Lanthanum-doped LiCoO2 cathode with high rate capability

• Published in: Electrochimica acta 2009-02, Vol.54 (5), p.1654-1661
• Main Authors: GHOSH, Paromita, MAHANTY, S, BASU, R. N
• Format: Article
• Language: English
• Subjects: Applied sciences; Direct energy conversion and energy accumulation; Electrical engineering. Electrical power engineering; Electrical power engineering; Electrochemical conversion: primary and secondary batteries, fuel cells; Exact sciences and technology
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2008.09.050

Lanthanum-doped LiCoO2 composite cathode materials, containing 0.1 -10 mol% of La were synthesized by citric acid aided combustion technique. Thermal analyses showed that the sharp decomposition reaction for pristine LiCoO2 became sluggish upon addition of lanthanum. X-ray diffraction analyses of the composites revealed existence of minute quantities of lanthanum-rich perovskite phases -rhombohedral LaCoO3 and tetragonal La2Li0.5Co0.5O4 (14/mmm), along with rhombohedral LiCoO2. Electron microscopy showed a distinct grain growth with increasing La content. An increase of about two orders of magnitude in the electrical conductivity (1.09 X 10-3 S cm-1) was observed for 1.0 mol% La-doped LiCoO2. An excellent cycling performance with capacity retention by a factor of 10 in comparison to the pristine LiCoO2 was observed for the composite cathode containing 5.0 mol% La, when 2032 type coin cells were cycled at 5C rate. This has been ascribed to the structural stability induced by La doping and presence of the ion-conducting phase La2Li0.5Co0.5O4 which acts as a solid electrolyte for Li+ ions. A negligible growth of impedance upon repeated cycling has been observed. Cyclic voltammetry showed a remarkable improvement in reversibility and stability of the La-doped electrodes. These composite cathodes might be very useful for high rate power applications.