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J. Renewable Sustainable Energy 1, 023102 (2009); doi:10.1063/1.3103483 (11 pages)

Spinel LiMn2−xNixO4 cathode materials for high energy density lithium ion rechargeable batteries

Rahul Singhal 1,
Jose J. Saavedra-Aries 1,
Rajesh Katiyar 2,
Yasuyuki Ishikawa 3,
Marius J. Vilkas 3,
Suprem R. Das 3,
Maharaj S. Tomar 4,
and Ram. S. Katiyar 1

1 Institute of Functional Nanomaterials, Department of Physics, University of Puerto Rico, San Juan, 00931, Puerto Rico Map This map
2 Institute of Functional Nanomaterials, Department of Mechanical Engineering, University of Puerto Rico, Mayaguez, 00681, Puerto Rico Map This map
3 Institute of Functional Nanomaterials, Department of Chemistry, University of Puerto Rico, San Juan, 00946, Puerto Rico Map This map
4 Institute of Functional Nanomaterials, Department of Physics, University of Puerto Rico, Mayaguez, 00681, Puerto Rico Map This map

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The practical limitations of fully lithium ion insertion and extraction into LiMn2O4 cathode structure without any structural instability make it unsuitable in commercial Li-ion rechargeable batteries. In this work, we showed that those partially substituted by Ni, i.e., LiMn2−xNixO4 (0 ≤ x ≤ 0.5), prepared by sol-gel technique, could be used as a potential candidate for high energy density and high voltage Li-ion battery applications with superior rate capabilities. The improved structural stability of the cathode was probed by x-ray diffraction and micro-Raman spectroscopy. The density-functional theoretical calculations were employed to identify the minimum energy needed for Li+ diffusion pathway and activation energy in the spinel framework with different Ni ion concentrations. Our results showed significant enhancement in the properties with 25 at. % of Ni solid-solution doping in LiMn2O4 host and the experimental results are in line with the theoretical computations.

© 2009 American Institute of Phyics

ACKNOWLEDGMENTS

The authors gratefully acknowledge partial support by the NASA Grant No. NNX08AB12A and NASA-URC Grant No. NNX08BA48A for this research work. We gratefully thank the High Performance Computing Facility (HPCF) at University of Puerto Rico for providing the facility for computational studies. The XRD measurements were carried out utilizing UPR Materials Characterization Center (MCC) facilities. J. J. S. A. is grateful to the IFN for providing a graduate fellowship.

Article Outline

  1. INTRODUCTION
  2. EXPERIMENTAL
  3. COMPUTATIONAL
  4. RESULTS AND DISCUSSION
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

cathodes, electrochemical electrodes, lithium, Raman spectroscopy, secondary cells, X-ray diffraction

PACS

ARTICLE DATA

History
Received 30 September 2008
Accepted 2 March 2009
Published 27 March 2009
Permalink
http://link.aip.org/link/JRSEBH/v1/i2/p023102/s1

PUBLICATION DATA

ISSN:

19417012 (print)  
19417012 (online)

Publisher:

$abstract.society.value is a Member of CrossRef American Institute of Phyics

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Figures (8) Tables (4)

Figures (click on thumbnails to view enlargements)

FIG. 1
Powder diffraction patterns of LiMn2−XNiXO4 cathodes before the charge-discharge cycling. Inset shows lattice parameter variation with different Ni concentrations.
FIG. 1 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 2
Cyclic voltammogram of LiMn2−XNiXO4/LiPF6+(EC+DMC)/Li coin cell in 3.0–5.0 V range at a voltage scan rate of 0.1 mV/s.
FIG. 2 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 3
Charge-discharge behavior of LiMn2−XNiXO4/LiPF6+(EC+DMC)/Li coin cell.
FIG. 3 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 4
Charge discharge behavior of first 15 cycles of LiMn1.5Ni0.5O4/LiPF6+(EC+DMC)/Li coin cell.
FIG. 4 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 5
The comparison of the cyclability of LiMn2−XNiXO4/LiPF6+(EC+DMC)/Li coin cells each charged and discharged at 0.2 mA/cm2 for 50 cycles.
FIG. 5 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 6
(a) Estimated Li+ hopping path in the Mn15Ni1O32 super-cell. (b) Estimated Li+ hopping path in the Mn12Ni4O32 super-cell, with four Ni substitutions in the structurally equivalent Mn positions.
FIG. 6 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 7
(a), (b) Density of states in pure Mn oxide spinel (top graph) and in admixed with 25% of Ni (bottom graph). (c), (d) Density of states of partially Li intercalated pure Mn oxide spinel (top graph) and in admixed with 25% of Ni (bottom graph).
FIG. 7 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint
FIG. 8
Comparison of the various phonon modes of pure LiMn2O4 and LiMn1.5Ni0.5O4 cathodes in the virgin state and after 50 cycles of charge discharge performance.
FIG. 8 View Enlargement | Download High Resolution Image (.zip file) | Export Figure to PowerPoint

Tables

Table I. Unit cell parameters of LiMn2−xNixO4 cathode materials.

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Table II. LixMn16O32 free and Li partial intercalation energies (eV). Li ultra soft pseudopotential energy of −0.238 eV is removed from the intercalation energy.

View Table
Table III. Li2NixMn16-xO32 and Li0NixMn16-xO32 free and Li partial intercalation energies (eV). Li ultra soft pseudopotential energy of 0.238 eV is removed.

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Table IV. Activation energy Eactiv (meV) for Li ion diffusion in Mn16−xNixO32 supercell

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