Copolymerization-Assisted Preparation of Porous LiMn2O4 Hollow Microspheres as High Power Cathode of Lithium-ion Batteries

doi:10.1016/j.jmst.2016.11.024

Abstract

Abstract:

Porous LiMn₂O₄ hollow microspheres were facilely prepared by incorporation of Li and Mn elements into a spherical polymeric precursor through copolymerization of lithium and manganese acetates with resorcinol and hexamethylenetetramine and then burning off the organic matrix at appropriate temperatures in air. The LiMn₂O₄ inherited the spherical morphology of the polymeric precursor but showed hollow porous structure assembled by nanocrystals of about 50-100 nm in size. When tested as cathode of Li-ion batteries, the LiMn₂O₄ hollow spheres exhibited excellent rate capability and cycle stability. A discharge capacity of above 90 mAh g^-1 was maintained at 10 C (1 C = 120 mA g^-1), and the cells can still deliver a discharge capacity over 100 mAh g^-1 after another 115 cycles at 0.5 C. With such excellent electrochemical properties, the prepared LiMn₂O₄ hollow microspheres could be promising cathode of Li-ion batteries for long term and high power applications.

Key words: Li-ion batteries, Cathode, LiMn₂O₄, Hollow spheres, Rate capability

Zou Zhimin, Li Zhaojin, Zhang Hui, Wang Xiaohui, Jiang Chunhai. Copolymerization-Assisted Preparation of Porous LiMn₂O₄ Hollow Microspheres as High Power Cathode of Lithium-ion Batteries[J]. J. Mater. Sci. Technol., 2017, 33(8): 781-787.

Figures/Tables 7

Fig. 1. Typical SEM images of the Li and Mn co-incorporated polymeric spheres (a), the porous LiMn2O4 hollow spheres sintered at 650°C (b) and 750°C (c), and their corresponding XRD patterns (d).

Fig. 2. TEM images of the porous LiMn2O4 hollow spheres sintered at 650 °C (a-c) and 750 °C (d and f) for 5 h at different magnifications.

Fig. 3. Nitrogen adsorption/desorption isotherms of the samples sintered at 650 °C (rectangular) and 750 °C (cycle) measured at 77 K. The figure inset shows the corresponding pore size distributions of both samples, w means pore width.

Fig. 4. Cyclic voltammograms (CV) of the samples sintered at 650 °C (a) and 750 °C (b) at scan rates of 0.1-1 mV s-1 within the potential range between 3.4 and 4.3 V (vs. Li/Li+), and the relations between the current densities of two anodic peaks and the square roots of scanning rates (v) for the samples sintered at 650 °C (c) and 750 °C (d).

Fig. 5. Charge/discharge capacities of the two porous LiMn2O4 hollow sphere electrodes measured at varied current rates from 0.5 C to 10 C and the subsequent cycle performance at 0.5 C.

Fig. 6. Preventative charge/discharge curves of the samples sintered at (a) 650 °C and (b) 750 °C at different current rates.

Fig. 7. Preventative charge/discharge curves of the samples sintered at (a) 650 °C and (b) 750 °C at different current rates.

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Copolymerization-Assisted Preparation of Porous LiMn₂O₄ Hollow Microspheres as High Power Cathode of Lithium-ion Batteries

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