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Title: Electrochemical cycling-induced spinel formation in high-charge-capacity orthorhombic LiMnO{sub 2}

Abstract

Li{sub x}Mn{sub 2}O{sub 4} spinel normally undergoes a transformation from its cubic to tetragonal phase when x exceeds 1 due to a collective Jahn-Teller distortion, resulting in poor cyclability when both the 4 and 3 V intercalation plateaus are utilized. In this study, the authors show that this transformation is suppressed in spinels of composition up to x {approx} 2 obtained through the electrochemical cycling of orthorhombic LiMnO{sub 2}. X-ray diffraction, transmission electron microscopy, and high-resolution electron microscopy studies together show the cycling produces a cubic spinel containing partial tetrahedral cation site occupancy and a nanodomain structure (20 to 50 nm size) within parent single-crystalline oxide particles. This structure is responsible for the cycling stability of electrochemically produced spinel. The reversible capacity (272 mAh/g) and energy density (853 Wh/kg) achieved at a low charge-discharge rate (3.33 mA/g) in the present samples are the highest among crystalline LiMnO{sub 2} materials reported to date.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Massachusetts Inst. of Tech., Cambridge, MA (US)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
20003173
DOE Contract Number:  
AC07-94ID13223
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 146; Journal Issue: 9; Other Information: PBD: Sep 1999
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; SPINELS; LITHIUM OXIDES; ENERGY DENSITY; CAPACITY; MANGANESE OXIDES; METAL-NONMETAL BATTERIES

Citation Formats

Jang, Y.I., Huang, B., Wang, H., Sadoway, D.R., and Chiang, Y.M. Electrochemical cycling-induced spinel formation in high-charge-capacity orthorhombic LiMnO{sub 2}. United States: N. p., 1999. Web. doi:10.1149/1.1392457.
Jang, Y.I., Huang, B., Wang, H., Sadoway, D.R., & Chiang, Y.M. Electrochemical cycling-induced spinel formation in high-charge-capacity orthorhombic LiMnO{sub 2}. United States. doi:10.1149/1.1392457.
Jang, Y.I., Huang, B., Wang, H., Sadoway, D.R., and Chiang, Y.M. Wed . "Electrochemical cycling-induced spinel formation in high-charge-capacity orthorhombic LiMnO{sub 2}". United States. doi:10.1149/1.1392457.
@article{osti_20003173,
title = {Electrochemical cycling-induced spinel formation in high-charge-capacity orthorhombic LiMnO{sub 2}},
author = {Jang, Y.I. and Huang, B. and Wang, H. and Sadoway, D.R. and Chiang, Y.M.},
abstractNote = {Li{sub x}Mn{sub 2}O{sub 4} spinel normally undergoes a transformation from its cubic to tetragonal phase when x exceeds 1 due to a collective Jahn-Teller distortion, resulting in poor cyclability when both the 4 and 3 V intercalation plateaus are utilized. In this study, the authors show that this transformation is suppressed in spinels of composition up to x {approx} 2 obtained through the electrochemical cycling of orthorhombic LiMnO{sub 2}. X-ray diffraction, transmission electron microscopy, and high-resolution electron microscopy studies together show the cycling produces a cubic spinel containing partial tetrahedral cation site occupancy and a nanodomain structure (20 to 50 nm size) within parent single-crystalline oxide particles. This structure is responsible for the cycling stability of electrochemically produced spinel. The reversible capacity (272 mAh/g) and energy density (853 Wh/kg) achieved at a low charge-discharge rate (3.33 mA/g) in the present samples are the highest among crystalline LiMnO{sub 2} materials reported to date.},
doi = {10.1149/1.1392457},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 146,
place = {United States},
year = {1999},
month = {9}
}