Novel synthesis process and structure refinements of Li4Mn5O12 for rechargeable lithium batteries

Toshimi Takada; Hiroshi Hayakawa; Etsuo Akiba; Fujio Izumi; Bryan C. Chakoumakos

doi:10.1016/S0378-7753(96)02570-0

Novel synthesis process and structure refinements of Li₄Mn₅O₁₂ for rechargeable lithium batteries

Toshimi Takada, Hiroshi Hayakawa, Etsuo Akiba, Fujio Izumi, Bryan C. Chakoumakos

Single Crystal Diffraction

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

Well-crystallized Li₄Mn₅O₁₂ powder with grain size of 0.1-0.4 μm was prepared by heating a eutectic mixture of lithium acetate (LiOAc), and manganese nitrate (Mn(NO³)₂), in an oxygen atmosphere. The structure of Li₄Mn₅O₁₂ crystallites was found to be a cubic spinel using Rietveld refinement of both neutron and X-ray powder diffraction data. We confirmed that lithium ions occupy both the tetrahedral 8a sites, and part of the octahedral 16d sites, but not the 16c sites in the space group Fd3̄m, while all the manganese ions occupy the 16d sites. The lattice parameter was found to be sensitive to the synthesis temperature as a result of the variation in manganese valence. Samples prepared at 500 °C showed better electrode performance. A rechargeable capacity of about 135 mAh/g for the cell Li/Li₄Mn₅O₁₂ was obtained in the 2.5-3.6 V range of cell voltages.

Original language	English
Pages (from-to)	613-617
Number of pages	5
Journal	Journal of Power Sources
Volume	68
Issue number	2
DOIs	https://doi.org/10.1016/S0378-7753(96)02570-0
State	Published - Oct 1997

Funding

The authors would like to thank Mr A. Goto, Dr M. Yosh-ikawa, Hitachi, and Dr T. Horiba, Shin-Kobe Electric Machinery, for performing the electrochemical measurements. The neutron diffraction work was conducted at Oak Ridge National Laboratory which is managed by Lockheed Martin Energy Research for the US Department of Energy under contract no. DE-AC05-96OR22464.

Keywords

Lithium batteries
Lithium manganese oxides
Rietveld method
Spinel
Structure refinement

Access to Document

10.1016/S0378-7753(96)02570-0

Cite this

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title = "Novel synthesis process and structure refinements of Li4Mn5O12 for rechargeable lithium batteries",

abstract = "Well-crystallized Li4Mn5O12 powder with grain size of 0.1-0.4 μm was prepared by heating a eutectic mixture of lithium acetate (LiOAc), and manganese nitrate (Mn(NO3)2), in an oxygen atmosphere. The structure of Li4Mn5O12 crystallites was found to be a cubic spinel using Rietveld refinement of both neutron and X-ray powder diffraction data. We confirmed that lithium ions occupy both the tetrahedral 8a sites, and part of the octahedral 16d sites, but not the 16c sites in the space group Fd{\=3}m, while all the manganese ions occupy the 16d sites. The lattice parameter was found to be sensitive to the synthesis temperature as a result of the variation in manganese valence. Samples prepared at 500 °C showed better electrode performance. A rechargeable capacity of about 135 mAh/g for the cell Li/Li4Mn5O12 was obtained in the 2.5-3.6 V range of cell voltages.",

keywords = "Lithium batteries, Lithium manganese oxides, Rietveld method, Spinel, Structure refinement",

author = "Toshimi Takada and Hiroshi Hayakawa and Etsuo Akiba and Fujio Izumi and Chakoumakos, {Bryan C.}",

year = "1997",

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T1 - Novel synthesis process and structure refinements of Li4Mn5O12 for rechargeable lithium batteries

AU - Takada, Toshimi

AU - Hayakawa, Hiroshi

AU - Akiba, Etsuo

AU - Izumi, Fujio

AU - Chakoumakos, Bryan C.

PY - 1997/10

Y1 - 1997/10

N2 - Well-crystallized Li4Mn5O12 powder with grain size of 0.1-0.4 μm was prepared by heating a eutectic mixture of lithium acetate (LiOAc), and manganese nitrate (Mn(NO3)2), in an oxygen atmosphere. The structure of Li4Mn5O12 crystallites was found to be a cubic spinel using Rietveld refinement of both neutron and X-ray powder diffraction data. We confirmed that lithium ions occupy both the tetrahedral 8a sites, and part of the octahedral 16d sites, but not the 16c sites in the space group Fd3̄m, while all the manganese ions occupy the 16d sites. The lattice parameter was found to be sensitive to the synthesis temperature as a result of the variation in manganese valence. Samples prepared at 500 °C showed better electrode performance. A rechargeable capacity of about 135 mAh/g for the cell Li/Li4Mn5O12 was obtained in the 2.5-3.6 V range of cell voltages.

AB - Well-crystallized Li4Mn5O12 powder with grain size of 0.1-0.4 μm was prepared by heating a eutectic mixture of lithium acetate (LiOAc), and manganese nitrate (Mn(NO3)2), in an oxygen atmosphere. The structure of Li4Mn5O12 crystallites was found to be a cubic spinel using Rietveld refinement of both neutron and X-ray powder diffraction data. We confirmed that lithium ions occupy both the tetrahedral 8a sites, and part of the octahedral 16d sites, but not the 16c sites in the space group Fd3̄m, while all the manganese ions occupy the 16d sites. The lattice parameter was found to be sensitive to the synthesis temperature as a result of the variation in manganese valence. Samples prepared at 500 °C showed better electrode performance. A rechargeable capacity of about 135 mAh/g for the cell Li/Li4Mn5O12 was obtained in the 2.5-3.6 V range of cell voltages.

KW - Lithium batteries

KW - Lithium manganese oxides

KW - Rietveld method

KW - Spinel

KW - Structure refinement

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