Surya Subianto

Composite Polymer Electrolyte Containing Ionic Liquid and Functionalized Polyhedral Oligomeric Silsesquioxanes for Anhydrous PEM Applications

A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

Interfacial interactions in aprotic ionic liquid based protonic membrane and its correlation with high temperature conductivity and thermal properties.

Novel supported liquid membranes (SLMs) have been developed by impregnating Nafion and Hyflon membranes with ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI). These supported liquid membranes were characterized in terms of their ionic liquid uptake behavior, leaching of ionic liquid by water, thermal stability, mechanical properties, glass transition temperature, ion exchange capacity, and proton conductivity. In general, modified membranes are more flexible than unmodified samples due to the plasticization effects of the ionic liquid. However, these supported liquid membranes exhibit a significant increase in their operational stability and proton conductivity over unmodified membranes. We also demonstrate that proton conductivity of these supported liquid membranes allows conduction of protons in anhydrous conditions with conductivity increasing with temperature. Conductivity of up to 3.58 mS cm(-1) has been achieved at 160 degrees C in dry conditions, making these materials promising for various electrochemical applications.

Single step elaboration of size-tuned Pt loaded titania nanofibres

Conductive titania nanofibres supporting Pt nanoparticles were synthesised in a one-pot method based on the electrospinning technique. The dimensions of both the oxide fibres and platinum particles were tuneable, leading to versatile nanomaterials with possible applications as electrodes for energy conversion devices.

Facile Fabrication of Polymerizable Ionic Liquid Based-Gel Beads via Thiol–ene Chemistry

Multipurpose gel beads prepared from natural or synthetic polymers have received significant attention in various applications such as drug delivery, coatings, and electrolytes because of their versatility and unique performance as micro- and nanocontainers.1 However, comparatively little work has been done on poly(ionic liquid)-based materials despite their unique ionic characteristics. Thus, in this contribution we report the facile preparation of polymerizable ionic liquid-based gel beads using thiol-ene click chemistry. This novel system incorporates pentaerythritol tetra (3-mercaptopropionate) (PETKMP) and 1,4-di(vinylimidazolium) butane bisbromide in a thiol-ene-based photopolymerization to fabricate the gel beads. Their chemical structure, thermal and mechanical properties have been investigated using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). The gel beads possess low Tg and their ionic functionalities attribute self-healing properties and their ability to uptake small molecules or organic compounds offers their potential use as pH sensing material and macrocontainers.

Composite Electrolyte Membranes from Partially Fluorinated Polymer and Hyperbranched, Sulfonated Polysulfone

Macromolecular modification of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) was done with various proportions of sulfonic acid terminated, hyperbranched polysulfone (HPSU) with a view to prepare ion conducting membranes. The PVDF-co-HFP was first chemically modified by dehydrofluorination and chlorosulfonation in order to make the membrane more hydrophilic as well as to introduce unsaturation, which would allow crosslinking of the PVDF-co-HFP matrix to improve the stability of the membrane. The modified samples were characterized for ion exchange capacity, morphology, and performance. The HPSU modified S-PVDF membrane shows good stability and ionic conductivity of 5.1 mS cm−1 at 80 °C and 100% RH for blends containing 20% HPSU, which is higher than the literature values for equivalent blend membranes using Nafion. SEM analysis of the blend membranes containing 15% or more HPSU shows the presence of spherical domains with a size range of 300–800 nm within the membranes, which are believed to be the HPSU-rich area.

Promising Aquivion Composite Membranes based on Fluoroalkyl Zirconium Phosphate for Fuel Cell Applications

Layered zirconium phosphate (ZP) that bears fluorinated alkyl chains bonded covalently to the layers (ZPR) was used as a nanofiller in membranes based on a short-side-chain perfluorosulfonic acid (PFSA) to mechanically reinforce the PFSA hydrophobic component. Compared to the pristine PFSA, membranes with a ZPR loading up to 30 wt% show enhanced mechanical properties, and the largest improvement of elastic modulus (E) and yield stress (σY ) are observed for the 10 wt% ZPR membrane: ΔE/E up to 90% and ΔσY /σY up 70% at 70°C and 80% relative humidity (RH). In the RH range 50-95%, the in-plane conductivity of the composite membranes reaches 0.43 S cm(-1) for 10 wt% ZPR at 110°C and is on average 30% higher than the conductivity of the pristine PFSA. The 10 wt % ZPR membrane is as hydrated as the neat PFSA membrane at 50% RH but becomes progressively less hydrated with increasing RH both at 80 and 110°C. The fuel cell performance of this membrane, at 80°C and 30% RH, is better than that of the unmodified PFSA.

Polymeric Ionic Liquid Nanoparticle Emulsions as a Corrosion Inhibitor in Anticorrosion Coatings

In this contribution, we report the facile preparation of cross-linked polymerizable ionic liquid (PIL)-based nanoparticles via thiol–ene photopolymerization in a miniemulsion. The synthesized PIL nanoparticles with a diameter of about 200 nm were fully characterized with regard to their chemical structures, morphologies, and properties using different techniques, such as Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. To gain an in-depth understanding of the physical and morphological structures of the PIL nanoparticles in an emulsion, small-angle neutron scattering and ultra-small-angle neutron scattering were used. Neutron scattering studies revealed valuable information regarding the formation of cylindrical ionic micelles in the spherical nanoparticles, which is a unique property of this system. Furthermore, the PIL nanoparticle emulsion was utilized as an inhibitor in a self-assembled nanophase particle (SNAP) coating. The corrosion protection ability of the resultant coating was examined using potentiodynamic polarization and electrochemical impedance spectroscopy. The results show that the PIL nanoparticle emulsion in the SNAP coating acts as an inhibitor of corrosion and is promising for fabricating advanced coatings with improved barrier function and corrosion protection.

Bulk heterojunction organic photovoltaics from water-processable nanomaterials and their facile fabrication approaches

Organic thin film photovoltaics based on bulk-heterojunction donor-acceptor combinations have received significant interest due to their potential for low-cost, large-scale solution processing. However, current state-of-the-art cells utilise materials soluble mainly in halogenated solvents which pose processing challenges due to their toxicity and thus environmental hazards. In this contribution, we look at various nanomaterials, and alternative processing of these solar cells using environmentally friendly solvents, and review recently reported different strategies and approaches that are making inroads in this field. Specifically, we focus on the use of water-dispersible donors and acceptors, use of aqueous solvents for fabrication and discuss the merits of the two main approaches of water-processable solar cells; namely, through the use of water-soluble materials and the use of aqueous dispersion rather than a solution, as well as review some of the recent advances in alternative fabrication techniques.

Reactive coaxial electrospinning of ZrP/ZrO2 nanofibres

Zirconium phosphate/zirconium oxide nanofibres have been fabricated using a novel, reactive coaxial electrospinning approach. In this approach, a zirconium precursor and a phosphorus source are spun together from separate solutions, using a coaxial needle, in order to delay formation of zirconium phosphate gel. The reaction between the zirconium and phosphorus sources is considered to initiate at the interface region in the coaxial fibres. The resultant nanofibres are calcined and further treated with H3PO4. The formation of ZrP/ZrO2 nanofibres was confirmed using 31P MAS NMR. Electron microscopy shows that the fibre morphology depends on solution parameters, and the X-ray amorphous fibres exhibit compositional homogeneity. Incorporation of the nanofibres into the short-side-chain perfluorosulfonic acid ionomer Aquivion™ yields membranes having significantly increased mechanical properties with greater elastic modulus and yield point as well as increased proton conductivity compared to both cast and commercial Aquivion™ membranes.

A Poly(ionic liquid) Gel Electrolyte for Efficient all Solid Electrochemical Double-Layer Capacitor

Polyionic liquid based gels have stimulated significant interest due to their wide applications in flexible electronics, such as wearable electronics, roll-up displays, smart mobile devices and implantable biosensors. Novel supported liquid gel electrolyte using polymerisable ionic liquid and an acrylate monomer, has been developed in this work by entrapping ionic liquid during polymerisation instead of post polymerisation impregnation. The chemically crosslinked polyionic liquid gel electrolyte (PIL) is prepared using 2-hydroxyethylmethacrylate (HEMA) monomer and a polymerisable ionic liquid, 1,4-di(vinylimidazolium)butane bisbromide (DVIMBr) in an ionic liquid (IL- 1-butyl-3 methylimidazolium hexafluorophosphate) as the polymerisation solvent, which resulted in in-situ entrapment of the IL in the gel during polymerisation and crosslinking of the polymer. The supported liquid gel electrolyte (SLG) material was characterised with thermal analysis, infrared spectroscopy, and dynamic mechanical analysis, and was found to be stable with good mechanical properties. The electrochemical analysis showed that these chemically cross-linked PIL gel electrolyte-supported ILs are suitable for solid-state, flexible supercapacitor applications.