Polymerization of the new double-charged monomer bis-1,3(N,N,N trimethylammonium dicyanamide)-2-propylmethacrylate and ionic conductivity of the novel polyelectrolytes

The achievement of high ionic conductivity in single-ion conducting polymer electrolytes is one of the important aims for various electrochemical devices including modern lithium batteries. One way to enhance the ionic conductivity in polyelectrolyte systems is to increase the quantity of charge carriers in each monomer unit. Highly charged poly(bis-1,3(N,N,N-trimethylammonium)-2-propylmethacrylate) with one of the most conducting anions, namely dicyanamide, was prepared via free radical bulk polymerization or using ionic liquids as reaction medium. The cationic polymers of the double-charged monomer have molar masses up to equation image = 1,830,000 g/mol and the ionic conductivity equal to 5.51 × 10−5 S/cm at 25°C. The film forming ability, crystallinity, thermal stability, and glass transition temperatures of the new polymeric ionic liquids obtained from detailed studies are presente

Unconventional poly(ionic liquid)s combining motionless main chain 1,2,3-triazolium cations and high ionic conductivity

International audienceWe report the synthesis of two novel alpha-azide-omega-alkyne monomers with short n-hexyl and diethylene glycol spacers. Their polyaddition by both copper(I)-catalyzed and thermal Huisgen azide-alkyne 1,3-dipolar cycloaddition followed by alkylation using N-methyl bis(trifluoromethylsulfonyl)imide affords the corresponding 1,2,3-triazolium-based poly(ionic liquid)s. Their physical, ion conducting and electrochemical properties are discussed based on the chemical structure of the spacer and the regiochemistry of the 1,2,3-triazolium groups. These novel polyelectrolytes combine motionless main chain 1,2,3-triazolium cations with low glass transition temperature (T-g = -38 degrees C), high ionic conductivity under anhydrous conditions (sigma(DC) = 1.0 x 10(-5) S cm(-1) at 25 degrees C) and high electrochemical stability (ESW = 5.9 V vs. Ag+/Ag and 3.7 V vs. Li+/Li)

Probing the Effect of Anion Structure on the Physical Properties of Cationic 1,2,3-Triazolium-Based Poly(ionic liquid)s

International audienceTo extensively explore the influence of anion structure on the physical properties of poly(ionic liquid) s (PILs) a series of PILs having main-chain 1,2,3-triazolium cations was synthesized via copper(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) followed by N-alkylation with iodomethane and anion metathesis with different metal salts, that is, Li(CF3SO2)(2)N, Li(CF3CF2SO2)(2)N, K(FSO2)(2)N, K(CF3SO2)N(CN), Ag(CN)(2)N, and sodium 4,5-dicyano-1,2,3-triazolate. To isolate the effect of anion on physical properties of PILs, a common iodide precursor was used to maintain constant the average degree of polymerization (DPn) and chain dispersity. Detailed structure/properties relationship analyses demonstrated a lack of correlation between anion chemical structure, ionic conductivity, and glass transition temperatures. Among synthesized series, the PIL derivative having bis(trifluoromethylsulfonyl) imide counter anion showed the best compromise in performance: low glass transition temperature (T-g=-268 degrees C), high thermal stability (T-onset = 340 degrees C) and superior ionic conductivity (sigma(DC) = 8.5 x 10(-6) S/cm at 30 degrees C), which makes it an interesting candidate for various key modern electrochemical applications

Copolymers Formation by Photopolymerization of (Meth)acrylates Containing Dissolved Polyheteroarylenes

International audienceRadical photopolymerization of (meth)acrylates in the presence of dissolved polyheteroarylenes has been investigated. The kinetics of radical polymerization of unsaturated monomers in the presence of polyheteroarylenes and model compounds has been studied by Differential Scanning Photocalorimetry and Infrared Spectroscopy. From the results of investigations into the kinetics and the polymer structures (Fourier Transform Infrared Spectroscopy, Nuclear Magnetic Resonance, Size-exclusion Chromatography, Thermogravimetric analysis), it has been established that radical photopolymerization of vinyl monomers in the presence of polyheteroarylenes leads to the formation of copolymers owing to chain transfer reactions and/or chain termination by the relevant condensation polymer. Using Electron Spin Resonance Spectroscopy the novel radicals upon the addition of model compounds for the polyheteroarylenes have been detected, and a mechanism of copolymer formation has been proposed

Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries

Polymer electrolytes have been proposed as replacement for conventional liquid electrolytes in lithium-ion batteries (LIBs) due to their intrinsic enhanced safety. Nevertheless, the power delivery of these materials is limited by the concentration gradient of the lithium salt. Single-ion conducting polyelectrolytes represent the ideal solution since their nature prevents polarization phenomena. Herein, the preparation of a new family of single-ion conducting block copolymer polyelectrolytes via reversible addition−fragmentation chain transfer polymerization technique is reported. These copolymers comprise poly(lithium 1-[3-(methacryloyloxy)-propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) and poly(ethylene glycol) methyl ether methacrylate blocks. The obtained polyelectrolytes show low Tg values in the range of −61 to 0.6 °C, comparatively high ionic conductivity (up to 2.3 × 10−6 and 1.2 ×10−5 S cm−1 at 25 and 55 °C, respectively), wide electrochemical stability (up to 4.5 V versus Li+/Li), and a lithium-ion transference number close to unity (0.83). Owing to the combination of all mentioned properties, the prepared polymer materials were used as solid polyelectrolytes and as binders in the elaboration of lithium−metal battery prototypes with high charge/discharge efficiency and excellent specific capacity (up to 130 mAh g−1) at C/15 rat

Truly solid state electrochromic devices constructed from polymeric ionic liquids as solid electrolytes and electrodes formulated by vapor phase polymerization of 3,4-ethylenedioxythiophene

International audienc

Ionic Polyureas—A Novel Subclass of Poly(Ionic Liquid)s for CO2 Capture

The growing concern for climate change and global warming has given rise to investigations in various research fields, including one particular area dedicated to the creation of solid sorbents for efficient CO2 capture. In this work, a new family of poly(ionic liquid)s (PILs) comprising cationic polyureas (PURs) with tetrafluoroborate (BF4) anions has been synthesized. Condensation of various diisocyanates with novel ionic diamines and subsequent ion metathesis reaction resulted in high molar mass ionic PURs (Mw = 12 ÷ 173 × 103 g/mol) with high thermal stability (up to 260 °C), glass transition temperatures in the range of 153–286 °C and remarkable CO2 capture (10.5–24.8 mg/g at 0 °C and 1 bar). The CO2 sorption was found to be dependent on the nature of the cation and structure of the diisocyanate. The highest sorption was demonstrated by tetrafluoroborate PUR based on 4,4′-methylene-bis(cyclohexyl isocyanate) diisocyanate and aromatic diamine bearing quinuclidinium cation (24.8 mg/g at 0 °C and 1 bar). It is hoped that the present study will inspire novel design strategies for improving the sorption properties of PILs and the creation of novel effective CO2 sorbents.This research was in part supported by Fonds National de la Recherche Luxembourg (FNR) with Agency Nationale de la Recherche (ANR) through the ANR-FNR project DISAFECAP (Agreement number INTER/ANR/18/13358226). Partial funding by the Spanish Agencia Estatal de Investigación (AEI), PCTI 2013-2017 del Principado de Asturias and ERDF through projects RTI2018-100832-B-I00 and IDI/2018/000233 is gratefully acknowledged. Partial funding by Russian Foundation for Basic Research (RFBR) through project 16-03-00768_a is acknowledged. Elemental analysis and IR spectroscopy were performed with the financial support from Ministry of Science and Higher Education of the Russian Federation using the equipment of Center for molecular composition studies of INEOS RAS.Peer reviewe

A New Volume-Based Approach for Predicting Thermophysical Behavior of Ionic Liquids and Ionic Liquid Crystals

Volume-based prediction of melting points and other properties of ionic liquids (ILs) relies on empirical relations with volumes of ions in these low-melting organic salts. Here we report an accurate way to ionic volumes by Bader’s partitioning of electron densities from X-ray diffraction obtained via a simple database approach. For a series of 1-tetradecyl-3-methylimidazolium salts, the volumes of different anions are found to correlate linearly with melting points; larger anions giving lower-melting ILs. The volume-based concept is transferred to ionic liquid crystals (ILs that adopt liquid crystalline mesophases, ILCs) for predicting the domain of their existence from the knowledge of their constituents. For 1-alkyl-3-methylimidazolium ILCs, linear correlations of ionic volumes with the occurrence of LC mesophase and its stability are revealed, thus paving the way to rational design of ILCs by combining suitably sized ions

A New Volume-Based Approach for Predicting Thermophysical Behavior of Ionic Liquids and Ionic Liquid Crystals

Volume-based prediction of melting points and other properties of ionic liquids (ILs) relies on empirical relations with volumes of ions in these low-melting organic salts. Here we report an accurate way to ionic volumes by Bader’s partitioning of electron densities from X-ray diffraction obtained via a simple database approach. For a series of 1-tetradecyl-3-methylimidazolium salts, the volumes of different anions are found to correlate linearly with melting points; larger anions giving lower-melting ILs. The volume-based concept is transferred to ionic liquid crystals (ILs that adopt liquid crystalline mesophases, ILCs) for predicting the domain of their existence from the knowledge of their constituents. For 1-alkyl-3-methylimidazolium ILCs, linear correlations of ionic volumes with the occurrence of LC mesophase and its stability are revealed, thus paving the way to rational design of ILCs by combining suitably sized ions

Novel phosphonated poly(1,3,4-oxadiazole)s: Synthesis in ionic liquid and characterization

International audienceA new class of poly(1,3,4-oxadiazole)s (PODs) with pendant phosphonic acid groups was synthesized via direct polycondensation of dicarboxylic acids and their dihydrazides using ionic liquid, namely 1-methyl-3-propylimidazoluium bromide ([mpim]Br), as a reaction medium, and triphenyl phosphite as a reaction activator. The polymers were obtained with inherent viscosities equal to 0.46–0.58 dL/g in two steps starting from polyhydrazides formation followed by thermal polycyclization under high vacuum. Polymers derived from 5-phosphonoisophtalic acid were soluble in traditional organic solvents, while application of 2-phosphonoterephthalic acid resulted in formation of insoluble gels. Such properties as thermal stability, glass transition temperatures, water uptake, molecular weights and proton conductivity of novel polymers were investigated in detail. A comparison between common poly(1,3,4-oxadiazole)s and their phosphorylated or phosphonated analogs having the same polymer backbone demonstrated that PODs with pendant phosphonic acid groups possess approximately the same thermal stability, but greater glass transition temperatures along with reduced solubility. Transparent flexible films cast from such novel polymers were characterized by high tensile properties, namely tensile strength of about 90–100 MPa and elongation up to 8%. The proton conductivity values measured at the temperature range from 20 to 90 °C varied from 4 × 10−7 to 5 × 10−6 S/cm at 100% relative humidity