Microstructural and electrochemical properties of rf-sputtered LiMn2O4 thin film cathodes

Lithium transition metal oxides have received considerable attention in recent years as high voltage positive electrode materials in the fabrication of all solid state microbatteries. Among various lithium-based cathode materials, LiMn2O4 is one of the most promising cathode materials as it offers high energy density, high cell voltage, low cost, and low toxicity over the other electrode materials. Thin films of LiMn2O4 were prepared by radio frequency magnetron sputtering on gold-coated silicon substrates under various substrate temperatures ranging from 373 to 673 K in a partial pressure of 3 x 10(-3) mbar with rf power 100 Watts. In the present investigation, the influence of substrate temperature on the growth and microstructural properties was studied. The films deposited at a substrate temperature less than 473 K was found to be X-ray amorphous. The initial crystallization has been observed at a substrate temperature of 523 K. The X-ray diffraction patterns of the films deposited in the substrate temperature range 523-673 K exhibited predominant (111) orientation representing cubic spinel structure with Fd3m symmetry. The grain size was found to be increased with the increase of substrate temperature as evidenced from SEM studies. However, additional impurity phases like Mn3O4 were observed for the films deposited at higher substrate temperatures (>673 K) because of re-evaporation of Li+ ions in the films. The electrochemical (EC) studies were carried for the films deposited at T-s = 673 K in aqueous media in the potential window of 0.0-1.2 V exhibited better electrochemical performance suggesting that the films are well suited as binder free thin film cathode material for commercially viable Li-ion secondary batteries.