A novel sPEEK nanocomposite membrane with well-controlled sPOSS aggregation in tunable nanochannels for fast proton conduction.

To greatly increase the proton conductivity of a sPEEK nanocomposite membrane without water swelling problems, sulfonated PEEK (sPEEK) nanocomposite membranes were prepared by regulating the nanocomposite concentration of sulfonated POSS (sPOSS). Incorporation of sPOSS into sPEEK afforded a 39% increase in proton conductivity at 80 °C/100% RH and a 70% increase in cell performance at 1.5 wt% sPOSS concentration. In particular, water swelling problems were not observed even with the attained proton conductivity, as with Nafion. The water swelling of the pristine sPEEK membrane was 18.8%; it increased to 24.4% at 5.0 wt% of sPOSS loading, which was 11.1% lower than that of Nafion. The high modulus of sPOSS and the good distribution of sPOSS also enhanced the tensile strength by 40.5% and the strain by 65.8% compared with the pristine sPEEK membrane. At more than 1.5 wt% sPOSS concentration, the conductivity and power output of the nanocomposite membranes decreased despite the increased IEC, which is highly related to aggregation of sPOSS nanoparticles in the proton conducting nanochannels and changes in the nanochannel size. The sizes of the nanochannels were measured by SAXS, and it was found that expansion of the nanochannels was enhanced at 1.5 wt% by the best distribution of sPOSS and absorption of water. The increased IEC, expanded nanochannels and distribution of sPOSS without aggregation promoted proton conduction through the nanochannels.

An enhanced electrochemical and cycling properties of novel boronic Ionic liquid based ternary gel polymer electrolytes for rechargeable Li/LiCoO2 cells.

A new generation of boronic ionic liquid namely 1-ethyl-3-methylimidazolium difluoro(oxalate)borate (EMImDFOB) was synthesized by metathesis reaction between 1-ethyl-3-methylimiazolium bromide and lithium difluoro(oxalate)borate (LiDFOB). Ternary gel polymer electrolyte membranes were prepared using electrolyte mixture EMImDFOB/LiDFOB with poly vinylidenefluoride-co-hexafluoropropylene (PVdF-co-HFP) as a host matrix by facile solvent-casting method and plausibly demonstrated its feasibility to use in lithium ion batteries. Amongst ternary gel electrolyte membrane, DFOB-GPE3, which contained 80 wt% of EMImDFOB/LiDFOB and 20 wt% PVdF-co-HFP, showed excellent electrochemical and cycling behaviors. The highest ionic conductivity was found to be 10-3 Scm-1 at 378 K. Charge-discharge profile of Li/DFOB-GPE3/LiCoO2 coin cell displayed a maximum discharge capacity of 148.4 mAhg-1 at C/10 rate with impressive capacity retention capability and columbic efficiency at 298 K.

A Rapid One-Pot Synthesis of Novel High-Purity Methacrylic Phosphonic Acid (PA)-Based Polyhedral Oligomeric Silsesquioxane (POSS) Frameworks via Thiol-Ene Click Reaction.

Herein, we demonstrate a facile methodology to synthesis a novel methacrylic phosphonic acid (PA)-functionalized polyhedral oligomeric silsesquioxanes (POSSs) via thiol-ene click reaction using octamercapto thiol-POSS and ethylene glycol methacrylate phosphate (EGMP) monomer. The presence of phosphonic acid moieties and POSS-cage structure in POSS-S-PA was confirmed by Fourier transform infrared (FT-IR) and nuclear magnetic resonance (¹H, 29Si and 31P-NMR) analyses. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrum of POSS-S-PA acquired in a dithranol matrix, which has specifically designed for intractable polymeric materials. The observed characterization results signposted that novel organo-inorganic hybrid POSS-S-PA would be an efficacious material for fuel cells as a proton exchange membrane and high-temperature applications due to its thermal stability of 380 °C.

Effect of variation of average pore size and specific surface area of ZnO electrode (WE) on efficiency of dye-sensitized solar cells.

Mesoporous ZnO nanoparticles have been synthesized with tremendous increase in specific surface area of up to 578 m(2)/g which was 5.54 m(2)/g in previous reports (J. Phys. Chem. C 113:14676-14680, 2009). Different mesoporous ZnO nanoparticles with average pore sizes ranging from 7.22 to 13.43 nm and specific surface area ranging from 50.41 to 578 m(2)/g were prepared through the sol-gel method via a simple evaporation-induced self-assembly process. The hydrolysis rate of zinc acetate was varied using different concentrations of sodium hydroxide. Morphology, crystallinity, porosity, and J-V characteristics of the materials have been studied using transmission electron microscopy (TEM), X-ray diffraction (XRD), BET nitrogen adsorption/desorption, and Keithley instruments.

Proton conductive nano-channel membranes based on polyaniline with phosphonic acid moieties for low relative humidity.

Most sulfonic acid based-membranes come to the limit because of high cost and low performance at low relative humidity (RH). Therefore, we synthesized phosphonic acid functionalized polyaniline (PA-PANI). PANI was used as polymer back bone because of excellent chemical mechanical stability and easy synthesis from relatively cheap monomer, and phosphonic acid presents the relatively high proton conducting in nano-channel without water because of its self dissociation nature. PA-PANI was synthesized by bonding chemically with phosphonic acid groups using 3-bromopropylamine as a reagent. PA-PANI nano-channel membrane showed high and stable conductivities (approximately 0.035 S/cm at 80 to approximately 180 degrees C) under low RH. And PA-PANI nano-channel membranes compared with Nafion (10(-4) S/cm at < 30% RH), have higher proton conductivities. This fact showed phosphonic acid groups were more effective at low RH than sulfonic acid groups. Because the proton conductivity of Nafion decreases considerably at elevated temperature due to dehydration, our low cost membranes using phosphonic acid moiety may be expected to substitute sulfonic acid based-membranes such as Nafion.

Plasticizing effect of K+ ions and succinonitrile on electrical conductivity of [poly(ethylene oxide)-succinonitrile]/KI-I2 redox-couple solid polymer electrolyte.

The plasticizing effect of the K(+) ions and succinonitrile on the electrical conductivity of a new redox-couple solid polymer electrolyte system, (1 - x)[0.5poly(ethylene oxide):0.5succinonitrile]:x[0.9KI:0.1I2] with x = 0-0.2 in weight fraction, is reported. An increase of x resulted in an increase of the electrical conductivity (σ25°C) of the electrolyte. The electrolyte with x = 0.15 exhibited the highest σ25°C value, ~7 × 10(-4) S cm(-1), and is referred to as the optimum conducting composition (OCC). In addition to an increase of the mobile ion concentration with increasing x, X-ray diffractometry, Fourier-transform infrared spectroscopy, polarized optical microscopy, UV-vis spectroscopy, and differential scanning calorimetry studies revealed a decrease of poly(ethylene oxide) crystallinity/an increase of ionic mobility, indicating the plasticizing effect of the K(+) ions. Plasticizing and molecular diffusing properties of the succinonitrile further helped to improve the electrical conductivity of the electrolyte.

Nafion/silane nanocomposite membranes for high temperature polymer electrolyte membrane fuel cell.

The polymer electrolyte membrane fuel cell (PEMFC) has been studied actively for both potable and stationary applications because it can offer high power density and be used only hydrogen and oxygen as environment-friendly fuels. Nafion which is widely used has mechanical and chemical stabilities as well as high conductivity. However, there is a drawback that it can be useless at high temperatures (> or = 90 degrees C) because proton conducting mechanism cannot work above 100 degrees C due to dehydration of membrane. Therefore, PEMFC should be operated for long-term at high temperatures continuously. In this study, we developed nanocomposite membrane using stable properties of Nafion and phosphonic acid groups which made proton conducting mechanism without water. 3-Aminopropyl triethoxysilane (APTES) was used to replace sulfonic acid groups of Nafion and then its aminopropyl group was chemically modified to phosphonic acid groups. The nanocomposite membrane showed very high conductivity (approximately 0.02 S/cm at 110 degrees C, <30% RH).

Characterization of sulfonated poly(ether ether ketone)/silane nanocomposite membrane for high temperature polymer electrolyte membrane fuel cells.

The perfluorosulfonic acid polymer membrane is most widely used in PEMFCs. However, its some major drawbacks like high cost and performance limitation at high temperature are obstacles of its commercialization. The goal of this study was to develop low cost membranes which have good conductivity in the range of PEMFCs operating temperature. We fabricated new sPEEK/3-APTES nanocomposite membrane where inorganic particles were chemically bonded to sulfuric acid group of sPEEK. PEEK is a thermally stable, mechanically tough and very cheap polymer. And the addition of 3-APTES and phosphorous acid increased the proton conductivity of composite membranes at high temperatures. This nanocomposite membranes maintained good conductivity at 110 degrees C.

Poly(dimethyl siloxane) membrane for high temperature proton exchange membrane fuel cells.

Sulfonic acid-based membrane gives the relatively high conductivity only in the presence of water, but phosphoric acid presents the relatively high proton conductivity without water because of its self dissociation natures to develop high temperature PEMFCs. We synthesized the thermostable material that has phosphorous groups based on poly(dimethyl siloxane) (PDMS). PDMS, which is intrinsically hydrophobic was modified to be amphiphilic by substituting end groups with hydrophilic phosphorous groups. Phase separation resulted in forming the proton conducting channels. The membranes maintained the constant proton conductivity above 130 degrees C under dry conditions. Also they were thermally stable up to 300 degrees C and may be used as high temperature proton conducting membrane at low humid conditions.

Characterization of Nafion/zirconium sulphophenyl phosphate nanocomposite membrane for direct methanol fuel cells.

Layered structure zirconium sulphophenyl phosphate (ZrSPP) was prepared from the precipitation of Zr4+ ion and m-sulphophenyl phosphonic (SPP) acid at a mole ratio of P to Zr = 2.0. The reflective index measurement indicated that the methanol permeability of unmodified Nafion 117 was 2.3 x 10(-6) cm2/s at RT while that of the Nafion/ZrSPP membrane (approximately 50 micro/m thick) decreased to 6.5 x 10(-7) cm2/s. Nafion/ZrSPP (10 wt%) nanocomposite membranes delivered constant power output 104 mW/cm2 at 0.4 V under 1 M MeOH/dry air at 70 degrees C even in the wide range of air stoichiometry from 1.5 to 3.0.

Nanocrystalline porous TiO2 electrode with ionic liquid impregnated solid polymer electrolyte for dye sensitized solar cells.

This communication reports the detailed fabrication of electrodes and solid polymer electrolyte with ionic liquid (IL) as an electrolyte for dye sensitized solar cell (DSSC). Thick porous TiO2 film has been obtained by spreading and sintering TiO2 colloidal paste using "doctor blade" and characterized by SEM, TEM and XRD. The polymer electrolyte was PEO:KI/I2 incorporated with 1-ethyl 3-methylimidazolium thiocyanate (EMImSCN) as IL. Dispersal of IL in the polymer electrolyte improved the ionic conductivity and cell efficiency.