Research Papers

Porous LiMn2O4 Microspheres With Different Pore Size: Preparation and Application as Cathode Materials for Lithium Ion Batteries

[+] Author and Article Information
Shiyou Li, Konglei Zhu, Jinliang Liu, Dongni Zhao, Xiaoling Cui

College of Petrochemical Technology,
Lanzhou University of Technology,
Lanzhou 730050, China

1Corresponding author.

Manuscript received January 28, 2018; final manuscript received June 19, 2018; published online July 2, 2018. Assoc. Editor: San Ping Jiang.

J. Electrochem. En. Conv. Stor. 16(1), 011006 (Jul 02, 2018) (8 pages) Paper No: JEECS-18-1010; doi: 10.1115/1.4040567 History: Received January 28, 2018; Revised June 19, 2018

Three types of LiMn2O4 (LMO) microspheres with different pore size are prepared by a facile method, using porous MnCO3–MnO2 and Mn2O3 microspheres as the self-supporting template, for lithium ion batteries (LIBs) cathode material. Briefly, Mn2O3 and MnO2 microspheres are heated in air at 600 °C for 10 h to synthesize porous Mn2O3 spheres. Then the mixture of as-prepared spherical Mn2O3 and LiNO3 is calcined to obtain the LMOs. The morphology and structure of LMOs are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and nitrogen adsorption/desorption analyses. The result shows that the maximum pore diameters of LMOs are 17 nm, 19 nm, and 11 nm, respectively. All LMOs microspheres are composed of similar sized nanoparticles; however, the surface of these microspheres is strewed with dense tinier pores or sparse larger pores. Generally, the nanoparticles will reduce the path of Li+ ion diffusion and increases the reaction sites for lithium insertion/extraction. Moreover, the pores can provide buffer spaces for the volume changes during charge–discharge process. The electrochemical performances of LMOs are investigated and LMO2 exhibits extremely good electrochemical behavior, especially the rate capability. The as-prepared LMO2 delivers a discharge capacity of 124.3 mAh g−1 at 0.5 C, retaining 79.6 mAh g−1 even at 5 C. The LMO2 sample also shows good capacity retention of 96.9% after 100 cycles at 0.5 C.

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Yuan, Z. , Zheng, H. , Wang, S. , and Feng, C. , 2016, “ Influences of Polyethylene Glycol (PEG) on the Performance of LiMn2O4 Cathode Material for Lithium Ion Battery,” J. Mater. Sci.: Mater. Electron., 27(5), pp. 5408–5414. [CrossRef]
Cheng, F. , Liang, J. , Tao, Z. , and Chen, J. , 2011, “ Functional Materials for Rechargeable Batteries,” Adv. Mater., 23(15), pp. 1695–1715. [CrossRef] [PubMed]
Jiang, Q. , Wang, X. , and Zhang, H. , 2016, “ One-Pot Hydrothermal Synthesis of LiMn2O4 Cathode Material With Excellent High-Rate and Cycling Properties,” J. Electron. Mater., 45(8), pp. 4350–4356. [CrossRef]
Li, S. , Lei, D. , Xue, Y. , Geng, S. , and Cui, X. , 2017, “ One-Step Solid-State Synthesis of Nanosized LiMn2O4 Cathode Material With Power Properties,” Ionics, 23(8), pp. 1–6. [CrossRef]
Lee, M. J. , Lee, S. , Oh, P. , Kim, Y. , and Cho, J. , 2014, “ High Performance LiMn2O4 Cathode Materials Grown With Epitaxial Layered Nanostructure for Li-Ion Batteries,” Nano Lett., 14(2), pp. 993–999. [CrossRef] [PubMed]
Zhu, X. , Doan, T. N. L. , Yu, Y. , Tian, Y. , Sun, K. E. K. , Zhao, H. , and Chen, P. , 2016, “ Enhancing Rate Performance of LiMn2O4 Cathode in Rechargeable Hybrid Aqueous Battery by Hierarchical Carbon Nanotube/Acetylene Black Conductive Pathways,” Ionics, 22(1), pp. 71–76. [CrossRef]
Wang, F. , Wang, J. , Ren, H. , Tang, H. , Yu, R. , and Wang, D. , 2016, “ Multi-Shelled LiMn2O4 Hollow Microspheres as Superior Cathode Materials for Lithium-Ion Batteries,” Inorg. Chem. Front., 3(3), pp. 365–369. [CrossRef]
Dai, K. , Mao, J. , Li, Z. , Zhai, Y. , Wang, Z. , Song, X. , Battaglia, V. , and Liu, G. , 2014, “ Microsized Single-Crystal Spinel LAMO for High-Power Lithium Ion Batteries Synthesized via Polyvinylpyrrolidone Combustion Method,” J. Power Sources, 248, pp. 22–27. [CrossRef]
Cui, X. , Feng, H. , Xue, Y. , Geng, S. , and Li, S. , 2017, “ Convenient Synthesis and Electrochemical Performance Investigation of Nano-Sized LiMn2O4,” J. Mater. Sci.: Mater. Electron., 28(12), pp. 8529–8536. [CrossRef]
Zhang, Q. , Mei, J. , Wang, X. , Guo, J. , Tang, F. , and Lu, W. , 2014, “ Facile Synthesis of Spherical Spinel LiMn2O4 Nanoparticles via Solution Combustion Synthesis by Controlling Calcinating Temperature,” J. Alloy. Compd., 617, pp. 326–331. [CrossRef]
Gao, X. , Sha, Y. , Lin, Q. , Cai, R. , Tade, M. O. , and Shao, Z. , 2015, “ Combustion-Derived Nanocrystalline LiMn2O4 as a Promising Cathode Material for Lithium-Ion Batteries,” J. Power Sources, 275, pp. 38–44. [CrossRef]
Cai, Y. , Huang, Y. , Wang, X. , Jia, D. , and Tang, X. , 2014, “ Long Cycle Life, High Rate Capability of Truncated Octahedral LiMn2O4 Cathode Materials Synthesized by a Solid-State Combustion Reaction for Lithium Ion Batteries,” Ceram. Int., 40(9), pp. 14039–14043. [CrossRef]
Li, Z. , Ma, Z. , Wang, Y. , Chen, R. , Wu, Z. , and Wang, S. , 2018, “ LDHs Derived Nanoparticle-Stacked Metal Nitride as Interlayer for Long-Life Lithium Sulfur Batteries,” Sci. Bull., 63(3), pp. 169–175. [CrossRef]
Koo, B. R. , and Ahn, H. J. , 2017, “ Polyacrylonitrile Template-Assisted Formation of LiMn2O4 Nanoparticles for Lithium-Ion Batteries,” J. Ceram. Process. Res., 18(3), pp. 207–213. http://jcpr.kbs-lab.co.kr/file/JCPR_vol.18_2017/JCPR18-3/07.2017-022_207-213.pdf
Xie, X. , Wang, X. , Zhang, Q. , and Tang, F. , 2016, “ Multiphase Combustion Synthesis and Enhanced Performance of LiMn2O4 Nanoparticles Using CNTs as a Fuel,” Mater. Res. Innovations, 20(5), pp. 327–331. [CrossRef]
Zhang, H. , Xu, Y. , and Liu, D. , 2015, “ Novel Nanostructured LiMn2O4 Microspheres for High Power Li-Ion Batteries,” RSC Adv., 5(15), pp. 11091–11095. [CrossRef]
Li, B. , Wei, X. , Chang, Z. , Chen, X. , Yuan, X. Z. , and Wang, H. , 2014, “ Facile Fabrication of LiMn2O4 Microspheres From Multi-Shell MnO2 for High-Performance Lithium-Ion Batteries,” Mater. Lett., 135, pp. 75–78. [CrossRef]
Wang, Y. Z. , Shao, X. , Xu, H. Y. , Xie, M. , Deng, S. X. , Wang, H. , Liu, J. B. , and Yan, H. , 2013, “ Facile Synthesis of Porous LiMn2O4 Spheres as Cathode Materials for High-Power Lithium Ion Batteries,” J. Power Sources, 226, pp. 140–148. [CrossRef]
Huang, X. , Yu, H. , Chen, J. , Lu, Z. , Yazami, R. , and Hng, H. H. , 2014, “ Ultrahigh Rate Capabilities of Lithium-Ion Batteries From 3D Ordered Hierarchically Porous Electrodes With Entrapped Active Nanoparticles Configuration,” Adv. Mater., 26(8), pp. 1296–1303. [CrossRef] [PubMed]
Kim, T. W. , and Choi, K. S. , 2014, “ Nanoporous BiVO4 Photoanodes With Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting,” Science, 343(6174), pp. 990–994. [CrossRef] [PubMed]
Cui, Z. , Zu, C. , Zhou, W. , Manthiram, A. , and Goodenough, J. B. , 2016, “ Mesoporous Titanium Nitride-Enabled Highly Stable Lithium-Sulfur Batteries,” Adv. Mater., 28(32), pp. 6926–6931. [CrossRef] [PubMed]
Ren, Y. , Ma, Z. , Morris, R. E. , Liu, Z. , Jiao, F. , Dai, S. , and Bruce, P. G. , 2013, “ A Solid With a Hierarchical Tetramodal Micro-Meso-Macro Pore Size Distribution,” Nat. Commun., 4, p. 2015. [CrossRef] [PubMed]
Yu, C. , Zhang, L. , Shi, J. , Zhao, J. , Gao, J. , and Yan, D. , 2008, “ A Simple Template‐Free Strategy to Synthesize Nanoporous Manganese and Nickel Oxides With Narrow Pore Size Distribution, and Their Electrochemical Properties,” Adv. Funct. Mater., 18(10), pp. 1544–1554. [CrossRef]
Shen, L. F. , Yuan, C. Z. , Luo, H. J. , Zhang, X. G. , and Xu, K. , 2010, “ Facile Synthesis of Hierarchically Porous Li4Ti5O12 Microspheres for High Power Lithium-Ion Batteries,” J. Mater. Chem., 20(33), pp. 6998–7004. [CrossRef]
Duan, L. , Zhang, X. , Yue, K. , Wu, Y. , Zhuang, J. , and Wei, L. , 2017, “ Synthesis and Electrochemical Property of LiMn2O4 Porous Hollow Nanofiber as Cathode for Lithium-Ion Batteries,” Nano. Res. Lett., 12, p. 109. [CrossRef]
Zhu, W. , Lu, Z. , Lu, X. , Yin, F. , Li, W. , Ji, H. , and Yang, G. , 2017, “ Microemulsion Concentration in Preparation of LiMn2O4 Submicron Spherical Particles as Cathode Materials for Highly Reversible Lithium-Ion Batteries,” ChemElectroChem, 4(12), pp. 3204–3211. [CrossRef]
Zou, Z. , Li, Z. , Zhang, H. , Wang, X. , and Jiang, C. , 2017, “ Copolymerization-Assisted Preparation of Porous LiMn2O4 Hollow Microspheres as High Power Cathode of Lithium-Ion Batteries,” J. Mater. Sci. Technol., 33(8), pp. 781–787. [CrossRef]
Yi, Z. , 2016, “ Rheological Phase Reaction Synthesis of Co-Doped LiMn2O4 Octahedral Particles,” J. Mater. Sci.: Mater. Electron., 27(10), pp. 10347–10352. [CrossRef]
Sun, X. , Li, J. , Shi, C. , Wang, Z. , Liu, E. , He, C. , Du, X. , and Zhao, N. , 2012, “ Enhanced Electrochemical Performance of LiFePO4 Cathode With In Situ Chemical Vapor Deposition Synthesized Carbon Nanotubes as Conductor,” J. Power Sources, 220, pp. 264–268. [CrossRef]


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Fig. 1

Scanning electron microscopy images under different magnifications of the mixtures of MnCO3 and MnO2 powders ((a) and (b)), and of the Mn2O3 powders by heating the mixtures of MnCO3 and MnO2 powders at 600 °C for 10 h ((c) and (d))

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Fig. 2

The XRD pattern of the LMO1 and LMO2

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Fig. 3

Scanning electron microscopy images under different magnifications of LMO1 ((a) and (b)) and LMO2 ((c) and (d))

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Fig. 4

The N2 adsorption–desorption isotherm loop ((a) and (b)) and a datagram of the pore size distribution data ((c) and (d)) for the synthesized LMO1 ((a) and (c)) and LMO2 ((b) and (d))

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Fig. 5

Cycle performance of LMO1 and LMO2 at 0.5 C rate

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Fig. 6

The XRD pattern of the LMO2 and LMO3

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Fig. 7

Scanning electron microscopy images under different magnifications of Mn2O3 ((a) and (b)) and LMO3 ((c) and (d))

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Fig. 8

The N2 adsorption–desorption isotherm loop (a) and a histogram of the pore size distribution data (b) for the synthesized LMO3

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Fig. 9

Variation of discharge capacity versus cycle number of LMO2 and LMO3 electrodes at the 0.2, 0.5, 1, 2, 5, and 1 C rates

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Fig. 10

Cycle performance of the LMO2 and LMO3 at 0.5 C rate

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Fig. 11

Electrochemical impedance spectra of the LMO2 and LMO3 in the frequency range between 0.01 Hz and 100 kHz

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Fig. 12

Schematic illustration of the variation of pores conditions before and after cycle




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