Utilizing an ionic liquid for synthesizing a soft matter polymer ``gel'' electrolyte for high rate capability lithium-ion batteries

A cross-linked polymer ``gel'' electrolyte obtained from free radical polymerization of a vinyl monomer (acrylonitrile; AN) in a room temperature ionic liquid electrolyte (N,N-methyl butyl pyrrolidinium-bis (trifluoromethanesulphonyl)imide-lithium bis(trifluoromethanesulphonyl) imide;LiTFSI-[Py(1,4)-TFSI]) for application in high rate capability rechargeable lithium-ion batteries is discussed here. This is a novel alternative compared to the often employed approach of using a molecular liquid as the medium for performing the polymerization reaction. The polymer ``gel'' electrolytes (AN:Py(1,4)-TFSI = 0.16-0.18, w/w) showed remarkable compliable mechanical strength and higher thermal stability compared to LiTFSI-[Py(1,4)-TFSI]. Despite two orders increase in magnitude of viscosity of polymer ``gels'', the room temperature ionic conductivity of the ``gels'' (1.1 x 10(-3)-1.7 x 10(-3) Omega(-1) cm(-1)) were nearly identical to that of the ionic liquid (1.8 x 10(-3) Omega(-1) cm(-1)). The present ``gel'' electrolytes did not exhibit any ageing effects on ionic conductivity similar to the conventional polymer gel electrolytes (e.g. high molecular weight polymer + salt + high dielectric constant molecular solvent). The disorder (ionic liquid) to a relative order (cross-linked polymer electrolyte) transformation does not at all influence the concentration of conducting species. The polymer framework is still able to provide efficient pathways for fast ion transport. Unlike the ionic liquid which is impossible to assemble without a conventional separator in a cell, the polymer ``gel'' electrolyte could be conveniently assembled without a separator in a Li vertical bar lithium iron phosphate (LiFePO(4)) cell. Compared to the ionic liquid, the ``gel'' electrolyte showed exceptional cyclability and rate capability (current density: 35-760 mA g(-1) with LiFePO(4) electronically wired with carbon (amorphous or multiwalled nanotube [MWCNT]).

Substrate integrated Lead-Carbon hybrid ultracapacitor with flooded, absorbent glass mat and silica-gel electrolyte configurations

Lead-Carbon hybrid ultracapacitors (Pb-C HUCs) with flooded, absorbent-glass-mat (AGM) and silica-gel sulphuric acid electrolyte configurations are developed and performance tested. Pb-C HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area carbon with graphite-sheet substrate as negative electrodes. The electrode and silica-gel electrolyte materials are characterized by XRD, XPS, SEM, TEM, Rheometry, BET surface area, and FTIR spectroscopy in conjunction with electrochemistry. Electrochemical performance of SI-PbO2 and carbon electrodes is studied using cyclic voltammetry with constant-current charge and discharge techniques by assembling symmetric electrical-double-layer capacitors and hybrid Pb-C HUCs with a dynamic Pb(porous)/PbSO4 reference electrode. The specific capacitance values for 2 V Pb-C HUCs are found to be 166 F/g, 102 F/g and 152 F/g with a faradaic efficiency of 98%, 92% and 88% for flooded, AGM and gel configurations, respectively.

Study of ion solvation and ion association in polymer gel electrolyte with polyethylene oxide-co-polypropylene oxide as a plasticizer

Using a molal conductance method, ion solvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel electrolytes with amorphous ethylene oxide-co-propylene oxide (EO-co-PO, <(M)over bar (n)>, = 1750) as the plasticizer were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) and ion pairs (alpha(p)) decreases, while that of triple ions (alpha(t)) increases linearly with increasing salt concentration. The dependence of these fractions on molecular weight of plasticizer was also examined. It was shown that alpha(i) and alpha(t) increase and alpha(p) decreases with increasing molecular weight. The result of temperature dependence of these fractions was very interesting: when the temperature is lower than 55 degrees C, alpha(i) increases while alpha(p) and alpha(t) decrease with increasing temperature; however, when the temperature is higher than 55 degrees C, the reverse is true.

The conductivity behavior of a polymer gel electrolyte

A new kind of polymer gel electrolyte which is composed of polytriethylene glycol dimethacrylate(PTREGD), propylene carbonate(PC) and LiPF6 has been prepared by thermal polymerization. The conductivity was measured as a function of temperature, and it was found that the Arrhenius equation was held very well through out the salt concentration studied. Maximum room temperature conductivity of 4.95 x 10(-4) S/cm, as well as a minimum activation energy value of 18.90 kJ/mol were obtained at the same salt concentration of 0.22 mol/L.

Ionic conductivity of gel electrolyte based on polydiethylene glycol dimethacrylate and its copolymer

Gel electrolytes were prepared by thermal polymerization of diethylene glycol dimethacrylate (DIEGD) or its copolymer with methoxy polyethylene glycol monomethacrylate, molecular weight 400 (PEM(400)), at a molar ratio of 3/1 in the presence of propylene carbonate (PC) and LiClO4. Conductivity was measured by impedance spectroscopy. It was found that the conductivity data follow the Arrhenius equation in the homopolymer gel system, while the VTF equation holds true in the copolymer gel system. An increase in conductivity was observed in the copolymer gel system. However, whether in the homopolymer or in the copolymer gel system, a maximum ambient temperature conductivity was found at a salt concentration near 1.50 mol/l. Further, the activation energy values calculated from Arrhenius plots for the homopolymer gel system tended to reach a minimum value with increasing salt concentration. (C) 1996 Elsevier Science Ltd

Agar-Based Gel Electrolyte for Electrochromic Device Application

Gel Polymer Electrolytes (GPE) based on agar and containing LiClO4 have been prepared, characterized and applied to electrochromic devices. The ionic conductivity revealed the best result of 6.5 x 10(-5) S/cm for the sample with 17 wt.% of LiClO4, which increased to 5.4 x 10(-4) S/cm at 72 degrees C. TheGPE have been used in electrochromic devices (ECD) with K-glass/WO3/GPE/CeO2-TiO2/K-glass configuration. The ECD changed transmittance values up to 30% between the colored and transparent states. The charge density measurements revealed an increase of 5.5 to 7.5 mC/cm(2) from the first to 500th cycles and then a decrease to 4.4 mC/cm(2) during the next 4500 cycles. Coloration efficiency (eta) of 25 cm(2)/C was obtained.

Application of a New Cyclic Guanidinium Ionic Liquid on Dye-Sensitized Solar Cells (DSCs)

A new cyclic guanidinium ionic liquid OGI (1,3-dimethyl-2-N ''-methyl-N ''-octylimidazoguanidinium iodide) has been used as a quasi-solid-state electrolyte for dye-sensitized solar cells (DSCs), and 6.38% conversion efficiency was achieved at AM 1.5 simulated sunlight (9.81 mW cm(-2)). Further gelation with SiO2 nanoparticles afforded the solid-state electrolyte, which presented overall conversion efficiency of 5.85%. The diffusion properties of these OGI-based electrolytes were investigated. In the meantime, the optimal structure and ion-pairing interaction in OGI have been proposed by density functional theoretical calculation (DFT) at the B3LYP/6-21G(d,p) level.

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

Gelatin-based protonic electrolyte for electrochromic windows

Proton-conducting gel polymer electrolytes based on gelatin plasticized with glycerol and containing acetic acid were investigated, characterized, and applied to electrochromic window. For glycerol contents varying from 7% to 48%, the conductivity of the uniform and predominantly amorphous gel electrolyte was found to follow a Vogel-Tamman-Fulcher behavior with the temperature. Typically, for the electrolyte chosen to make 7 x 2 cm(2) electrochromic smart window with the configuration: glass/fluor-doped tin oxide (FTO)/WO(3)/gelatin electrolyte/CeO(2)-TiO(2)/FTO/glass and containing 28% of glycerol, the conductivities were found to be of the order of 5 x 10(-5) S/cm at room temperature and 3.6 x 10(-4) S/cm at 80 A degrees C. The device was characterized by spectroelectrochemical techniques and was tested up to 10,000 cycles showing a fast coloring/bleaching behavior, where the coloring process was achieved in 10 s and the bleaching in 2 s. The transmission variation at the wavelength of 550 nm was about 15%. The cyclic voltammograms showed a very good reversibility of the cathodic/anodic processes, and the charge density was about 3.5 mC/cm(2). The memory tests showed that the transmittance in the colored state increased by 8% in 90 min after removing the potential.

Plasticized pectin-based gel electrolytes

Pectin is a natural polymer present in plants and, as all natural polymers has biodegradation properties. Chemically, pectin is a polysaccharide composed of a linear chain of 1 -> 4 linked galacturonic acids, which is esterified with methanol at 80%. The pectin-based gel electrolytes in a transparent film form were obtained by a plasticization process with glycerol and addition of LiClO(4). The films showed good ionic conductivity results, which increased from 10(-5) S/cm for the samples with 37 wt.% of glycerol to 4.7 x 10(-4) S/cm at room temperature for the sample with 68 wt.% of glycerol. The electrochemical behaviors of the samples were studied by electrochemical impedance spectroscopy (EIS), and Nyquist graphs are showed and discussed. The obtained pectin-based samples also presented good adherence to the glass, flexibility, homogeneity (SEM) and transparency (about 70% in the vis) properties. They are good candidates to be applied as gel electrolytes in electrochromic devices. (C) 2009 Elsevier Ltd. All rights reserved.

Comparison of performance parameters of poly(3,4 ethylenedioxythiophene) (PEDOT) based electrochromic device on glass with and without counter electrode

Conjugated polymers are promising materials for electrochromic device technology. Aqueous dispersions of poly(3,4-ethylenedioxythiophene)-(PEDOT) were spin coated onto transparent conducting oxide (TCO) coated glass substrates. A seven-layer electrochromic device was fabricated with the following configuration: glass/transparent conducting oxide (TCO)/PEDOT (main electrochromic layer)/gel electrolyte/prussian blue (counter electrode)/TCO/glass. The device fabricated with counter electrode (Prussian blue) showed a contrast of 18% and without counter electrode showed visible contrast of 5% at 632 nm at a voltage of 1.9 V. The comparison of the device is done in terms of the colouration efficiency of the devices with and without counter electrode.

Studies on 12 V substrate-integrated lead-carbon hybrid ultracapacitors

A cost-effective 12 V substrate-integrated lead-carbon hybrid ultracapacitor is developed and performance tested. These hybrid ultracapacitors employ flexible-graphite sheets as negative plate current-collectors that are coated amperometrically with a thin layer of conducting polymer, namely poly-aniline to provide good adhesivity to activated-carbon layer. The positive plate of the hybrid ultracapacitors comprise conventional lead-sheet that is converted electrochemically into a substrate-integrated lead-dioxide electrode. 12 V substrate-integrated lead-carbon hybrid ultracapacitors both in absorbent-glass-mat and polymeric silica-gel electrolyte configurations are fabricated and characterized. It is possible to realize 12 V configurations with capacitance values of similar to 200 F and similar to 300 F, energy densities of similar to 1.9 Wh kg(-1) and similar to 2.5 Wh kg(-1) and power densities of similar to 2 kW kg(-1) and similar to 0.8 kW kg(-1), respectively, having faradaic-efficiency values of similar to 90 % with cycle-life in excess of 100,000 cycles. The effective cost of the mentioned hybrid ultracapacitors is estimated to be about similar to 4 US$/Wh as compared to similar to 20 US$/Wh for commercially available ultracapacitors.

Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached.

Dye-sensitized solar cells with solvent-free ionic liquid electrolytes

We systematically studied the temperature-dependent physicochemical properties, such as density, conductivity, and fluidity, of 1,3-dialkylimidazolium iodides. In combination with the amphiphilic Z907Na sensitizer, we have found that it is important to use low-viscosity iodide melts with small cations to achieve high-efficiency dye-sensitized solar cells. By employing high-fluidity eutectic-based melts the device efficiencies considerably increased compared to those for cells with the corresponding state of the art ionic liquid electrolytes.

N-Methyl-N-Allylpyrrolidinium Based Ionic Liquids for Solvent-Free Dye-Sensitized Solar Cells

We prepared four new ionic liquids consisting of N-methyl-N-allylpyrrolidinium cation in conjunction with anions including iodide, nitrate, thiocyanate, and dicyanamide, respectively, and measured their physical properties of density, viscosity, and conductivity. Owing to the relatively lower melting point of electroactive N-methyl-N-allylpyrrolidinium iodide, in combination with three other nonelectroactive ionic liquids, we could construct solvent-free electrolytes possessing high iodide concentrations for dye-sensitized solar cells. We correlated temperature-dependent electrolyte viscosity with molar conductivity and triiodide mobility through applying an empirical Walden's rule and a modified Stokes-Einstein equation, respectively. We have further found that these anions (nitrate, thiocyanate, and dicyanamide) have different influences on surface states and electron transport in the mesoporous titania film, resulting in different photovoltages and photocurrents of dye-sensitized solar cells.