Highly Frustrated Poly(ionic liquid) ABC Triblock Terpolymers with Exceptionally High Morphology Factors.

In this work, we report the successful synthesis of 17 unique compositions of a poly(ionic liquid) (PIL) ABC triblock terpolymer, poly(S-b-VBMIm-TFSI-b-HA), where S is styrene, VBMIm-TFSI is vinylbenzyl methylimidazolium bis(trifluoromethanesulfonyl)imide, and HA is hexyl acrylate. Nine distinct morphologies were observed, including two-phase and three-phase disordered microphase separated (D2 and D3), two-phase hexagonally packed cylinders (C2), core-shell hexagonally packed cylinders (CCS), three-phase lamellae (L3), two-phase lamellae (L2), core-shell double gyroid (Q230), spheres-in-lamellae (LSI), and a three-phase hexagonal superlattice of cylinders (CSL). The LSI morphology was unambiguously confirmed using small-angle X-ray scattering and transmission electron microscopy. Morphology type significantly impacted the ion conductivity of the PIL ABC triblock terpolymers, where remarkable changes in morphology factor (normalized ion conductivity) were observed with only small changes in the conducting volume fraction, i.e., PIL block composition. An exceptionally high morphology factor of 2.0 was observed from the PIL ABC triblock terpolymer with a hexagonal superlattice morphology due to the three-dimensional narrow, continuous PIL nanodomains that accelerate ion conduction. Overall, this work demonstrates the first systematic study of highly frustrated single-ion conducting ABC triblock terpolymers with a diverse set of morphologies and exceptionally high morphology factors, enabling the exploration of transport-morphology relationships to guide the future design of highly conductive polymer electrolytes.

Modifying the Electrocatalyst-Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells.

Polymer electrolyte membrane fuel cell (PEMFC) electrodes with a 0.07 mgPt cm-2 Pt/Vulcan electrocatalyst loading, containing only a sulfonated poly(ionic liquid) block copolymer (SPILBCP) ionomer, were fabricated and achieved a ca. 2× enhancement of kinetic performance through the suppression of Pt surface oxidation. However, SPILBCP electrodes lost over 70% of their electrochemical active area at 30% RH because of poor ionomer network connectivity. To combat these effects, electrodes made with a mix of Nafion/SPILBCP ionomers were developed. Mixed Nafion/SPILBCP electrodes resulted in a substantial improvement in MEA performance across the kinetic and mass transport-limited regions. Notably, this is the first time that specific activity values determined from an MEA were observed to be on par with prior half-cell results for Nafion-free Pt/Vulcan systems. These findings present a prospective strategy to improve the overall performance of MEAs fabricated with surface accessible electrocatalysts, providing a pathway to tailor the local electrocatalyst/ionomer interface.

Synthesis and High Alkaline Chemical Stability of Polyionic Liquids with Methylpyrrolidinium, Methylpiperidinium, Methylazepanium, Methylazocanium, and Methylazonanium Cations.

Herein, we present the synthesis of five styrene-based poly(ionic liquids) (PILs) containing (covalently linked) saturated N-heterocyclic cations with various ring sizes (i.e., methylpyrrolidinium, methylpiperidinium, methylazepanium, methylazocanium, and methylazonanium). High alkaline chemical stability was confirmed by 1H NMR spectroscopy after 4 weeks in 40 mol equiv of KOH (1.0 M KOH in D2O) at 80 °C for PILs with 5-, 6-, 7-, and 8-membered ring cations; a requirement for polymer electrolyte separators in long-lasting alkaline fuel cells. Additionally, ion conductivity of PILs increased by 4 orders of magnitude with increasing water content, where a master percolation power law curve was observed, that is, similar conductivity versus water volume fraction for all PILs, regardless of cation size.

Sulfonated Polymerized Ionic Liquid Block Copolymers.

The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions.

Polymerized ionic liquid diblock copolymers: impact of water/ion clustering on ion conductivity.

Herein, we examine the synergistic impact of both ion clustering and block copolymer morphology on ion conductivity in two polymerized ionic liquid (PIL) diblock copolymers with similar chemistries but different side alkyl spacer chain lengths (ethyl versus undecyl). When saturated in liquid water, water/ion clusters were observed only in the PIL block copolymer with longer alkyl side chains (undecyl) as evidenced by both small-angle neutron scattering and intermediate-angle X-ray scattering, i.e., water/ion clusters form within the PIL microdomain under these conditions. The resulting bromide ion conductivity in the undecyl sample was higher than the ethyl sample (14.0 mS cm(-1)versus 6.1 mS cm(-1) at 50 °C in liquid water) even though both samples had the same block copolymer morphology (lamellar) and the undecyl sample had a lower ion exchange capacity (0.9 meq g(-1)versus 1.4 meq g(-1)). No water/ion clusters were observed in either sample under high humidity or dry conditions. The resulting ion conductivity in the undecyl sample with lamellar morphology was significantly higher in the liquid water saturated state compared to the high humidity state (14.0 mS cm(-1)versus 4.2 mS cm(-1)), whereas there was no difference in ion conductivity in the ethyl sample when comparing these two states. These results show that small chemical changes to ion-containing block copolymers can induce water/ion clusters within block copolymer microdomains and this can subsequently have a significant effect on ion transport.

Binder-free three-dimensional high energy density electrodes for ionic-liquid supercapacitors.

We demonstrate a facile methodology to fabricate binder-free porous carbon nanofiber electrodes for room temperature ionic-liquid supercapacitors. The device provides an energy density of 80 W h kg(-1) based on the mass of two electrodes while retaining the high rate capability of supercapacitors with near-ideal CV curves at a high scan rate of 200 mV s(-1).

Prediction and validation of diffusion coefficients in a model drug delivery system using microsecond atomistic molecular dynamics simulation and vapour sorption analysis.

Diffusion of small to medium sized molecules in polymeric medical device materials underlies a broad range of public health concerns related to unintended leaching from or uptake into implantable medical devices. However, obtaining accurate diffusion coefficients for such systems at physiological temperature represents a formidable challenge, both experimentally and computationally. While molecular dynamics simulation has been used to accurately predict the diffusion coefficients, D, of a handful of gases in various polymers, this success has not been extended to molecules larger than gases, e.g., condensable vapours, liquids, and drugs. We present atomistic molecular dynamics simulation predictions of diffusion in a model drug eluting system that represent a dramatic improvement in accuracy compared to previous simulation predictions for comparable systems. We find that, for simulations of insufficient duration, sub-diffusive dynamics can lead to dramatic over-prediction of D. We present useful metrics for monitoring the extent of sub-diffusive dynamics and explore how these metrics correlate to error in D. We also identify a relationship between diffusion and fast dynamics in our system, which may serve as a means to more rapidly predict diffusion in slowly diffusing systems. Our work provides important precedent and essential insights for utilizing atomistic molecular dynamics simulations to predict diffusion coefficients of small to medium sized molecules in condensed soft matter systems.

Water clustering in glassy polymers.

In this study, water solubility and water clustering in several glassy polymers, including poly(methyl methacrylate) (PMMA), poly(styrene) (PS), and poly(vinylpyrrolidone) (PVP), were measured using both quartz spring microbalance (QSM) and Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Specifically, QSM was used to determine water solubility, while FTIR-ATR spectroscopy provided a direct, molecular-level measurement of water clustering. The Flory-Huggins theory was employed to obtain a measure of water-polymer interaction and water solubility, through both prediction and regression, where the theory failed to predict water solubility in both PMMA and PVP. Furthermore, a comparison of water clustering between direct FTIR-ATR spectroscopy measurements and predictions from the Zimm-Lundberg clustering analysis produced contradictory results. The failure of the Flory-Huggins theory and Zimm-Lundberg clustering analysis to describe water solubility and water clustering, respectively, in these glassy polymers is in part due to the equilibrium constraints under which these models are derived in contrast to the nonequilibrium state of glassy polymers. Additionally, FTIR-ATR spectroscopy results were compared to temperature-dependent diffusivity data, where a correlation between the activation energy for diffusion and the measured water clustering was observed.

Ion dynamics in porous carbon electrodes in supercapacitors using in situ infrared spectroelectrochemistry.

Electrochemical double layer capacitors (EDLCs), or supercapacitors, rely on electrosorption of ions by porous carbon electrodes and offer a higher power and a longer cyclic lifetime compared to batteries. Ionic liquid (IL) electrolytes can broaden the operating voltage window and increase the energy density of EDLCs. Herein, we present direct measurements of the ion dynamics of 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide in an operating EDLC with electrodes composed of porous nanosized carbide-derived carbons (CDCs) and nonporous onion-like carbons (OLCs) with the use of in situ infrared spectroelectrochemistry. For CDC electrodes, IL ions (both cations and anions) were directly observed entering and exiting CDC nanopores during charging and discharging of the EDLC. Conversely, for OLC electrodes, IL ions were observed in close proximity to the OLC surface without any change in the bulk electrolyte concentration during charging and discharging of the EDLC. This provides experimental evidence that charge is stored on the surface of OLCs in OLC EDLCs without long-range ion transport through the bulk electrode. In addition, for CDC EDLCs with mixed electrolytes of IL and propylene carbonate (PC), the IL ions were observed entering and exiting CDC nanopores, while PC entrance into the nanopores was IL concentration dependent. This work provides direct experimental confirmation of EDLC charging mechanisms that previously were restricted to computational simulations and theories. The experimental measurements presented here also provide deep insights into the molecular level transport of IL ions in EDLC electrodes that will impact the design of the electrode materials' structure for electrical energy storage.