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Structural complexity of layered-spinel composite electrodes for Li-ion batteries

Published online by Cambridge University Press:  31 January 2011

Jordi Cabana ,
Christopher S. Johnson ,
Xiao-Qing Yang ,
Kyung-Yoon Chung ,
Won-Sub Yoon ,
Sun-Ho Kang ,
Michael M. Thackeray  and
Clare P. Grey
Jordi Cabana
Affiliation:
Chemistry Department, State University of New York at Stony Brook, Stony Brook, New York 11794
Christopher S. Johnson
Affiliation:
Department of Electrochemical Energy Storage, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439
Kyung-Yoon Chung
Affiliation:
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973
Won-Sub Yoon*
Affiliation:
School of Advanced Materials Engineering, Kookmin University, 861-1 Jeongneung-dong, Seongbuk-gu, Seoul 136-702, Korea
Michael M. Thackeray
Affiliation:
Department of Electrochemical Energy Storage, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439
Clare P. Grey*
Affiliation:
Chemistry Department, State University of New York at Stony Brook, Stony Brook, New York 11794
*
a)Address all correspondence to this author. e-mail: wsyoon@kookmin.ac.kr
b)Address all correspondence to this author. e-mail: cgrey@notes.cc.sunysb.edu
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Abstract

The complexity of layered-spinel yLi2MnO3·(1 – y)Li1+xMn2–xO4 (Li:Mn = 1.2:1; 0 ≤ x ≤ 0.33; y ≥ 0.45) composites synthesized at different temperatures has been investigated by a combination of x-ray diffraction (XRD), x-ray absorption spectroscopy (XAS), and nuclear magnetic resonance (NMR). While the layered component does not change substantially between samples, an evolution of the spinel component from a high to a low lithium excess phase has been traced with temperature by comparing with data for pure Li1+xMn2–xO4. The changes that occur to the structure of the spinel component and to the average oxidation state of the manganese ions within the composite structure as lithium is electrochemically removed in a battery have been monitored using these techniques, in some cases in situ. Our 6Li NMR results constitute the first direct observation of lithium removal from Li2MnO3 and the formation of LiMnO2 upon lithium reinsertion.

Keywords

Energy storageNuclear magnetic resonance (NMR)X-ray diffraction (XRD)
Type
Articles
Information
Journal of Materials Research , Volume 25 , Issue 8: Materials for Electrical Energy Storage , August 2010 , pp. 1601 - 1616
Copyright
Copyright © Materials Research Society 2010

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