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Journal of Renewable and Sustainable Energy / Volume 1 / Issue 2 / REGULAR ARTICLES

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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 Singhal1, Jose J. Saavedra-Aries1, Rajesh Katiyar2, Yasuyuki Ishikawa3, Marius J. Vilkas3, Suprem R. Das3, Maharaj S. Tomar4, and Ram. S. Katiyar1

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

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(Received 30 September 2008; accepted 2 March 2009; published online 27 March 2009)

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

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

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http://link.aip.org/link/doi/10.1063/1.3103483

PUBLICATION DATA

ISSN:

1941-7012 (print)  
1941-7012 (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 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 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 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 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 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 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 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 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.

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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

View Table


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