Polymerized Ionic Liquids: Correlation of Ionic Conductivity with Nanoscale Morphology and Counterion Volume

Iacob, Ciprian; Matsumoto, Atsushi; Brennan, Marissa; Liu, Hongjun; Paddison, Stephen J.; Urakawa, Osamu; Inoue, Tadashi; Sangoro, Joshua; Runt, James

doi:10.1021/acsmacrolett.7b00335

Cited by 68 publications

(115 citation statements)

References 41 publications

(56 reference statements)

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“…3). In contrast to (several) previous studies where this transition has been discussed to be exactly at T g , [24][25][26]33,34,38 this is the first time one obtained T s 0 consequently above T g with considerable deviations in the range of 40-80 K (see Table 1). Disregarding this novel temperature peculiarity the idiosyncrasy of a change in the thermal activation of s 0 , which seems to be characteristic for many PILs, 24,33 has been studied by J. R. Sangoro and coworkers in a comparative framework of BDS and NMR.…”

Section: Broadband Dielectric Spectroscopycontrasting

confidence: 91%

“…18,19,23 In contrast to low molecular weight ILs the thermal activation of DC conductivity for all polymeric systems studied so far changes from a Vogel-Fulcher-Tammann-to an Arrheniusdependence at a (sample specific) temperature T s 0 . [24][25][26][32][33][34][35][36][37] Sangoro and coworkers demonstrated, by combining broadband dielectric spectroscopy (BDS) with pulse-field gradient nuclear magnetic resonance (PFG-NMR), that this transition is caused by tremendous demobilization of the polymeric backbone including the attached ionic species, whereas the counterions are still diffusing through the polymer matrix and thence contributing to s 0 . 24 The fact that T s 0 was found to be close to the calorimetric glass transition temperature T g of the PILs under study leads to the conjecture of decoupling between charge transport and glassy dynamics.…”

Section: Introductionmentioning

confidence: 99%

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Charge transport and glassy dynamics in polymeric ionic liquids as reflected by their inter- and intramolecular interactions

et al. 2019

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Polymeric ionic liquids (PILs) form a novel class of materials in which the extraordinary properties of ionic liquids (ILs) are combined with the mechanical stability of polymeric systems qualifying them for multifold applications. In the present study broadband dielectric spectroscopy (BDS), Fourier transform infrared spectroscopy (FTIR), AC-chip calorimetry (ACC) and differential scanning calorimetry (DSC) are combined in order to unravel the interplay between charge transport and glassy dynamics. Three low molecular weight ILs and their polymeric correspondents are studied with systematic variations of anions and cations. For all examined samples charge transport takes place by glassy dynamics assisted hopping conduction. In contrast to low molecular weight ILs the thermal activation of DC conductivity for the polymeric systems changes from a Vogel-Fulcher-Tammann-to an Arrhenius-dependence at a (sample specific) temperature T s 0 . This temperature has been widely discussed to coincide with the glass transition temperature T g , a refined analysis, instead, reveals T s 0 of all PILs under study at up to 80 K higher values. In effect, below the T s 0 charge transport in PILs becomes more efficient -albeit on a much lower level compared to the low molecular weight pendants -indicating conduction paths along the polymer chain. This is corroborated by analysing the temperature dependence of specific IR-active vibrations showing at T s 0 distinct changes in the spectral position and the oscillator strength, whereas other molecular units are not affected. This leads to the identification of charge transport responsive (CTR) as well as charge transport irresponsive (CTI) moieties and paves the way to a refined molecular understanding of electrical conduction in PILs.platinum sensor to determine the water content of the P(ILs) after synthesis. HYDRANAL Coulomat AG water standards from Riedel-de Haën were used for calibration.

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Section: Broadband Dielectric Spectroscopycontrasting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Charge transport and glassy dynamics in polymeric ionic liquids as reflected by their inter- and intramolecular interactions

et al. 2019

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“…21 However, when ionic groups are closer to the polymer backbone, this trend may reverse. 51 Detailed BDS studies are planned to investigate the origin of these trend differences and their dependence on the spacing between ionic moiety and polymer backbone.…”

Section: Dsc Data Shown Inmentioning

confidence: 99%

Polymerized ionic liquids: Effects of counter‐anions on ion conduction and polymerization kinetics

Chen

Dugger

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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A novel imidazolium‐containing monomer, 1‐[ω‐methacryloyloxydecyl]‐3‐(n‐butyl)‐imidazolium (1BDIMA), was synthesized and polymerized using free radical and controlled free radical polymerization followed by post‐polymerization ion exchange with bromide (Br), tetrafluoroborate (BF4), hexafluorophosphate (PF6), or bis(trifluoromethylsulfonyl)imide (Tf2N). The thermal properties and ionic conductivity of the polymers showed a strong dependence on the counter‐ions and had glass transition temperatures (Tg) and ion conductivities at room temperature ranging from 10 °C to −42 °C and 2.09 × 10−7 S cm−1 to 2.45 × 10−5 S cm−1. In particular, PILs with Tf2N counter‐ions showed excellent ion conductivity of 2.45 × 10−5 S cm−1 at room temperature without additional ionic liquids (ILs) being added to the system, making them suitable for further study as electro‐responsive materials. In addition to the counter‐ions, solvent was found to have a significant effect on the reversible addition‐fragmentation chain‐transfer polymerization (RAFT) for 1BDIMA with different counter‐ions. For example, 1BDIMATf2N would not polymerize in acetonitrile (MeCN) at 65 °C and only achieved low monomer conversion (< 5%) at 75 °C. However, 1BDIMA‐Tf2N proceeded to high conversion in dimethylformamide (DMF) at 65 °C and 1BDIMABr polymerized significantly faster in DMF compared to MeCN. NMR diffusometry was used to investigate the kinetic differences by probing the diffusion coefficients for each monomer and counter‐ion in MeCN and DMF. These results indicate that the reaction rates are not diffusion limited, and point to a need for deeper understanding of the role electrostatics plays in the kinetics of free radical polymerizations. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1346–1357

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“…The type of materials employed was the group of cationic polymer ionic liquids. From the condensed knowledge reported in the literature, as briefly summarized above, it was assumed that imidazolium-TFSI-based PILs [31,[34][35][36][37]53] could serve as suitable candidates and starting points due to sufficient electrochemical stability. For that reason, the incorporation of (ethylene oxide) units was avoided.…”

Section: Introductionmentioning

confidence: 99%

In Situ Preparation of Crosslinked Polymer Electrolytes for Lithium Ion Batteries: A Comparison of Monomer Systems

et al. 2020

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Solid polymer electrolytes for bipolar lithium ion batteries requiring electrochemical stability of 4.5 V vs. Li/Li+ are presented. Thus, imidazolium-containing poly(ionic liquid) (PIL) networks were prepared by crosslinking UV-photopolymerization in an in situ approach (i.e., to allow preparation directly on the electrodes used). The crosslinks in the network improve the mechanical stability of the samples, as indicated by the free-standing nature of the materials and temperature-dependent rheology measurements. The averaged mesh size calculated from rheologoical measurements varied between 1.66 nm with 10 mol% crosslinker and 4.35 nm without crosslinker. The chemical structure of the ionic liquid (IL) monomers in the network was varied to achieve the highest possible ionic conductivity. The systematic variation in three series with a number of new IL monomers offers a direct comparison of samples obtained under comparable conditions. The ionic conductivity of generation II and III PIL networks was improved by three orders of magnitude, to the range of 7.1 × 10−6 S·cm−1 at 20 °C and 2.3 × 10−4 S·cm−1 at 80 °C, compared to known poly(vinylimidazolium·TFSI) materials (generation I). The transition from linear homopolymers to networks reduces the ionic conductivity by about one order of magnitude, but allows free-standing films instead of sticky materials. The PIL networks have a much higher voltage stability than PEO with the same amount and type of conducting salt, lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). GII-PIL networks are electrochemically stable up to a potential of 4.7 V vs. Li/Li+, which is crucial for a potential application as a solid electrolyte. Cycling (cyclovoltammetry and lithium plating-stripping) experiments revealed that it is possible to conduct lithium ions through the GII-polymer networks at low currents. We concluded that the synthesized PIL networks represent suitable candidates for solid-state electrolytes in lithium ion batteries or solid-state batteries.

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Polymerized Ionic Liquids: Correlation of Ionic Conductivity with Nanoscale Morphology and Counterion Volume

Cited by 68 publications

References 41 publications

Charge transport and glassy dynamics in polymeric ionic liquids as reflected by their inter- and intramolecular interactions

Charge transport and glassy dynamics in polymeric ionic liquids as reflected by their inter- and intramolecular interactions

Polymerized ionic liquids: Effects of counter‐anions on ion conduction and polymerization kinetics

In Situ Preparation of Crosslinked Polymer Electrolytes for Lithium Ion Batteries: A Comparison of Monomer Systems

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