Effect of Nanoparticles on Ion Transport in Polymer Electrolytes

Mogurampelly, Santosh; Ganesan, Venkat

doi:10.1021/ma502578s

Cited by 83 publications

(115 citation statements)

References 84 publications

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“…[320][321][322][323][324] While some atomistic simulations have examined the mechanism of ion transport in PNCs and pointed the importance of features such as polymer segmental motion, NP interaction with ions and the polymer segments, and changes in polymer conformations induced by nanoparticles, a number of important features are still unaccounted. [325][326][327][328][329][330][331][332][333] Specifically, due to the detailed and atomistic nature of such simulations, the influence of filler structure and its impact on ionic conductivity has still not been clarified. Moreover, much of the studies (with some exceptions 325,333 ) have been concerned with systems of specified chemistries, and hence there is still a lack of general principles underlying the ionic conductivity and their mechanisms in polymer nanocomposites.…”

Section: Ionic Conductivity Of Polymer Nanocompositesmentioning

confidence: 99%

Perspective: Outstanding theoretical questions in polymer-nanoparticle hybrids

Kumar

Ganesan

Riggleman

2017

The Journal of Chemical Physics

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164

143

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This topical review discusses the theoretical progress made in the field of polymer nanocomposites, i.e., hybrid materials created by mixing (typically inorganic) nanoparticles (NPs) with organic polymers. It primarily focuses on the outstanding issues in this field and is structured around five separate topics: (i) the synthesis of functionalized nanoparticles; (ii) their phase behavior when mixed with a homopolymer matrix and their assembly into well-defined superstructures; (iii) the role of processing on the structures realized by these hybrid materials and the role of the mobilities of the different constituents; (iv) the role of external fields (electric, magnetic) in the active assembly of the NPs; and (v) the engineering properties that result and the factors that control them. While the most is known about topic (ii), we believe that significant progress needs to be made in the other four topics before the practical promise offered by these materials can be realized. This review delineates the most pressing issues on these topics and poses specific questions that we believe need to be addressed in the immediate future. Published by AIP Publishing. [http://dx

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Section: Ionic Conductivity Of Polymer Nanocompositesmentioning

confidence: 99%

Perspective: Outstanding theoretical questions in polymer-nanoparticle hybrids

Kumar

Ganesan

Riggleman

2017

The Journal of Chemical Physics

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164

143

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“…This is due to the high crystallinity (up to 70%) for high molar-mass SPEs. [5][6][7]18,30] Thus, various approaches have been made to enhance to conductivity of SPEs such as addition of plasticizers [31][32][33] and fillers, [34][35][36][37][38][39][40] polymer blending, [4,26,[41][42][43] polymer hosts using copolymers [44][45][46][47][48] etc. Blending PEO with another component is one of the cost-effective and convenient ways for the enhancement of the conductivity of SPEs by compositional change of the blends.…”

Section: Introductionmentioning

confidence: 99%

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Ramli

Chan

Ali

2018

Macromolecular Symposia

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From the thermodynamic point of view, most of the high molar‐mass binary polymer blends are immiscible due to the entropic contribution to the free energy of mixing is relatively small. The miscibility of the systems on the molecular scale can be assessed by the thermal properties such as quantities of glass transition temperature (Tg) and change in heat capacity (ΔCp) of the polymers. For a semi‐crystalline polymer such as poly(ethylene oxide) (PEO), the crystallinity (X*) and the melting temperature (Tm) can also give some hints on the miscibility. Apart from the thermal properties, additional scientific findings such as morphology of the blends are needed as supplementary evidences to support the results. We focus on the PEO as the polymer host, blends with poly(n‐butyl methacrylate) (PnBMA) which were prepared using solution casting technique. Thermal properties of PEO/PnBMA polymer blends were investigated by modulated differential scanning calorimeter (MDSC) on the isothermal crystallized samples at 25 °C. Tg of PEO in the blends do not show significant variation with addition of PnBMA for entire composition range while for Tg of PnBMA in the blends, it is challenging to be estimated under the experimental condition due to the overlapping of the Tg of PnBMA and melting endotherm of PEO. Constancy of quantity Tg of PEO and ΔCp of PEO corresponding to the content of PEO in the blends suggest that PEO and PnBMA are immiscible for entire blend composition. X* and Tm of PEO in the blends show insignificant variation in PEO/PnBMA blends, when PEO as major component. This implies that these blends are immiscible under the experimental conditions as agreed with results of Tg and ΔCp. Spherulitic morphologies of PEO in the blends were studied by polarized optical microscopy (POM). PnBMA phase disperses randomly in PEO matrix when PEO in excess. The absence of significant change for the fibrillar spherulitic structures of PEO spherulites with addition of PnBMA (when PEO is the major component) suggests that immiscibility of PEO and PnBMA. Besides, the crystalline structure of PEO in PEO/PnBMA blends using X‐ray diffraction (XRD) reveals that the crystalline structure of PEO is not disturbed with the addition of PnBMA when PEO is in excess as the two distinct peaks of PEO do not shift as compared to neat PEO. Impedance spectroscopy (IS) studies show that the ionic conductivities (σDC) of the polymer blends at room temperature slightly increase with increasing of PEO with the order of magnitude of 10−11–10−10 S cm−1. This system serves as a potential polymer host as solid polymer electrolytes when added with inorganic salt.

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“…For instance, the ion distributions in the lamella can depend on the molecular weight and the degree of segregation between the blocks (such effects were investigated in our earlier work). Moreover, the segmental dynamics themselves can be affected by the coordination between the ions and the polymer . Studying such effects would require consideration of models involving explicit ions in block copolymer matrices, which we plan to present in a future publication.…”

Section: Introductionmentioning

confidence: 99%

Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers

Sethuraman

Pryamitsyn

Ganesan

2016

J. Polym. Sci. Part B: Polym. Phys.

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Experiments in the context of block copolymer electrolyte materials have observed intriguing dependence of the ionic conductivities upon the polymer molecular weight and the degree of segregation between the blocks. Such results have been partly rationalized by invoking the spatial extent of dynamical inhomogeneities that manifest in ordered phases of block copolymers comprised of a rubbery and a glassy block. Motivated by such observations, we use molecular dynamics simulations to study the extent of spatial inhomogeneities in segmental dynamics of lamellar diblock copolymer systems where the blocks possess different mobilities. We probed the local average relaxation times and the dynamical heterogeneities as a function of distance from the interface. Our results suggest that the relaxation times of rubbery segments are strongly influenced by both the spatial proximity to the interface and the relative mobility of the glassy segments. Scaling of our results indicate that the interfacial width of the ordered phases serves as the length scale underlying the spatial inhomogeneities in segmental dynamics of the fast monomers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 859–864

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Effect of Nanoparticles on Ion Transport in Polymer Electrolytes

Cited by 83 publications

References 84 publications

Perspective: Outstanding theoretical questions in polymer-nanoparticle hybrids

Perspective: Outstanding theoretical questions in polymer-nanoparticle hybrids

Thermal Properties and Morphology of Poly(ethylene oxide)/Poly(n‐butyl methacrylate) Blends

Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers

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