The electrochemical behavior of organo-fluorine compounds with antioxidation ability has been investigated. Oxidation currents of fluorine-compound-containing ethylene carbonate (EC)/diethyl carbonate (DEC) solutions were much smaller than those of EC/DEC and EC/DEC/propylene carbonate (PC) at potentials higher than 6 V vs
Li/Li+
. Electrochemical reduction of fluorine compounds started at ca. 2 V vs
Li/Li+
, higher than those for EC, DEC, and PC. However the first coulombic efficiencies for natural graphite electrodes in fluorine-compound-containing EC/DEC mixtures were nearly the same as those in EC/DEC without an increase in irreversible capacities. Furthermore the first coulombic efficiencies in fluorine-compound-containing EC/DEC/PC mixtures were much larger than those in EC/DEC/PC itself. The results show that the fluorine compounds used in the present study can be used as nonflammable solvents for lithium ion batteries.
Differential scanning calorimetry study demonstrated that mixing of fluoro-ethers and fluoro-carbonates improved the thermal stability of 0.67 mol/L
LiClO4
–ethylene carbonate (EC)/diethyl carbonate (DEC)/propylene carbonate (PC) (1:1:1 by volume). The oxidation currents were smaller in the fluorine compound-mixed electrolyte solutions than in 0.67 mol/L
LiClO4
–EC/DEC/PC, which also shows a high stability of the fluorine compound-mixed electrolyte solutions against electrochemical oxidation. Electrochemical reduction of fluorine compounds took place at the higher potentials than EC, DEC, and PC, as suggested by the highest occupied molecular orbital and lowest unoccupied p-molecular orbital energies of the fluorine compounds. However, charge/discharge experiments using natural graphite (NG) electrodes showed that the fluorine compounds increased first coulombic efficiencies due to the quick formation of the solid electrolyte interphase on NG in PC-containing solvents.
An asymmetric polymer capacitor was prepared from pyrene (PY), aniline (ANI), and commercially available activated carbon (AC) through a solvent-free preparation. PY and ANI were adsorbed into the AC host material in the gas phase and electrochemically polymerized exclusively inside the AC pores in an aqueous H2SO4 electrolyte (1 M). No volumetric expansion of the AC particles occurred upon the adsorption of monomers and their subsequent polymerizations; thus, the volumetric capacitance was enhanced by the inclusion of pseudocapacitive polypyrene (PPY) and polyaniline (PANI). The PPY and PANI structures formed inside the AC pores are very thin and have a large contact area with the conductive carbon surfaces. Therefore, the charge transfer distance between the polymers and the carbon surfaces was drastically shortened, significantly reducing the charge transfer resistance; i.e., high power density. The maximum volumetric capacitances for the PPY- and PANI-hybridized AC reached 314 and 299 F cm-3, respectively. Moreover, the strong adhesion derived from their large contact areas and adsorption capability of AC endow these materials with long cycle lifetimes. The PPY- and PANI-hybridized AC have different redox potentials and can be assembled into an asymmetric capacitor. The volumetric capacitance obtained for the asymmetric capacitor further surpassed that of the symmetric capacitor consisting of pristine AC, with high power density and long cycle lifetimes.
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