Nano-sized LiMn2O4 particles were prepared at 1023K by electrospray pyrolysis in which they were directly deposited on a Pt substrate in gas phase. Cyclic voltammetry gave very sharp and symmetrical redox peaks at ca. 4.0 and 4.1V vs. Li/Li+ owing to the insertion and extraction of lithium-ion at LiMn2O4. However, the redox peaks broadened and their peak separation in an electrode potential increased when aggregated nano-sized LiMn2O4 particles were used. In Nyquist plots, a semi-circle due to lithium-ion transfer resistance appeared at potentials above 3.90V. The values of the lithium-ion transfer resistances were small for dispersed nano-sized LiMn2O4 particles. On the other hand, the lithium-ion transfer resistances increased and the Warburg impedance became obvious as the nano-sized LiMn2O4 particles aggregated. These results clearly indicate that the apparent rapid diffusion of lithium-ion can be attained using well-dispersed nano-sized particles of electroactive materials.