Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids

Keith, Jordan R.; Rebello, Nathan; Cowen, Benjamin; Ganesan, Venkat

doi:10.1021/acsmacrolett.9b00070

Cited by 57 publications

(89 citation statements)

References 39 publications

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“…In past studies on polymerized ionic liquids, we established correlations between ion‐association relaxation timescales and ion mobilities . In particular, the ion‐association structural relaxation time τ C represents the average time required for two ions to permanently separate from each other.…”

Section: Introductionsupporting

confidence: 91%

“…In our past studies of polymerized ionic liquids, we examined the probabilities of ionic coordination states as a function of coordination number and identified key aspects of ion‐transport mechanisms through such a characterization. Coordination was determined in the present study by direct atomic coordination using cutoff distances informed by the radial distribution functions, such as those displayed in Figure .…”

Section: Resultsmentioning

confidence: 97%

“…Specifically, we use atomistic molecular dynamics (MD) simulations to probe the ion mobilities, and the underlying structural features in Motifs B and C at various concentrations of Li + ‐TFSI − to understand the origins of the differences noted in their conductivities. Within such a context, we also seek to clarify the ion‐transport mechanisms in salt‐doped polyZIs and examine parallels to the physics identified in our recent studies of polymerized ionic liquids …”

Section: Introductionmentioning

confidence: 99%

“…In recent studies, Shao et al reported extensive set of MD investigations on ZI/salt solubility and association phenomena . We adopt the optimized potential for liquid simulations (OPLSs) used by Shao et al, which has also been used in other studies on ionic liquids and polymerized ionic liquids . The simulations are effected at temperature of 600K to facilitate faster ion mobilities which can be probed in reasonable timescales in simulations.…”

Section: Introductionmentioning

confidence: 99%

“…The monomers in our present study were optimized in the gas phase at a B3LYP/6‐311++G** level of theory using Gaussian16 . The electrostatic potential was mapped at Merz–Singh–Kollman points, and partial charges were computed using Amber Antechamber and scaled by 0.8, a scaling constant used in previous work to mimic charge transfer and capture average polarization effects in ionic liquids . Simulation boxes were packed with polymers of Motifs B or C, along with Li + ‐TFSI − salt in systematically varied fractions relative to polyZI monomers ( r mol salt /mol ZI ).…”

Section: Introductionmentioning

confidence: 99%

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Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Keith

Ganesan

2020

Journal of Polymer Science

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Polyzwitterions (polyZIs), macromolecules with repeating ampholytic monomers, are a novel class of materials with attractive properties for battery electrolytes. In this study, we probe the ion transport characteristics and underlying mechanisms in two salt‐doped (Li+‐TFSI−) polyZIs of similar composition with contrasting zwitterion (ZI) ionic organization: pendant monomers organized via backbone‐anion‐cation (B‐ZI−‐ZI+, Motif B) and backbone‐cation‐anion (B‐ZI+‐ZI−, Motif C). Within both Motifs B and C, the counterion of the pendant‐end ZI moiety shows higher mobility. Similarly, when comparing Li+ or TFSI− across motifs, it is seen that the respective pendant‐end counterion possesses higher mobility than its backbone‐adjacent counterpart. Furthermore, when comparing counterions to same‐position ZI moieties, TFSI− is seen to possess higher mobility than Li+ in each case, a result rationalized by invoking the lower interaction strength between the TFSI− and ZI+. Analysis of ion‐transport mechanisms demonstrate that the mobility of countercharges to the pendant‐end ZI moiety correlates with the ion‐association relaxation timescale, similar to ideas noted in polymerized ionic liquids in past studies. However, the mobility of countercharges to the backbone‐adjacent ZI moiety is shown to be correlated with a cage relaxation time, which incorporates the combined effects of frustrated motion due to the presence of the polymer backbone and pendant‐end ZI moiety and the higher mobility in a population of lightly ZI‐coordinated ions. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 578–588

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Section: Introductionsupporting

confidence: 91%

Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Keith

Ganesan

2020

Journal of Polymer Science

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Tailoring Charged Block Copolymer Architecture for Performance

White¹,

Liu²,

Drummey³

et al. 2022

Macromolecular Engineering

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Charged block copolymers (BCPs) find use in numerous applications spanning from gene delivery to electromechanical transducers. Recent advances in polymer synthesis have provided researchers with the necessary tools to study the properties of a wide variety of BCPs bearing cationic and anionic substituents. Controlling the architecture of these charged BCPs plays a key role in tailoring their performances in the desired application. Likewise, the polymer morphology significantly affects ion transport and thermomechanical properties of the charged BCP. This article aims to compare the structure–property relationships in charged BCPs across a variety of different polymer architectures including linear, branched, segmented, and multiply charged BCPs with a focus on tailoring properties for specific applications. Linear BCPs comprise of diblock, triblock, and multiblock copolymers. Diblocks frequently serve as micelles for drug delivery while triblocks, multiblocks, and segmented BCPs act as ion exchange membranes for transducers and fuel cells. The section on branched BCPs discusses polymer brushes, stars, micelles, and cross‐linked networks. The final section describes synthetic routes toward synthesizing multiply charged monomers and polymers while also emphasizing the challenges and benefits associated with these materials.

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Predictive Molecular Models for Charged Materials Systems: From Energy Materials to Biomacromolecules

Jeong

Lee

et al. 2022

Advanced Materials

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Electrostatic interactions play a dominant role in charged materials systems. Understanding the complex correlation between macroscopic properties with microscopic structures is of critical importance to develop rational design strategies for advanced materials. But the complexity of this challenging task is augmented by interfaces present in the charged materials systems, such as electrode–electrolyte interfaces or biological membranes. Over the last decades, predictive molecular simulations that are founded in fundamental physics and optimized for charged interfacial systems have proven their value in providing molecular understanding of physicochemical properties and functional mechanisms for diverse materials. Novel design strategies utilizing predictive models have been suggested as promising route for the rational design of materials with tailored properties. Here, an overview of recent advances in the understanding of charged interfacial systems aided by predictive molecular simulations is presented. Focusing on three types of charged interfaces found in energy materials and biomacromolecules, how the molecular models characterize ion structure, charge transport, morphology relation to the environment, and the thermodynamics/kinetics of molecular binding at the interfaces is discussed. The critical analysis brings two prominent field of energy materials and biological science under common perspective, to stimulate crossover in both research field that have been largely separated.

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Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids

Cited by 57 publications

References 39 publications

Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Ion transport mechanisms in salt‐doped polymerized zwitterionic electrolytes

Tailoring Charged Block Copolymer Architecture for Performance

Predictive Molecular Models for Charged Materials Systems: From Energy Materials to Biomacromolecules

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