Main-chain anionic polymers with lithium cations, which have oligo(oxyethylene)aluminate chain backbones attached with two side chains of endo-methoxy[oligo(oxyethylene)], were prepared, and their ionic conductivities are reported. The ac conductivity of aluminate polymer complex was about 10 -6 -10 -7 S cm -11 at room temperature. As the constant current was observed for [Li/aluminate polymer complex/Li] cells under dc electric field, the single-ionic conduction was confirmed.
A hollandite-type manganese dioxide (HolMO), without foreign metal cations (K +, NH~, Na +) in the (2 • 2) tunnel, was prepared directly by reacting LiMnO4 with Mn(NO3)2 in an H2SO4 acidic solution. The HoIMO belonged to a body-centered tetragonal system (space group 14/m) and could be expressed by the formula H4xMns-xO16 -yH20. A preliminary electrochemical study suggested that the HoIMO is promising as the cathode for a lithium rechargeable battery.
The electrochemical characteristics of fullerenes and fluorinated fullerenes have been investigated by cyclic voltammetry and galvanostatic discharge using solid-state lithium cells Li/Li+-(MEP-7)/A (A = C,,, C70, C60F,, and C70F., MEP-7 = a polyphosphazene derivative). In the cyclic voltammograms of C,, and C70, the first half-wave potential of C70 is found to be 0.2 V more positive than that of C,,, suggesting that the electron affinity of C70 is slightly larger than that of C60. For the fluorinated fullerenes, cyclic voltammetry gives one irreversible reduction peak at a high potential, which has been verified to be due to the reduction of the C-F bonds by x-ray photoelectron spectroscopy. From the discharge curves of C,0F, and C,,0F, a high utility of 90% is obtained. Changes in electronic structure of the cathode materials upon discharge are examined by x-ray photoelectron spectroscopy and open-circuit voltage dependence on cathode utilities, and the discharge reaction mechanism is deduced. The open-circuit voltage dependence reveals that the electronic structure of fluorinated fullerenes changes continuously as a homogeneous electrochemical reduction proceeds.
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