Hydrothermal Preparation and Characterization of LiMn2O4 for LI-ION Battery Application

"A novel hydrothermal method was applied to prepare the precursor of LiMn2O4 using pre-treated electrolytic manganese dioxide (EMD) and lithium hydroxide as the main raw materials. The precursor was subjected to heat treatment between 400 and 900ºC to obtain spinel Li1.05Mn1.95O4 and Li1.035Co0.035Mn1.930O4 positive materials for lithium ion batteries. The structure and morphology of the obtained powder materials were studied in detail by means of X-ray diffraction (XRD) and scanning electron microscope (SEM). It is found that the precursor has an amorphous structure and a high reactivity, which is easily transferred to spinel structure during heat treatment, obtaining a positive material with an uniform structure and good performances. The XRD patterns reveal that single phase spinel Li1.05Mn1.95O4 can be obtained from the precursor after heat treatment at 600°C in air. The final Li-rich Li1.05Mn1.95O4 product obtained showed a well-defined stable spinel structure and distinctive crystal faces with particle size between 200 and 300 nm. The as-prepared Co-doped spinel sample exhibited a excellent electrochemical performance with an initial discharge capacity of 113.0 mAh/g and 93.8% of its original value was retained after 100 charge-discharge cycling at 0.5 C.INTRODUCTIONThe increasing demand for portable electronic devices and hybrid or full electric vehicles is driving the development of cheap, efficient, compact lightweight and environmental friendly rechargeable batteries systems (Chung et al., 2002; Scrosati, 1995). Lithium ion secondary batteries have satisfied this demand to a greater degree than other battery systems. The cathode material plays a critical role in the performance of Li-ion batteries. The high cost and toxicity of cobalt compounds for the cathode material of LiCoO2 has prompted a search for alternative materials. LiMn2O4-based spinels offer a potentially attractive alternative to LiCoO2, due to its abundance, low price, ease of preparation, environmentally friendly characteristics, better thermal stability, and its effortless recycling (Tarascon et al., 1991; Yabuuchi and Ohzuku, 2003; Amatucci et al., 1999; Tsai et al., 2003). Some achievements have been created to meet the requirements (Guo et al., 2010; Kang et al., 2005; Park et al., 2008; Takahashi et al., 2006; Lee et al., 2001; Yoshio et al., 2001; Arumugam et al., 2008). However, the largest obstacle encountered in the practical applications of LiMn2O4 is its fast capacity fading during long term cycling, which is due to Jahn-Teller distortion of the [MnO6] framework, the electrolyte decomposition at high potentials and manganese dissolution into the electrolyte (Fey et al., 2003). The electrochemical performance of LiMn2O4 is also strongly dependent on its morphological properties, such as crystallinity, phase purity, surface area, grain shape and particle size distribution, etc. All these morphological properties are closely related to the material synthetic routines and heat treatment processes (Huang et al., 2000; Myung et al., 2000; Takada et al., 1998)."