Impedance study of (PEO)(10)LiClO4-Al2O3 composite polymer electrolyte with blocking electrodes

A composite solid polymer electrolyte (SPE) of (PEO)(10)LiClO4-Al2O3 was prepared and Pt and stainless steel(SS) blocking electrodes were used for an impedance study. It was found that the semicircle in the high frequency range and the straight line in the low frequency range depend upon different blocking electrodes and polarization potentials applied in the experiments. In the equivalent circuit. two constant phase elements (CPE) have been used instead of the pure geometrical and double layer capacitances. respectively. A theoretical line calculated from their estimated values has a good correlation with the experiment data. Moreover. the equivalent circuit also can be used to explain the impedance properties of Pt and stainless steel (SS) blocking electrodes both in the high and the low frequency ranges. (C) 2001 Elsevier Science Ltd. All rights reserved.

The electrochemical reversibility of the polyaniline/organodisulfide composite cathode containing an organomonothiol

Organomonothiols were used to control the extent of 2,5-dimercapto-1,3,4-thiadiazole polymerization. When organomonothiols were incorporated into polyaniline/2,5-dimercapto-1,3, 4-thiadiazole composite cathode materials for lithium batteries, their electrochemical reversibility and charge-discharge capacities were improved significantly. (C) 1999 The Electrochemical Society. S0013-4651(99)01-078-2. All rights reserved.

The luminescence of Eu2+ in mixed phase system

The dependence of the structure of the hosts on the M ion radius in MMgAl10O17 (M = Be, Mg, Ca, Sr, Ba, Pb, Eu, Mn, Fe, Co, Ni, Zn, Cd, Sn) system was studied and the luminescence of Eu2+ the mixed phase system was discussed. When M ion radius is less than 0.10 nm, the system MMgAl10O17 constructs by the mixed phases consisting of manegtoplumbite and spinel, alpha-alumina or spinel and alpha-alumina. In the mixed phase of manegtoplumbite and spinel and alpha-alumina, Eu2+ ion preferentially occupies lattice site of the cations in manegtoplumbite well matched with the radius and charge of Eu2+. There exists only d-->f transition emission of Eu2+ and no characteristic emission of Eu3+ occurs in those hosts. In the mixed phase of spinel and alpha-alumina, Eu2+ can enter the lattice site of Mg2+ ion or Al3+ ion and the d-->f and f-->f transition of Eu2+ can been observed respectively. Meanwhile, since the radius and charge of matrix lattice ions substituted by Eu2+ do not match with those of Eu2+, the valence state of Eu2+ is unstable. Eu2+ is partly changed into Eu3+ and the emission of Eu3+ is obviously observed even under the condition of reduction atmosphere. If reaction temperature is more than 1 150 degrees C, Al2O3 forms alpha-Al2O3 structure, the f-->f transition of Eu2+ appears. If reaction temperature is less than 1 150 degrees C, a mixed phase of alpha-Al2O3 and gamma-Al2O3 is formed, the f-->f transition of Eu2+ disappears and a new band emission from d-->f transition of Eu2+ occurs.

Enhanced redox processes of disulfides with partially N-methylated polyaniline

Partially N-methylated polyaniline (NMPAn) is used instead of polyaniline (PAn) to make a composite with organodisulfides for cathodes of lithium secondary batteries. NMPAn displays a better electrocatalytic effect on the redox processes of organodisulfides than PAn. (C) 1998 Elsevier Science S.A. All rights reserved.

The effect of stoichiometry on nonlinear optical properties of LiNbO3

From the chemical bond viewpoint, second-order nonlinear optical (NLO) tensor coefficients of LiNbO3 have been investigated. The single-bond contributions to the second-order NLO susceptibility and the linear susceptibility were determined. The tensor values thus calculated are in good agreement with experimental data. Based on theoretical results of LiNbO3 with Li/Nb = 1, we also have calculated linear and nonlinear optical properties of nonstoichiometric samples with Li/Nb < 1. In the calculation, we find that the Li-O bond is an important type of chemical bond in these LiNbO3 samples, which have large NLO contributions to the total nonlinearities. The refractive indices and second-order NLO tensor coefficients have been determined as a function of the stoichiometry.

Synthesis, characterization and ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Three comb polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and the ionic conductivity of CP/salt complexes is reported. The conductivity of these complexes was about 10(-5)-10(-6) S cm(-1) at room temperature. The conductivity, which displayed non-Arrhenius behaviour, was analysed using the Vogel-Tammann-Fulcher equation. The conductivity maxima appear at lower salt concentration, when CP has longer side chains. Infrared (i.r.) was used to study the cation-polymer interaction. I.r. results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring. (C) 1997 Elsevier Science Ltd.

Asymmetric polymerization of the mixture of TrMA and MMA initiated by chiral complexes

A mixture of triphenylmethyl methacrylate (TrMA) and methyl methacrylate (MMA) was polymerized with chiral anionic initiator, such as fluorenyl lithium-(-)-sparteine [FlLi-(-)-Sp] and fluorenyl lithium-(+)-2S,3S-dimethoxy-1,4-bis(dimethylamino) butane [FlLi-(+)-DDB] in toluene at -78 degrees C. The results show that after the stable helix formed, when FlLi-(+)-DDB was used as the initiator, TrMA and MMA could be copolymerized, whereas when FlLi-(-)-Sp was used, the two monomers tended to be selectively polymerized into two polymers. This phenomenon has been explained by the existence of helix-selective polymerization. (C) 1997 John Wiley & Sons, Inc.

Ion-conducting polymers based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CPs) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo(oxyethylene) side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. Maximum conductivity close to 1.38 x 10(-4) S/cm was achieved at room temperature and at a [Li]/[EO] ratio (EO = ethylene oxide) of about 0.066. The temperature dependence of ionic conductivity suggested that the ion transport was controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moved to a higher salt concentration as the temperature increased, indicating that a larger number of charge carriers can be transferred through polymer chains, of which free volume is increased at higher temperature. IR results indicated that the ester in CPs might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

A new solid-state electrolyte: Rubbery 'polymer-in-salt' containing LiN(CF3SO2)(2)

A new class of rubbery 'polymer-in-salt' electrolytes for application in solid-state lithium batteries has been explored by differential scanning calorimetry and a.c. impedance analysis. Simple phase diagrams of LiN(CF3SO2)(2)+LiClO4 and LiC(CF3SO2)(3)+LiN(CF3SO2)(2) have been drawn, which are very important to determine polymer-in-salt electrolyte materials. The conductivities obtained by a.c. impedance measurement are smaller for the electrolyte that contains acetate LiOAc salt than for the electrolyte without this salt.

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.

Comb polymer electrolytes - Ionic conductivity and cation-polymer interaction

Three comb polymers(CP) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were prepared from methyl vinyl ether/maleic anhydride alternating copolymer. Homogeneous amorphous polymer electrolytes were made from CP and LiCF3SO3 or LiClO4 by solvent-casting method, and their conductivities were measured as a function of temperature and salt concentration. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation. The conductivity maximum appears at lower salt concentration when CP has longer side chains. XPS was used to study the cation-polymer interaction.

The ion selectivity of monensin incorporated phospholipid/alkanethiol bilayers

Monensin was incorporated into phospholipid/alkanethiol bilayers on the gold electrode surface by a new, paint-freeze method to deposit a lipid monolayer on the self-assembled monolayers (SAMs) of alkanethiol. The advantages of this assembly system with a suitable function for investigating the ion selective transfer across the mimetic biomembrane are based on the characteristics of SAMs of alkanethiols and monensin. On the one hand, the SAMs of alkanethiols bring out their efficiency of packing and coverage of the metal substrate and relatively long-term stability; on the other hand, monensin improves the ion selectivity noticeably. The selectivity coefficients K-Na+,K-K+, K-Na+,K-Rb+ and K-Na+,K-Ag+ are 6 x 10(-2), 7.2 x 10(-3) and 30 respectively. However, the selectivity coefficient K-Na+,K-Li+ could not be obtained by a potentiometric method due to the specific interaction between Li+ and phospholipid and the lower degree of complexion between Li+ and monensin. The potential response of this bilayer system to monovalent ions is fairly good. For example, the slope of the response to Na+ is close to 60 mV per decade and its linearity range is from 10(-1) to 10(-5) M with a detection limit of 2 x 10(-6) M, The bilayer is stable for at least two months without changing its properties. This monensin incorporated lipid/alkanethiol bilayer is a good mimetic biomembrane system, which provides great promise for investigating the ion transfer mechanism across the biomembrane and developing a practical biosensor.

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.