IMPEDANCE STUDY OF THE INTERFACES BETWEEN LITHIUM, POLYANILINE, LITHIUM-DOPED MNO2 AND MODIFIED POLY(ETHYLENE OXIDE) ELECTROLYTE

Impedance study was carried out for the interfaces between lithium, polyaniline (PAn), lithium-doped MnO2 and modified poly(ethylene oxide) (PEO) electrolyte under various' conditions. The interfacial charge-transfer resistances R(ct) on PEO/PAn, R(ct) on PEO/LiMn2O4 increase with depth-of-discharge and decrease after the charge of the cell containing modified PEO as electrolyte. The charge-transfer resistance R(ct) on PEO/PAn is higher than R(ct) on PEO/LiMn2O4 under the same condition, since inserted species and mechanism are different for both cases. In the case of PAn, an additional charge-transfer resistance might be related to the electronic conductivity change in discharge/charge potential range, as it was evident from a voltammetry curve. With increasing cycle numbers, the charge-transfer resistance increases gradually. The impedance results also have shown that at low frequency the diffusion control is dominant in the process of the charge and discharge of Li/PEO/PAn or Li/PEO/LiMn2O4 cell. The diffusion coefficients have been calculated from impedance data.

STUDIES OF SPINEL LICRXMN2-XO4 FOR SECONDARY LITHIUM BATTERY

X-ray and electrochemical studies of spinel-related manganese chromium oxides, LiCrxMn2-xO4 (0 less-than-or-equal-to x less-than-or-equal-to 1) were carried out in a lithium nonaqueous cell. X-ray diffraction spectra indicated that the substitution of manganese in LiMn2O4 by trivalent transition metals (Cr3+) cause the linear decrease of lattice parameter with the x in the LiCrMn2-xO4. Some discharge-capacity loss was obtained due to the lattice contraction of LiCrMn2-xO4, but it has a better rechargeability than LiMn2O4. Cyclic voltammetry and electrochemical impedance experiments have shown that the excellent rechargeability of LiCrxMn2-xO4 may be attributed to the good reversibility of the change in its crystal structure for the insertion and extraction of lithium ions.