Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers

Choi, U Hyeok; Mittal, Anuj; Price, Terry L.; Lee, Minjae; Gibson, Harry W.; Runt, James; Colby, Ralph H.

doi:10.1016/j.electacta.2014.12.140

Cited by 80 publications

(129 citation statements)

References 80 publications

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“…The results for the MSDs of the ions and the slopes of a power law fit to such results are presented in Supporting Information Section IIA. From the results displayed in Figure (a) at a specified temperature, diffusivity is seen to increase as the linker length increases, matching the experimental results of Choi et al…”

supporting

confidence: 86%

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Influence of side chain linker length on ion‐transport properties of polymeric ionic liquids

Keith

Mogurampelly

Wheatle

et al. 2017

J Polym Sci B Polym Phys

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We used atomistic molecular dynamics simulations to study the properties of polymerized 1‐alkene‐3‐butylimidazolium‐hexafluorophosphate, a polymerized ionic liquid electrolyte, and characterized the influence of the linear alkene length on the mobility of the hexafluorophosphate ions. Consistent with experimental observations, our simulations indicate that as the alkene length increases, the diffusivity of hexafluorophosphate anion monotonically increases. We demonstrate that such a trend arises from the influence of linker segments on the intermolecular ion hopping rates, which is in turn modulated by intermolecular cationic separation distances. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1718–1723

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confidence: 86%

“…In contrast, Choi et al reported increasing ionic conductivity with increasing Group 2 alkyl length (Fig. ) for a similar imidazolium‐based polyIL . Together, such observations have raised the question, “what are the mechanisms underlying the influence of the linker side‐chain length on the transport properties of polyILs?”…”

mentioning

confidence: 97%

Influence of side chain linker length on ion‐transport properties of polymeric ionic liquids

Keith

Mogurampelly

Wheatle

et al. 2017

J Polym Sci B Polym Phys

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“…On average, there are more adjacent tethered anions with increased crosslinker length for materials with the same overall ion content. Anions adjacent along the chain are more likely to have polarizability volume overlap, which results in a lower degree of cation dissociation and therefore a lower effective mobile ion number [49,50]. These combined effects explain the non-monotonic relationship of ionic conductivity and network crosslinker length at various temperatures.…”

Section: Introductionmentioning

confidence: 93%

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

et al. 2018

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Solvent-free, single-ion conducting electrolytes are sought after for use in electrochemical energy storage devices. Here, we investigate the ionic conductivity and how this property is influenced by segmental mobility and conducting ion number in crosslinked single-ion conducting polyether-based electrolytes with varying tethered anion and counter-cation types. Crosslinked electrolytes are prepared by the polymerization of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) methyl ether acrylate, and ionic monomers. The ionic conductivity of the electrolytes is measured and interpreted in the context of differential scanning calorimetry and Raman spectroscopy measurements. A lithiated crosslinked electrolyte prepared with PEG 31 DA and (4-styrenesulfonyl)(trifluoromethanesulfonyl)imide (STFSI) monomers is found to have a lithium ion conductivity of 3.2 × 10 −6 and 1.8 × 10 −5 S/cm at 55 and 100 • C, respectively. The percentage of unpaired anions for this electrolyte was estimated at about 23% via Raman spectroscopy. Despite the large variances in metal cation-STFSI binding energies as predicted via density functional theory (DFT) and large variations in ionic conductivity, STFSI-based crosslinked electrolytes with the same charge density and varying cations (Li, Na, K, Mg, and Ca) were estimated to all have unpaired anion populations in the range of 19 to 29%.

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“…Experimental studies based on dielectric spectroscopy by Choi et al. suggested that the static dielectric constant of ionic liquids may significantly increase as they are polymerized . When imidazolium acrylates and methacrylates are polymerized, their dielectric constants may increase by up to a factor of ∼140.…”

Section: Dielectric Response Of Ionic Liquidsmentioning

confidence: 99%

Theoretical Aspects of Ionic Liquids for Soft‐Matter Sciences

Nakamura

Shock

Eggart

et al. 2018

Israel Journal of Chemistry

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The thermodynamic and electrochemical properties of ionic liquids produce a broad spectrum of unconventional phenomena both microscopically and macroscopically. However, despite numerous theoretical and experimental studies, the fundamental roles of the relevant interactions such as electrostatic interactions and hydrogen bonding often remain unclear at the molecular level. The complexity of the molecular interactions typically increases when ionic liquids dissolve polymers or polar substances such as water. Accordingly, recent studies have revealed new features of ionic liquids. Further insights into the role of the molecular polarity of ionic liquids are required. This article presents an overview of the important phenomena of ionic liquids concerning soft‐matter sciences based on selected experimental and theoretical studies. We focus on the effect of the dielectric response of ionic liquids to distinguish ionic liquids from common inorganic salts, such as alkali metal halides.

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Molecular Volume Effects on the Dynamics of Polymerized Ionic Liquids and their Monomers

Cited by 80 publications

References 80 publications

Influence of side chain linker length on ion‐transport properties of polymeric ionic liquids

Influence of side chain linker length on ion‐transport properties of polymeric ionic liquids

Ion Transport in Solvent-Free, Crosslinked, Single-Ion Conducting Polymer Electrolytes for Post-Lithium Ion Batteries

Theoretical Aspects of Ionic Liquids for Soft‐Matter Sciences

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