Improved Electrochemical Performance of Multi-Phase Layered-Spinel Cathodes for Li-Ion Batteries
In the present study, we have synthesized layered-spinel composite cathode materials LiNi1/3Mn2/3O2 and LiNi0.33Mn0.54Co0.13O2 involving Li2MnO3 (monoclinic), LiNiO2 (rhombohedral) and LiNi0.5Mn1.5O4 (spinel) by self-combustion reaction (SCR). The Reitveld analysis and TEM study clearly indicates the presence of these phases. Interestingly, these cathode materials exhibited superior cycling stability when cycled in a wide potential range of 2.3-4.9 V vs. Li (Fig. 1). LiNi1/3Mn2/3O2 exhibited an initial specific capacity of 80 mAh g-1 which increased to about 220 mAh g-1 after 20 cycles and then a stable capacity is observed even after 100 cycles. On the other hand, the specific capacity decreases from 190 to 150 mAh g-1 with 79 % capacity retention for the spinel LiNi0.5Mn1.5O4. Also, LiNi0.33Mn0.54Co0.13O2 exhibited a stable specific capacity of about 170 mAh g-1 after 100 cycles when cycled in the potential range of 2.3-4.9 V. On the other hand, the specific capacity of LiNi0.33Mn0.33Co0.33O2 decreased from 208 mAh g-1 to a value of 130 mAh g-1 after only 50 cycles. The structural studies of cycled electrodes indicate that the spinel content in the active mass increases upon cycling due to structural layered-to-spinel transformation. However, the presence of untransformed Li2MnO3 in the active mass stabilizes the structure even after cycling in a wide potential range. These results indicate that neither layered nor spinel can be cycled in a too wide potential range while multiphase layered-spinel cathode materials can be cycled in a wide potential range with a stable high specific capacity in Li-ion batteries. Thus, the order of stability of these cathode materials can be presented as layered-spinel> spinel > layered.
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