Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol.341, 959-966, 2000
Thermodynamic approach to electrochemical lithium intercalation into Li1-delta Mn2O4 electrode prepared by sol-gel method
Electrochemical lithium intercalation into Li(1-)delta Mn2O4 electrode prepared by sol-gel method was investigated from the thermodynamic view point by using galvanostatic intermittent titration technique (GITT) combined with EMF-temperature measurement. The electrode potential vs. lithium content curve was theoretically calculated with the aid of the lattice gas model based upon the Bragg-Williams approximation for the cubic spinel composed of two sub-lattices, Considering the considerable difference between both lithium contents in two sub-lattices due to the ordering of the intercalated lithium ions, the theoretical partial molar enthalpy and entropy were calculated at various lithium contents by a numerical method. From the comparison between the theoretical partial molar quantities and experimental results, the electrochemical lithium intercalation into the Li1-deltaMn2O4 electrode was discussed in terms of the ordering of the intercalated lithium ions.
Keywords:Li1-delta Mn2O4 electrode;order-disorder phase transition;partial molar enthalpy and entropy;lattice gas model;Bragg-Williams approximation