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1.
《Current Applied Physics》2010,10(5):1255-1260
A new type of inorganic–organic hybrid solid state polymer electrolyte consisting of heteropolytungsticacid impregnated polyepichlorohydrin with iodine/iodide and TiO2 nanofiller have been prepared for their potential application in dye sensitized solar cells. The prepared polymer electrolytes were well characterized by FT-IR, Scanning electron microscopy (SEM), X-ray diffraction (XRD), Electrochemical Impedance analysis (EIS) and Thermal analysis (TGA). The prepared polymer electrolyte with TiO2 nanofiller shows reasonable ionic conductivity (20.4 × 10−6 S cm−1) compared to pure polyepichlorohydrin (2.0 × 10−9 S cm−1) at ambient temperature. The presence of negatively charged redox species heteropolytungsticacid in the polymer matrix prevents the photo reduction of iodide (back electron transfer) and the presence of TiO2 nanofiller increases the degree of amorphousity of the polymer which in turn prolongs the stability of the fabricated dye sensitized solar cell over a long period compared to bare polymer electrolyte.  相似文献   

2.
《Solid State Ionics》2006,177(11-12):1091-1097
The effects of compositions on properties of PEO/KI/I2 salts polymer electrolytes were investigated to optimize the photovoltaic performance of solid state DSSCs. XRD pattern for the mole ratio 12:1 of [EO:KI] was showed the formation of complete amorphous complex. DSC results also confirmed the amorphous nature of the polymer electrolyte. The highest value of ionic conductivity is 8.36 × 10 5 S/cm at 303 K (ambient temperature) and 2.32 × 10 4 S/cm at 333 K (moderate temperature) for the mole ratio 12:1 of EO:KI complex. The effect of contribution of [I] and [I3] concentration with conductivity were also evaluated. FTIR spectrum reveals that the alkali metal cations were co-ordinated to ether oxygen of PEO. The formation of polyiodide ions, such as symmetric I3 (114 cm 1) and I5 (145 cm 1) caused by the addition of iodine was confirmed by FT Raman spectroscopic measurements. The optimum composition of PEO–KI–I2 polymer electrolyte system for higher conductivity at ambient and moderate temperatures was reported. A linear Arrhenius type behaviour was observed for all the PEO–KI polymer complexes. Transport number measurements were carried out for several polymer electrolyte compositions. Dye-sensitized solar cells were fabricated by using higher conductivity polymer electrolyte compositions and its photoelectrochemical performance was investigated. The fill factor, short-circuit current, photovoltage and energy conversion efficiency of the DSSC assembled with optimized electrolyte composition were calculated to be 0.563, 6.124 mA/cm2, 593 mV and 2.044% respectively.  相似文献   

3.
Poly(ethylene glycol)/poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PEG/PAMPS) with a transparent appearance were prepared in the presence of ammonium persulfate (APS) as an initiator at 70 °C for 24 h. PEG/PAMPS-based polymer gel electrolytes in a motionless and uniform state were obtained by adding the required amount of liquid electrolytes to a dry PEG/PAMPS polymer. Liquid electrolytes include organic solvents with high boiling points (-1-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL)) and a redox couple (alkali metal iodide salt/iodine). The optimized conditions for PEG/PAMPS-based gel electrolytes based on the salt type, the concentration of alkali metal iodide salt/iodine, and solvent volume ratio were determined to be NaI, 0.4 M NaI/0.04 M I2, and NMP:GBL (7:3, v/v), respectively. The highest ionic conductivity and the liquid electrolyte absorbency were 2.58 mS cm?1 and 3.6 g g?1 at 25 °C, respectively. The ion transport mechanism in both the polymer gel electrolytes and liquid electrolytes is investigated extensively, and their best fits with respect to the temperature dependence of the ionic conductivity are determined with the Arrhenius equation.  相似文献   

4.
《Solid State Ionics》2006,177(35-36):3141-3146
Quasi-solid state polymer electrolytes have been prepared from poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) as gelator for 1-ethyl-3-methylimidazolium based ionic liquids (with anions like trifluoromethanesulfonate [EMIM][TfO], bis(trifluoromethanesulfonyl)imide [EMIM][Tf2N]) and polyacrylonitrile (PAN) for gelation of 1-ethyl-3-methylimidazolium dicyanamide [EMIM][DCA] as well as I/I3 as the redox couple. All electrolytes exhibit high ionic conductivity in the range of 10 3 S/cm. The effect of gelation, redox couple concentration, I/I3 ratio, choice of cations and additives on the triiodide diffusion and charge-transfer resistance of the platinum/electrolyte interface (Rct) were studied. The apparent diffusion coefficient of triiodide ion (D(I3)) at various iodide/triiodide ratios in liquid and gelified electrolytes has been calculated from measurements of the diffusion limited current (Ilim) in electrochemical cell resembling the set-up of a dye-sensitized solar cell. The charge-transfer resistance of the platinum/electrolyte interface as well as the capacitance of the electrical double layer (Cdl) have been calculated from impedance measurements. Electrolytes with reduced content of polymer (2.5 wt.%) were doped with Al2O3 particles of different sizes (50 nm, 300 nm, 1 μm). The dispersion of the particles proceeds by speedy stirring of the hot electrolyte and the addition of PAN provides a homogeneous suspension. The addition of Al2O3 particles causes a slight increase of the triiodide diffusion constants. Furthermore the suggested enhancement of the charge transfer rate shows a dependence on the size of the particles.  相似文献   

5.
《Solid State Ionics》2006,177(3-4):343-346
Solid polymer electrolyte PEO9 Mg(ClO4)2 incorporating 10 wt.% nano-porous Al2O3 filler grains has been prepared by the solvent casting technique using acetonitrile as the common solvent. Al2O3 powder (activated acidic, Aldrich) with grain size 104 μm and pore size 5.8 nm were incorporated as an inert filler. Electrolyte films have been characterized by differential scanning calorimetry, complex impedance and dc polarization measurements. The nano-composite electrolyte as well as the filler-free electrolyte appear to be predominantly anionic conductors with ClO4 ions being the migrating species. The presence of the alumina filler has enhanced the ionic conductivity significantly. The conductivity enhancement has been attributed to Lewis acid–base type interactions between H groups at the filler grain surface and the ClO4 ions. Transient H-bonding through these interactions is expected to provide additional hopping sites and favourable conducting pathways for migrating ionic species.  相似文献   

6.
《Solid State Ionics》2006,177(1-2):65-71
A comb-like EVOH based single ion polymer electrolyte (EVOH-g-SPEG) was synthesized by sulfonification of EVOH grafts 2-(2-chloroethoxy) ethanol (C4H9O2Cl)/2-[2-(2-chloroethxy) ethoxy] ethanol (C6H13O3Cl) with 1, 3-propane sultone. The main chain of the comb-like polymer is hydrophobic polyethylene segments; the side chain is hydrophilic poly (ethylene glycol) (PEG) segment, which can solubilize large amounts of inorganic salts. The sulfonic acid group was introduced onto the end of the PEG side chain. The acid form of SPE was successfully obtained by being dialyzed from the products with acid solution. The saturation water sorption of EVOH-g-SPEG membrane increased with the side chain length and the immersion time. The XRD results indicate that the water in SPE membrane region can destroy the membrane crystalline structure and the water absorption membranes are nearly amorphous. AFM phase images of the hydration membranes clearly show the hydrophilic domains, with sizes increasing from 10 to 35 nm as a function of the side chain length. A phase inversion could be observed when n  5, which was consistent with a rapid increase in water absorption. And the ion conductivity is also measured by AC impedance. The conductivity is greatly influenced by ion exchange capacity and water sorption. The comb-like EVOH-g-SPEG polymer electrolyte grafts with 2 PEG side chain provides the highest ionic conductivity (1.65 × 10 3 S cm 1). The comb-like polymer could be a candidate as new polymeric electrolyte material for fuel cells and other electrochemical devices.  相似文献   

7.
Effect of micron-sized MgO particles dispersion on poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF–HFP) based magnesium-ion (Mg2+) conducting gel polymer electrolyte has been studied using various electrical and electrochemical techniques. The composite gel films are free-standing and flexible with enough mechanical strength. The optimized composition with 10 wt% MgO particles offers a maximum electrical conductivity of ∼6×10−3 S cm−1 at room temperature (∼25°C). The Mg2+ ion conduction in gel film is confirmed from cyclic voltammetry, impedance spectroscopy and transport number measurements. The applicability of the composite gel electrolyte to a rechargeable battery system has been examined by fabricating a prototype cell consisting of Mg (or Mg–MWCNT composite) and V2O5 as negative and positive electrodes, respectively. The rechargeability of the cell has been improved, when Mg metal was substituted by Mg–MWCNT composite as negative electrode.  相似文献   

8.
《Solid State Ionics》2006,177(26-32):2683-2686
New type polymer electrolyte films based on poly(acrylonitrile), (PAN), and cyanoethylated poly(vinyl alcohol), (CN-PVA), were prepared and their conducting behaviors were investigated. CN-PVA was prepared from poly(vinyl alcohol), (PVA) and acrylonitrile in the presence of sodium hydroxide and quaternary ammonium halide as a phase transfer catalyst. Free standing PAN- and CN-PVA-based electrolyte films were prepared by casting the propylene carbonate (PC) solution containing PAN, CN-PVA and LiClO4 and removing some amount of PC. Ionic conductivity of the electrolyte film, (PAN)10(CN-PVA) 10(LiClO4)8(PC)4 composite film was 14.6 mS cm 1 at 30 °C and 22.4 mS cm 1 at 60 °C. FTIR results for the electrolyte films suggest that the nitrile groups in the CN-PVA matrix mainly interact with the lithium ions in the films and enhance dissolution of the lithium salt in the electrolyte films.  相似文献   

9.
Nithya  S.  Selvasekarapandian  S.  Premalatha  M. 《Ionics》2017,23(10):2767-2774

Solid polymer electrolytes based on polyacrylonitrile (PAN) doped with ammonium iodide (NH4I) have been prepared by solution casting method with different molar ratios of polymer and salt using DMF as solvent. The XRD pattern confirms the dissociation of salt. The FTIR analysis confirms the complex formation between the polymer and the salt. A shift in glass transition temperature (T g ) of the PAN/NH4I electrolytes has been observed from the DSC thermograms, which indicates the interaction between the polymer and the salt. The conductivity analysis shows that the polymer electrolyte with 20 mol% NH4I has the highest conductivity equal to 1.106 × 10−3 S cm−1 at room temperature. The activation energy (E a ) has been found to be low for the highest conductivity sample. The dielectric permittivity (ε*) and modulus (M*) have been calculated from the alternating current (AC) impedance spectroscopy in the frequency range 42 Hz–1 MHz. The DC polarization measurement shows that the conductivity is mainly due to ions.

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10.

Solid polymer electrolytes (SPEs) based on polyethylene oxide (PEO) complexed with magnesium triflate Mg(Tf)2 or Mg(CF3SO3)2) and incorporating the ionic liquid (IL) (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI)) were prepared by solution cast technique. The electrolyte was optimized and characterized using electrical conductivity, cationic transport number measurements, and cyclic voltammetry. The highest conductivity of the PEO/Mg(Tf)2, 15:1 (molar ratio), electrolyte at room temperature was 1.19 × 10−4 S cm−1 and this was increased to 3.66 × 10−4 S cm−1 with the addition of 10 wt.% ionic liquid. A significant increase in the Mg2+ ion transport number was observed with increasing content of the ionic liquid in the PEO-Mg(Tf)2 electrolyte. The maximum Mg2+ ion transport number obtained was 0.40 at the optimized electrolyte composition. A battery of the configuration Mg/ and [(PEO)15:Mg(Tf)2+10%IL]/TiO2-C was assembled and characterized. Preliminary studies showed that the discharge capacity of the battery was 45 mA h g−1.

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11.
Preparation of P(AN-MMA) gel electrolyte for Li-ion batteries   总被引:1,自引:0,他引:1  
Phase inversion technique was used to prepare poly(acrylonitrile-methyl methacrylate) [P(AN-MMA)]-based microporous gel electrolyte with addition of SiO2 via in-situ composition for Li-ion batteries. The P(AN-MMA) was synthesized by emulsion polymerization and was dissolved into N,N-dimethylformamide (DMF) to form a uniform solution, while tetraethyl orthosilicate (TEOS) was added into the solution and was hydrolyzed by catalysis of alkali ammonia solution to form SiO2. Then the solution was cast onto a glass plate using a doctor blade and exposed to humidified atmosphere produced by ultrasonic humidifier, followed by washing, rinsing, and drying, successively. The gel electrolyte was obtained by putting the P(AN-MMA) microporous membrane in a liquid electrolyte. The gelled microporous membrane sucked with 755 wt% of liquid electrolyte vs the dried membrane. It had a porosity of 70%, about 1∼5 μm of pores, and presented an ionic conductivity of 0.94 × 10−3 S/cm at room temperature. Electrochemical stability window of the porous gel polymer electrolyte was determined by running a linear sweep voltammetry. The decomposition voltage of the polymer electrolyte exceeds 4.5 V vs Li. The coin test cell with the microporous gel electrolyte showed a good cycling performance. The discharge capacity retention was above 87% at 0.1 C for 45 cycles.  相似文献   

12.
Boopathi  G.  Pugalendhi  S.  Selvasekarapandian  S .  Premalatha  M.  Monisha  S.  Aristatil  G. 《Ionics》2017,23(10):2781-2790

A proton-conducting polymer electrolyte based on agar and ammonium nitrate (NH4NO3) has been prepared through solution casting technique. The prepared polymer electrolytes were characterized by impedance spectroscopy, X-ray diffraction, and Fourier transform infra-red spectroscopy. Impedance analysis shows that sample with 60 wt.% NH4NO3 has the highest ionic conductivity of 6.57 × 10−4 S cm−1 at room temperature. As a function of temperature, the ionic conductivity exhibits an Arrhenius behaviour increasing from 6.57 × 10−4 S cm−1 at room temperature to 1.09 × 10−3 S cm−1 at 70 °C. Transport parameters of the samples were calculated using Wagner’s polarization method and thus shows that the increase in conductivity is due to the increase in the number of mobile ions. Fuel cell has been constructed with the highest proton conductivity polymer 40agar/60NH4NO3 and the open circuit voltage is found to be 558 mV.

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13.
The effect of phenothiazine (PTZ) as dopant on PVDF/KI/I2 electrolyte was studied for the fabrication of efficient dye-sensitized solar cell (DSSC). The different weight percentage (wt%) ratios (0, 20, 30, 40 and 50%) of PTZ doped PVDF/KI/I2 electrolyte films were prepared by solution casting method using DMF as a solvent. The following techniques such as Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), X-ray diffractometer (XRD) and AC-impedance analysis have been employed to characterize the prepared polymer electrolyte films. The FT-IR studies revealed the complex formation between PVDF/KI/I2 and PTZ. The crystalline and amorphous nature of polymer electrolytes were confirmed by DSC and XRD analysis respectively. The ionic conductivities of polymer electrolyte films were calculated from the AC-impedance analysis. The undoped PVDF/KI/I2 electrolyte exhibited the ionic conductivity of 4.68×10−6 S cm−1 and this value was increased to 7.43×10−5 S cm−1 when PTZ was added to PVDF/KI/I2 electrolyte. On comparison with different wt% ratios, the maximum ionic conductivity was observed for 20% PTZ-PVDF/KI/I2 electrolyte. A DSSC assembled with the optimized wt % of PTZ doped PVDF/KI/I2 electrolyte exhibited a power conversion efficiency of 2.92%, than the undoped PVDF/KI/I2 electrolyte (1.41%) at similar conditions. Hence, the 20% PTZ-PVDF/KI/I2 electrolyte was found to be optimal for DSSC applications.  相似文献   

14.
Vijaya  N.  Selvasekarapandian  S.  Sornalatha  M.  Sujithra  K.S.  Monisha  S. 《Ionics》2017,23(10):2799-2808

Research has been undertaken to develop polymer electrolytes based on biodegradable natural polymers such as cellulose acetate, starch, gelatin, and chitosan, which are being used as polymer hosts for obtaining new polymer electrolytes for their applications in various electrochemical devices such as batteries, sensors, and electrochromic windows. Pectin is a naturally available material which is extracted from the skin of citrus fruits. Pectins, also known as pectic polysaccharides, are rich in galacturonic acid. The present study focuses on the proton-conducting polymer electrolytes based on the biopolymer pectin doped with ammonium chloride (NH4Cl) and ammonium bromide (NH4Br) prepared by solution casting technique. The prepared membranes are characterized using XRD, FTIR, and AC impedance techniques to study their complexation behavior, amorphous nature, and electrical properties. The conductivity of pure pectin membrane has been found to be 9.41 × 10−7 S cm−1. The polymer systems with 30 mol% NH4Cl-doped pectin and 40 mol% NH4Br-doped pectin have been found to have maximum ionic conductivity of 4.52 × 10−4 and 1.07 × 10−3 S cm−1, respectively. The conductivity value has increased by three orders of magnitude compared to pure pectin membrane. The dielectric behavior of both the systems has been explained using dielectric permittivity and electric modulus spectra.

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15.
《Solid State Ionics》2006,177(15-16):1281-1286
Composite electrolyte comprising phosphotungstic acid (PWA) filler and 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF4) room temperature ionic liquid (RTIL) in poly(2-hydroxyethyl methacrylate) (PHEMA) matrix has been prepared. The polymer matrix was formed by free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) monomers. BMImBF4 was used as both ionic source and plasticizer, and PWA filler provided the proton conductivity in this system. The interactions and structure changes of the PHEMA-RTIL-PWA composites were investigated by Fourier transform infrared spectra, differential scanning calorimetry, and X-ray diffraction. PWA fillers maintained their Keggin structure within a limited range and enhanced the ionic conductivity of the composite electrolyte. The electrolyte with PWA at the 2 wt.% showed the highest ionic conductivity of 8 × 10 4 S cm 1 at room temperature and 96% relative humidity.  相似文献   

16.
Nanocomposite polymer electrolyte consisting of polyvinyl alcohol (PVA) and lithium acetate with TiO2 filler has been synthesised by combination of solution cast technique and sol–gel process. The composite electrolyte films were characterised by different experimental techniques. The average particle size of composite electrolytes lies between 25 and 30?nm. System is essentially ionic with maximum conductivity of polymer electrolyte 90[80PVA–20LiAc]:10TiO2 (~4.5?×?10?6?S?cm?1) at room temperature.  相似文献   

17.
Pb2+ ion conducting polymer composite electrolyte films, based on polyvinyl alcohol and polyethylene glycol doped with Pb(NO3)2 salt, were prepared using the solution cast technique. X-ray diffraction patterns of polymer composite with salt reveal the decrease in the degree of crystallinity with increasing concentration of the salt. The dielectric plots show an increase in dielectric permittivity at low frequency side with increasing salt concentration as well as temperature. The frequency dependence of ac conductivity obeys the Jonscher power law, and the maximum dc conductivity value is found to be 2.264×10?7 S/m at 303?K for the polymer composite with 30?mol% Pb(NO3)2. The activation energy for the ion in polymer electrolyte has been calculated from the modulus plots, and is in good agreement with the activation energy calculated from the temperature-dependent dc conductivity plot. The modulus plots indicate the non-Debye nature of the sample. For pure and doped films at room temperature, the impedance plots exhibit only one semicircle, indicating the presence of one type of conduction mechanism, whereas for 30?mol% salt doped with electrolyte film at different temperatures, it demonstrated the existence of bulk and electrode?Celectrolyte interface properties. Optical absorption spectra show a broad peak for all complexes, while compared with pure polymer composite, due to the complex formation of polymer electrolyte with Pb(NO3)2 and their absorption edge, direct band gap and indirect band gap were calculated. It was found that the absorption edge and energy gap values decreased on doping with Pb(NO3)2 dopant.  相似文献   

18.
PEO/LiCF3SO3 (LiTFS) /Ethylene carbonate (EC) polymer electrolyte membranes were prepared with a solution casting method followed by a hot pressing process. The effect of the hot pressing process on the in-plane conductivity of the PEO electrolyte membranes was evaluated using a four-electrode AC impedance method. The composition, morphology, and microstructure of the composite polymer electrolyte were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The AC impedance measurement results indicate that the hot pressing process can increase the room temperature conductivity of the membranes 14 times to 1.7 × 10− 3 S cm− 1 depending upon the duration of the hot pressing process. The SEM, FTIR, XRD, and DSC results indicate that the hot pressing process could increase the amorphous part of the polymer electrolyte membrane or convert large spherulite crystals into nano-sized crystals.  相似文献   

19.
Thin films of ZnSe and PEO–chitosan blend polymer doped with NH4I and iodine crystals were prepared to form the two sides of a semiconductor electrolyte junction. ZnSe was electrodeposited on indium tin oxide (ITO) conducting glass. The polymer is a blend of 50 wt% chitosan and 50 wt% polyethylene oxide. The polymer blend was complexed with ammonium iodide (NH4I), and some iodine crystals were added to the polymer–NH4I solution to provide the I/I3−redox couple. The room temperature ionic conductivity of the polymer electrolyte is 4.32 × 10−6 S/cm. The polymer film was sandwiched between the ZnSe semiconductor and an ITO glass to form a ZnSe/polymer electrolyte/ITO photovoltaic cell. The open circuit voltage (V oc) of the fabricated cells ranges between 200 to 400 mV and the short circuit current between 7 to 10 μA.  相似文献   

20.
The search for anionic conductors based on solid polymer electrolytes is important for the development of photo-electrochemical (PEC) solar cells due to their many favourable chemical and physical properties. Although solid polymer electrolytes have been extensively studied as cation, mainly lithium ion, conductors for applications in secondary batteries, their use as anionic conductors have not been studied in greater detail. In a previous paper we reported the application of a PEO based iodide ion conducting electrolyte in a PEC solar cell. This electrolyte had the composition PEO: Pr4N+I? = 9:1 with 50 wt.% ethylene carbonate (EC). In this work we have studied the effect of incorporating alumina filler on the properties of this electrolyte. The investigation was extended to electrical and dielectric measurements including high frequency impedance spectroscopy and thermal analysis.In the DSC themograms two endothermic peaks have been observed on heating, one of these peaks is attributed with the melting of the PEO crystallites, while the other peak with a melting temperature ~ 30 °C is attributed to the melting of the EC rich phase. The melting temperature of both these peaks shows a marked variation with alumina content in the electrolyte. The temperature dependence of the conductivity shows that there is an abrupt conductivity increase in the first heating run evidently due to the melting of the EC rich phase. High conductivity values are retained at lower temperatures in the second heating. Conductivity isotherms show the existence of two maxima, one at ~ 5% Al2O3 content and the other at ~ 15%. The occurrence of these two maxima has been explained in terms of the interactions caused by alumina grains, the crystallinity and melting of the PEO rich phase. As seen from latent heat of melting, the crystallinity of the electrolyte has reduced considerably during the first heating run. In contrast to the conductivity enhancement caused by ceramic fillers in PEO-based cation containing electrolytes, no conductivity enhancement has been observed in the present PEO based anionic conducting materials by adding alumina except at low temperatures.  相似文献   

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