Design of Highly Conductive PILs by Simple Modification of Poly(epichlorohydrin--ethylene oxide) with Monosubstituted Imidazoles.

High ionic conductivity poly(ionic liquid)s (PILs) are of growing interest for their thermal and electrochemical stability, processability, and potential in safe, flexible all-solid-state electrochemical devices. While various approaches to enhance the ionic conductivity are reported, the influence of cation substituents is rarely addressed. Moreover, some of the asymmetric anions recently developed for high-conductivity ionic liquids were never tested in PILs.

A New (Trifluoromethane)Sulfonylimide Single-Ion Conductor with PEG Spacer for All-Solid-State Lithium-Based Batteries.

The choice of ionic-liquid-like monomers (ILM) for single-ion conducting polyelectrolytes (SICPs) is crucial for the performance of all-solid-state lithium batteries. In the current study, we propose a novel approach for development of SICPs via design and synthesis of a new ILM with long poly(ethylene oxide) spacer between methacrylic group and (trifluoromethane)sulfonylimide anion. Its homopolymer shows an ionic conductivity that is ∼5 orders of magnitude higher (9.

Diffusion and structure of propylene carbonate-metal salt electrolyte solutions for post-lithium-ion batteries: From experiment to simulation.

The diffusion of cations in organic solvent solutions is important for the performance of metal-ion batteries. In this article, pulsed field gradient nuclear magnetic resonance experiments and fully atomistic molecular dynamic simulations were employed to study the temperature-dependent diffusive behavior of various liquid electrolytes representing 1M propylene carbonate solutions of metal salts with bis(trifluoromethylsulfonyl)imide (TFSI-) or hexafluorophosphate (PF6-) anions commonly used in lithium-ion batteries and beyond. The experimental studies revealed the temperature dependence of the diffusion coefficients for the propylene carbonate (PC) solvent and for the anions following an Arrhenius type of behavior.

Dynamic Ion Gels from the Complex Coacervation of Oppositely Charged Poly(ionic liquid)s.

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition-fragmentation chain-transfer radical copolymerization, respectively. Upon mixing solutions of these two PILs in acetone with stoichiometric amounts of ion pairs, ionic exchanges induce coacervation and, after solvent evaporation, lead to the formation of a dynamic ion gel (DIG) and the concomitant release of free [1-methyl-3-butyl imidazolium]TFSI ionic liquid (IL). A comparison of thermal (), ion conducting (σ), and viscoelastic (elastic moduli (')) properties for DIGs and their parent polyelectrolytes, as well as extracted and IL-doped DIGs, demonstrates the formation of ionic cross-links and the ability to easily produce polymer electrolytes with enhanced ionic conductivity (σ up to 4.

Unique Method for Facile Postsynthetic Modification of Nonisocyanate Polyurethanes.

Nonisocyanate polyurethanes (NIPUs) are broadly investigated as a potential replacement for conventional polyurethanes (PUs) to eliminate the use of toxic isocyanates and reduce occupational hazards. One of the most popular approaches to NIPU synthesis is the polyaddition of cyclic bis(carbonate)s and diamines to form poly(hydroxyurethane)s (PHUs). However, such PHUs are highly hydrophilic due to the presence of two hydroxyl groups per repeat unit, and the resulting moisture absorption significantly degrades their thermomechanical performance and physical stability upon exposure to humidity, thus limiting their utility.

Unravelling the functionality of anionic and non-ionic plant seed gums on milk protein cryogels conveying Lacticaseibacillus rhamnosus GG.

Cryogels offer a promising macroporous platform that can be employed as either a functional ingredient in food composites or a colloidal template for incorporating bioactives, including probiotic living cells. The aim of the present work is to explore the functionality of two plant seed polysaccharides, flaxseed gum (FG) and alfalfa galactomannan (AAG), in individual and combined (1:1 ratio) milk protein-based cryogels, namely sodium caseinate (NaCas) and whey protein isolate (WPI). These cryogels were created by freeze-drying hydrogels formed via L.

A New Method to Prepare Stable Polyaniline Dispersions for Highly Loaded Cathodes of All-Polymer Li-Ion Batteries.

A new method for the preparation of polyaniline (PANI) films that have a 2D structure and can record high active mass loading (up to 30 mg cm) via acid-assisted polymerization in the presence of concentrated formic acid was developed. This new approach represents a simple reaction pathway that proceeds quickly at room temperature in quantitative isolated yield with the absence of any byproducts and leads to the formation of a stable suspension that can be stored for a prolonged time without sedimentation. The observed stability was explained by two factors: (a) the small size of the obtained rod-like particles (50 nm) and (b) the change of the surface of colloidal PANI particles to a positively charged form by protonation with concentrated formic acid.

Mechanically Robust Poly(ionic liquid) Block Copolymers as Self-Assembling Gating Materials for Single-Walled Carbon-Nanotube-Based Thin-Film Transistors.

The proliferation of high-performance thin-film electronics depends on the development of highly conductive solid-state polymeric materials. We report on the synthesis and properties investigation of well-defined cationic and anionic poly(ionic liquid) AB-C type block copolymers, where the AB block was formed by random copolymerization of highly conductive anionic or cationic monomers with poly(ethylene glycol) methyl ether methacrylate, while the C block was obtained by post-polymerization of 2-phenylethyl methacrylate. The resulting ionic block copolymers were found to self-assemble into a lamellar morphology, exhibiting high ionic conductivity (up to 3.

Tunning CO Separation Performance of Ionic Liquids through Asymmetric Anions.

This work aims to explore the gas permeation performance of two newly-designed ionic liquids, [Cmim][CFBF] and [Cmim][CFSOC(CN)], in supported ionic liquid membranes (SILM) configuration, as another effort to provide an overall insight on the gas permeation performance of functionalized-ionic liquids with the [Cmim] cation. [Cmim][CFBF] and [Cmim][CFSOC(CN)] single gas separation performance towards CO, N, and CH at T = 293 K and T = 308 K were measured using the time-lag method. Assessing the CO permeation results, [Cmim][CFBF] showed an undermined value of 710 Barrer at 293.

Structure conformation, physicochemical and rheological properties of flaxseed gums extracted under alkaline and acidic conditions.

The present work aimed at investigating an extraction protocol based on consecutive steps of isoelectric point (pH ~ 4.25) mediated gum swelling and deproteinisation as an alternative method to produce flaxseed gum extracts of enhanced techno-functional characteristics. The osidic and proximate composition, structure conformation, flow behaviour, dynamic rheological and thermal properties of gums isolated from brown and golden flaxseeds were assessed.

Unique Carbonate-Based Single Ion Conducting Block Copolymers Enabling High-Voltage, All-Solid-State Lithium Metal Batteries.

Safety and high-voltage operation are key metrics for advanced, solid-state energy storage devices to power low- or zero-emission HEV or EV vehicles. In this study, we propose the modification of single-ion conducting polyelectrolytes by designing novel block copolymers, which combine one block responsible for high ionic conductivity and the second block for improved mechanical properties and outstanding electrochemical stability. To synthesize such block copolymers, the ring opening polymerization (ROP) of trimethylene carbonate (TMC) monomer by the RAFT-agent having a terminal hydroxyl group is used.

Reinforcement of Styrene Butadiene Rubber Employing Poly(isobornyl methacrylate) (PIBOMA) as High Thermoplastic Polymer.

A set of poly(isobornyl methacrylate)s (PIBOMA) having molar mass in the range of 26,000-283,000 g mol was prepared either via RAFT process or using free radical polymerization. These linear polymers demonstrated high glass transition temperatures ( up to 201 °C) and thermal stability ( up to 230 °C). They were further applied as reinforcing agents in the preparation of the vulcanized rubber compositions based on poly(styrene butadiene rubber) (SBR).

Ionic Polyureas-A Novel Subclass of Poly(Ionic Liquid)s for CO 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 CO capture. In this work, a new family of poly(ionic liquid)s (PILs) comprising cationic polyureas (PURs) with tetrafluoroborate (BF) anions has been synthesized. Condensation of various diisocyanates with novel ionic diamines and subsequent ion metathesis reaction resulted in high molar mass ionic PURs (M = 12 ÷ 173 × 10 g/mol) with high thermal stability (up to 260 °C), glass transition temperatures in the range of 153-286 °C and remarkable CO capture (10.

Li Coordination of a Novel Asymmetric Anion in Ionic Liquid-in-Li Salt Electrolytes.

We analyze the influence of the asymmetry of the anion on coordination and transport processes in a Li salt/ionic liquid system. The relatively new asymmetric 2,2,2-trifluoromethylsulfonyl--cyanamide (TFSAM) anion was investigated in PyrTFSAMLiTFSAM over a broad concentration range (up to = 0.7 Li salt) and was compared to the well-known bis(trifluoromethanesulfonyl)amide (TFSA) anion.

Neat ionic liquids versus ionic liquid mixtures: a combination of experimental data and molecular simulation.

Simple mixtures of ionic liquids (IL-IL mixtures) can become a promising approach for the substitution of task-specific ILs. Such a concept was explored in this article by comparison of the thermophysical properties of neat 1-ethyl-3-methylimidazolium 2,2,2-trifluoromethylsulfonyl-N-cyanoamide, [Cmim][TFSAM], and equimolar mixtures of two structurally similar ILs having more common ions. Molecular dynamics (MD) simulations were additionally used to further highlight structural aspects of these systems at a molecular level.

Ionic liquids with anions based on fluorosulfonyl derivatives: from asymmetrical substitutions to a consistent force field model.

Herein, seven anions including four imide-based, namely bis[(trifluoromethyl)sulfonyl]imide (TFSI), bis(fluorosulfonyl)imide (FSI), bis[(pentafluoroethyl)sulfonyl]imide (BETI), 2,2,2-trifluoromethylsulfonyl-N-cyanoamide (TFSAM) and 2,2,2-trifluoro-N-(trifluoromethylsulfonyl) acetamide (TSAC), and two sulfonate anions, trifluoromethanesulfonate (triflate, TF) and nonafluorobutanesulfonate (NF), are considered and compared. The volumetric mass density and dynamic viscosity of five ionic liquids containing these anions combined with the commonly used 1-ethyl-3-methylimidazolium cation (CCim), [CCim][FSI], [CCim][BETI], [CCim][TFSAM], [CCim][TSAC] and [CCim][NF] are measured in the temperature range of 293.15 ≤ T/K ≤ 353.

Exploring the effect of fluorinated anions on the CO/N separation of supported ionic liquid membranes.

The CO and N permeation properties of ionic liquids (ILs) based on the 1-ethyl-3-methylimidazolium cation ([Cmim]) and different fluorinated anions, namely 2,2,2-trifluoromethylsulfonyl-N-cyanoamide ([TFSAM]), bis(fluorosulfonyl) imide ([FSI]), nonafluorobutanesulfonate ([CFSO]), tris(pentafluoroethyl)trifluorophosphate ([FAP]), and bis(pentafluoroethylsulfonyl)imide ([BETI]) anions, were measured using supported ionic liquid membranes (SILMs). The results show that pure ILs containing [TFSAM] and [FSI] anions present the highest CO permeabilities, 753 and 843 Barrer, as well as the greatest CO/N permselectivities of 43.9 and 46.

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.

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.