Controllable preparation and superior rate performance of spinel LiMn₂O₄ hollow microspheres as cathode material for lithium-ion batteries

Abstract

Spinel LiMn₂O₄ microspheres and hollow microspheres with adjustable wall thickness have been prepared using controllable oxidation of MnCO₃ microspheres precursors and following solid reactions with lithium salts. Scanning electron microscopy (SEM) investigations demonstrate that the microsphere morphology and hollow structure of precursors are inherited. The effect of hollow structure properties of as-prepared LiMn₂O₄ on their performance as cathode materials for lithium-ion batteries has been studied. Electrochemical performance tests show that LiMn₂O₄ hollow microspheres with small wall thickness exhibit both superior rate capability and better cycle performance than LiMn₂O₄ solid microspheres and LiMn₂O₄ hollow microspheres with thick wall. The LiMn₂O₄ hollow microspheres with thin wall have discharge capacity of 132.7 mA·h·g^-1 at C/10 (14.8 mA·g^-1) in the first cycle, 94.1% capacity retention at C/10 after 40 cycles and discharge capacity of 116.5 mAh·g^-1 at a high rate of 5C. The apparent lithium-ion diffusion coefficient (D _app) of as-prepared LiMn₂O₄ determined by capacity intermittent titration technique (CITT) varies from 10^-11 to 10^-8.5 cm²·s^-1 showing a regular “W” shape curve plotted with test voltages. The Dapp of LiMn₂O₄ hollow microspheres with thin wall has the largest value among all the prepared samples. Both the superior rate capability and cycle stability of LiMn₂O₄ hollow microspheres with thin wall can be ascribed to the facile ion diffusion in the hollow structures and the robust of hollow structures during repeated cycling.

Keywords

hollow microsphere / spinel LiMn₂O₄ / spherical MnCO₃ / rate capability / diffusion coefficient

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