Vibrational Spectroscopic Study on Ion Solvation and Association of Lithium Perchlorate in 4-Methoxymethyl-ethylene Carbonate

Solvation interaction and ion association in solutions of lithium perchlorate/4-methoxymethyl-ethylene carbonate （MEC） have been studied by using Infrared and Raman spectra as a function of concentration of lithium perchlorate. The splitting of ring deformation band and ring ether asymmetric stretching band, and the change of carbonyl stretching band suggest that there should be a strong interaction between Li^＋ and the solvent molecules, and the site of solvation should be the oxygen atom of carbonyl group. The apparent solvation number of Li^＋ was calculated by using band fitting technique. The solvation number was decreased from 3.3 to 1.1 with increasing the concentration of LiClO4/MEC solutions. On the other hand, the band fitting for the ClO4^- band revealed the presence of contact ion pair, and free ClO4^- anion in the concentrated solutions.

Measurement of the association constants through micro-Raman spectra of supersaturated lithium perchlorate droplets

High quality micro-Raman spectra of the LiClO4 droplet with mass of nanogram scale were obtained at various concentrations from dilute to supersaturated state. From component band analysis of the v1-ClO4^- band, four peaks at 933.3, 936.8, 942.1 and 950.7 cm^-1 were identified and assigned to free solvated perchlorate anion, solvent-shared ion pair, contact ion pair and com- plex ion aggregates, respectively. As expected, the signature of free solvated CIO4 ion was observed to decrease in intensity with the increase in concentration. The intensity of the signature from solvent-shared ion pair was observed to rise with in- crease in concentration from 1.8 mol/kg to 5.0 mol/kg before decreasing as the concentration was further increased to 5.6 mol/kg. Signatures of contact ion pair and of complex ion aggregates were shown to increase as the concentration was enhanced. Based upon the Eigen mechanism, we show that three association equilibria can be used to describe the transfor- mations between free solvated perchlorate anion, solvent-shared ion pair, contact ion pair and complex ion aggregates. The overall association constant, K, and the stepwise association constants Ki （i = 1 to 3） in the Eigen mechanism were determined separately with values of 0.025 ± 0.003, 0.023 ± 0.002, 0.068 ± 0.033 and 0.686 ± 0.174. Based on these constants, the electronic performance can be reasonably predicted by the optimum choice of electrolyte concentrations.

LITHIUM ION CONDUCTING POLYMER ELECTROLYTES BASED ON ALTERNATING MALEIC ANHYDRIDE COPOLYMER WITH OLIGO-OXYETHYLENE SIDE CHAINS

A comb polymer with oligo-oxyethylene side chains of the type -(CH2CB2O)(12)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethylene glycol) methyl ether. The polymer can dissolve LiClO4 salt to form homogeneous amorphous polymer electrolyte. The ac ion conduction was measured using the complex impedance method, and conductivities were investigated as functions of temperatures and salt concentration. The complexes were first found to have two classes of glass transition which increase with increasing salt content, The optimum conductivity attained at 25 degrees C is in the order of 5.50 x 10(-6)Scm(-1). IR spectroscopy was used to study the cation-polymer interaction.

CONDUCTING BLENDS OF POLY (2-VINYL PYRIDINE) AND POLYETHYLENE OXIDE WITH HIGH MOLECULAR WEIGHT

Ionic, electronic and mixed (ionic-electronic) conductivities of blends of poly(2-vinyl pyridine) (P2VP) and poly(ethylene oxide) (PEO) with high molecular weight after doped with LiClO4, TCNQ or LiClO4 and TCNQ were investigated. Effects of LiClO4 and TCNQ concentrations on the conductivity of PEO/P2VP/LiClO4 or TCNQ blend were studied. The ionic conductivity of PEO/P2VP/LiClO4 blend increases with increasing PEO content. At a Li/ethylene bride molar ratio of 0.10 and a TCNQ/2-vinyl pyridine molar ratio of 0.5, the mixed conductivity of PEO/P2VP/LiClO4/TCNQ is higher than the total of ionic conductivity of PEO/P2VP/LiClO4 and electronic conductivity of PEO/P2VP/TCNQ when the weight ratio of PEO and P2VP is 6/4 or 5/5. Scanning electron microscopy (SEM) on the broken cross-section of the PEO/P2VP/LiClO4 blend and differential scanning calorimetry (DSC) results show that LiClO4 could act as a compatibilizer in the blend.

Capacitive properties of low potential electro-polymerized polyfluorene and activated carbon composite electrode

Polyfluorene (PF) film has been successfully electropolymerized at lower potential (0.91 V vs.Ag/AgCl) in the mixed electrolyte of boron trifluoride diethyl etherate and trifluoroacetic acid.The PF film is characterized to have about 10 repeat units and no presence of ketonic defect site.UV-vis and photoluminescent spectral studies indicate that the PF film is blue light emitting.From cyclic voltammetry and galvanostatic charge-discharge tests in 1 M lithium perchlorate/acetonitrile electrolyte,the polyfluorene/activated carbon electrode shows a specific capacitance of 227.1 F g-1 (per active layer mass) and reversible redox reaction at the potential of 1.4 V in a three electrode configuration.An asymmetric electrochemical capacitor based on this composite electrode and activated carbon electrode exhibits a specific energy of 14.7 Wh kg-1 (per active layer mass).These results indicate that electrochemically prepared polyfluorene could be used as energy storage component for electrochemical application.