macroscopic properties of the Li-glyme SILs, HCEs, and REs.

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Molecular Level Origin of Ion Dynamics in Highly Concentrated Electrolytes

Cited by 5 publications

References 81 publications

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

Unraveling the Morphology of [C_nC₁Im]Cl Ionic Liquids Combining Cluster and Aggregation Analyses

Transitioning from Regular Electrolytes to Solvate Ionic Liquids to High-Concentration Electrolytes: Changes in Transport Properties and Ionic Speciation

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Molecular Level Origin of Ion Dynamics in Highly Concentrated Electrolytes

Cited by 5 publications

References 81 publications

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

Unraveling the Morphology of [CnC1Im]Cl Ionic Liquids Combining Cluster and Aggregation Analyses

Transitioning from Regular Electrolytes to Solvate Ionic Liquids to High-Concentration Electrolytes: Changes in Transport Properties and Ionic Speciation

Contact Info

Product

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Unraveling the Morphology of [C_nC₁Im]Cl Ionic Liquids Combining Cluster and Aggregation Analyses