Electrochemistry
Online ISSN : 2186-2451
Print ISSN : 1344-3542
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80 巻 , 1 号
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  • Tsutomu TAKAMURA
    80 巻 (2012) 1 号 p. 3-14
    公開日: 2012/01/05
    ジャーナル フリー
    During the course of investigating carbonaceous materials for the active materials of Li-ion batteries (LIB) or supercapacitors (SPC) we have found interesting properties and behaviors of the carbon in contact with an electrolyte containing Li+. In this article the author would like to exhibit these attractive matters. Especially use of carbon fiber (CF) attracted our attention since we can use a single fiber as the working electrode, which enables us to measure not only the conductivity change but also the volume change during Li insertion/extraction. Determination of the lithium diffusion coefficient in carbon could be performed with ease. Surprisingly propylene carbonate showed no decomposition during cathodic polarization of graphite in propylene carbonate electrolyte when we use a single graphitzed fiber. On the other hand, by the use of rounded graphite particle we suggested presence of holes on the graphene layer. We proved that homogeneous distribution of conductivity over the surface of coated electrode is the key factor to keep long cycle life.
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  • Johan SCHEERS, Erlendur JÓNSSON, Per JACOBSSON, Patrik JOHANSSO ...
    80 巻 (2012) 1 号 p. 18-25
    公開日: 2012/01/05
    ジャーナル フリー
    New lithium imide salts have been studied using computational chemistry methods. Intrinsic anion oxidation potentials and ion pair dissociation energies are presented for six lithium sulfonyl imides (R-O2S-N-SO2-R) and six lithium phosphoryl imides (R2-OP-N-PO-R2), as a function of -F, -CF3, and -C≡N substitution. The modelled properties are used to estimate the electrochemical oxidation stability of the anions and the relative ease of charge carrier creation in lithium battery electrolytes. The results show that both properties are improved with cyano-substitution, which in part is corroborated when comparing with other classes of lithium salts. However, the comparison also shows ambiguous oxidation stability results for cyano-substituted reference salts of the type PFx(CN)6−x and BFx(CN)4−x, using two different approaches – we present a tentative explanation for this. For the imide anions and PF6, the bond dissociation energy is introduced as a third property, to gauge the thermal stability of the imide anions. The results suggest that the C-S and C-P bonds are the most liable to break and that the thermal stability is inversely related to the ion pair dissociation energy.
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  • Jian-guang YANG, Yuan-lin ZHOU, Guo-qiang XIONG
    80 巻 (2012) 1 号 p. 26-29
    公開日: 2012/01/05
    ジャーナル フリー
    Pentakis(diethylamido)tantalum (PDEAT) was synthesized by electrochemical reaction involving diethylamide with a sacrificial tantalum anode and stainless steel cathode in the presence of tetraethylammonium bromine as the conductive additive and acetonitrile as the inert support electrolyte. The condensates were isolated by the reduced pressure distillation of as-synthesized crude PDEAT below 5 kPa. The final product was characterized by FT-IR and NMR spectroscopy. The thermal properties of the resulting PDEAT were analyzed by TG-DTG. Results indicate that the resulting compound was indeed PDEAT. The vapor pressure of the compound was calculated from the Langmuir equation, while the enthalpy of vaporization was calculated from vapor pressure-temperature data using the Clausius-Clapeyron equation. The concentration of the impurities in the sample were detected via ICP-Mass spectroscopy, and it was found that the purity of the compound synthesized could reach 99.995%.
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