Abstract
The kinetics of the electrochemical lithium insertion reaction in the as-prepared Li7MnN4 has been investigated using ac impedance spectroscopy as a function of cycles and temperature. The results are compared and discussed with that obtained for an optimized Li7MnN4 sample obtained by ball-milling. From this comparison, a promoting effect of a lower crystallite size on the electrochemical kinetics is evidenced. For the first time an experimental evaluation of the activation energy for Li diffusion in the as-prepared and the ball-milled Li7MnN4 is obtained. The lower activation energy obtained for the ball-milled nitride, Ea = 0.28 eV against Ea = 0.42 eV for the pristine material is responsible of the better rate capability and significant improvement of the electrochemical behaviour especially in terms of cycling properties: at high rate of 5C, a remarkable and stable capacity of 120 mAh g−1 is obtained over 50 cycles which competes very well with the LTO anode material.
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