Graphical Abstract

Solid and hollow microspheres of LiMn2O4 have been synthesized by lithiating MnCO3 solid microspheres and MnO2 hollow microspheres, respectively. The LiMn2O4 solid microspheres and hollow microspheres had a similar size of about 1.5 μm, and the shell thickness of the hollow microspheres was only 100 nm. When used as a cathode material in lithium ion batteries, the hollow microspheres exhibited better rate capability than the solid microspheres. However, the tap density of the LiMn2O4 solid microspheres (1.0 g/cm3) was about four times that of the hollow microspheres (0.27 g/cm3). The results show that controlling the particle size of LiMn2O4 is very important in terms of its practical application as a cathode material, and LiMn2O4 with moderate particle size may afford acceptable values of both rate capability and tap density.
Kim, D. K.; Muralidharan, P.; Lee, H. W.; Ruffo, R.; Yang, Y.; Chan, C. K.; Peng, H.; Huggins, R. A.; Cui. Y. Spinel LiMn2O4 nanorods as lithium ion battery cathodes. Nano Lett. 2008, 8, 39484–39488.
Pasquier, A. D.; Huang, C. C.; Spitler, T. Nano Li4Ti5O12–LiMn2O4 batteries with high power capability and improved cycle-life. J. Power Sources 2009, 186, 508–514.
Ying, J. R.; Jiang, C. Y.; Wan, C. R. Preparation and characterization of high-density spherical LiCoO2 cathode material for lithium ion batteries. J. Power Sources 2004, 129, 264–269.
He, X. M.; Li, J. J.; Cai, Y.; Wang, Y.; Ying, J. R.; Jiang, C. Y.; Wan, C. R. Preparation of co-doped spherical spinel LiMn2O4 cathode materials for Li-ion batteries. J. Power Sources 2005, 150, 216–222.
Liu, Z. L.; Zhang, X. H.; Hong, L. Preparation and electrochemical properties of spherical LiFePO4 and LiFe0.9Mg0.1PO4 cathode materials for lithium rechargeable batteries. J. Appl. Electrochem. 2009, 39, 2433–2438.
Gao, J.; Jiang, C. Y.; Ying, J. R.; Wan, C. R. Preparation and characterization of high-density spherical Li4Ti5O12 anode material for lithium secondary batteries. J. Power Sources 2006, 155, 364–367.
Gao, J.; Ying, J. R.; Jiang, C. Y.; Wan, C. R. High-density spherical Li4Ti5O12/C anode material with good rate capability for lithium ion batteries. J. Power Sources 2007, 166, 255–259.
Fei, J. B.; Cui, Y.; Yan, X. H.; Qi, W.; Yang, Y.; Wang, K. W.; He, Q.; Li, J. B. Controlled preparation of MnO2 hierarchical hollow nanostructures and their application in water treatment. Adv. Mater. 2008, 20, 452–456.
Cao, J.; Zhu, Y. C.; Bao, K. Y.; Shi, L.; Liu, S. Z.; Qian, Y. T. Microscale Mn2O3 hollow structures: Sphere, cube, ellipsoid, dumbbell, and their phenol adsorption properties. J. Phys. Chem. C 2009, 113, 17755–17760.
Aricò, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J. M.; von Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 2005, 4, 366–377.
Armand, M.; Tarascon, J. M. Building better batteries. Nature 2008, 451, 652–657.
Guo, X. W.; Lu, X.; Fang, X. P.; Mao, Y.; Wang, Z. X.; Chen, L. Q.; Xu, X. X.; Yang, H.; Liu, Y. N. Lithium storage in hollow spherical ZnFe2O4 as anode materials for lithium ion batteries. Electrochem. Commun. 2010, 12, 847–850.
Zaghib, K.; Goodenough, J. B.; Mauger, A.; Julien, C. Unsupported claims of ultrafast charging of LiFePO4 Li-ion batteries. J. Power Sources 2009, 194, 1021–1023.
Guo, Y. G.; Hu, J. S.; Wan, L. J. Nanostructured materials for electrochemical energy conversion and storage devices. Adv. Mater. 2008, 20, 2878–2887.
Wu, X. L.; Liu, Q.; Guo, Y. G.; Song, W. G. Superior storage performance of carbon nanosprings as anode materials for lithium-ion batteries. Electrochem. Commun. 2009, 11, 1468–1471.
Ma, H.; Zhang, S. Y.; Ji, W. Q.; Tao, Z. L.; Chen, J. α-CuV2O6 nanowires: Hydrothermal synthesis and primary lithium battery application. J. Amer. Chem. Soc. 2008, 130, 5361–5367.
Xiao, X. L.; Wang, L.; Wang, D. S.; He, X. M.; Peng, Q.; Li, Y. D. Hydrothermal synthesis of orthorhombic LiMnO2 nanoparticles and LiMnO2 nanorods and comparison of their electrochemical performances. Nano Res. 2009, 2, 923–930.
Chou, S. L.; Wang, J. Z.; Choucair, M.; Liu, H. K.; Stride, J. A.; Dou, S. X. Enhanced reversible lithium storage in a nanosize silicon/graphene composite. Electrochem. Commun. 2010, 12, 303–306.
Wang, D. S.; Ma, X. L.; Yang, Y. G.; Wang, L.; Wang, Z. Y.; Zheng, W.; He, X. M.; Li, J.; Peng, Q. Li, Y. D. Shape control of CoO and LiCoO2 nanocrystals. Nano Res. 2010, 3, 1–7.