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Title: Structural and electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material

Abstract

Li(Ni{sub 0.4}Co{sub 0.15}Al{sub 0.05}Mn{sub 0.4})O{sub 2} was investigated to understand the effect of replacement of the cobalt by aluminum on the structural and electrochemical properties. In situ X-ray absorption spectroscopy (XAS) was performed, utilizing a novel in situ electrochemical cell, specifically designed for long-term X-ray experiments. The cell was cycled at a moderate rate through a typical Li-ion battery operating voltage range. (1.0-4.7 V) XAS measurements were performed at different states of charge (SOC) during cycling, at the Ni, Co, and the Mn edges, revealing details about the response of the cathode to Li insertion and extraction processes. The extended X-ray absorption fine structure (EXAFS) region of the spectra revealed the changes of bond distance and coordination number of Ni, Co, and Mn absorbers as a function of the SOC of the material. The oxidation states of the transition metals in the system are Ni{sup 2+}, Co{sup 3+}, and Mn{sup 4+} in the as-made material (fully discharged), while during charging the Ni{sup 2+} is oxidized to Ni{sup 4+} through an intermediate stage of Ni{sup 3+}, Co{sup 3+} is oxidized toward Co{sup 4+}, and Mn was found to be electrochemically inactive and remained as Mn{sup 4+}. The EXAFS results during cyclingmore » show that the Ni-O changes the most, followed by Co-O, and Mn-O varies the least. These measurements on this cathode material confirmed that the material retains its symmetry and good structural short-range order leading to the superior cycling reported earlier.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Environmental Energy Technologies Division; Materials Sciences Division
OSTI Identifier:
1050692
Report Number(s):
LBNL-4883E
Journal ID: ISSN 0013-4651; JESOAN; TRN: US201218%%897
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 157; Journal Issue: 12; Related Information: Journal Publication Date: 2010; Journal ID: ISSN 0013-4651
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; ABSORPTION; ABSORPTION SPECTROSCOPY; ALUMINIUM; CATHODES; COBALT; COORDINATION NUMBER; ELECTROCHEMICAL CELLS; FINE STRUCTURE; SPECTRA; SYMMETRY; TRANSITION ELEMENTS; VALENCE

Citation Formats

Rumble, C, Conry, T E, Doeff, Marca, Cairns, Elton J, Penner-Hahn, James E, and Deb, Aniruddha. Structural and electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material. United States: N. p., 2010. Web.
Rumble, C, Conry, T E, Doeff, Marca, Cairns, Elton J, Penner-Hahn, James E, & Deb, Aniruddha. Structural and electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material. United States.
Rumble, C, Conry, T E, Doeff, Marca, Cairns, Elton J, Penner-Hahn, James E, and Deb, Aniruddha. 2010. "Structural and electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material". United States. https://www.osti.gov/servlets/purl/1050692.
@article{osti_1050692,
title = {Structural and electrochemical Investigation of Li(Ni0.4Co0.2-yAlyMn0.4)O2 Cathode Material},
author = {Rumble, C and Conry, T E and Doeff, Marca and Cairns, Elton J and Penner-Hahn, James E and Deb, Aniruddha},
abstractNote = {Li(Ni{sub 0.4}Co{sub 0.15}Al{sub 0.05}Mn{sub 0.4})O{sub 2} was investigated to understand the effect of replacement of the cobalt by aluminum on the structural and electrochemical properties. In situ X-ray absorption spectroscopy (XAS) was performed, utilizing a novel in situ electrochemical cell, specifically designed for long-term X-ray experiments. The cell was cycled at a moderate rate through a typical Li-ion battery operating voltage range. (1.0-4.7 V) XAS measurements were performed at different states of charge (SOC) during cycling, at the Ni, Co, and the Mn edges, revealing details about the response of the cathode to Li insertion and extraction processes. The extended X-ray absorption fine structure (EXAFS) region of the spectra revealed the changes of bond distance and coordination number of Ni, Co, and Mn absorbers as a function of the SOC of the material. The oxidation states of the transition metals in the system are Ni{sup 2+}, Co{sup 3+}, and Mn{sup 4+} in the as-made material (fully discharged), while during charging the Ni{sup 2+} is oxidized to Ni{sup 4+} through an intermediate stage of Ni{sup 3+}, Co{sup 3+} is oxidized toward Co{sup 4+}, and Mn was found to be electrochemically inactive and remained as Mn{sup 4+}. The EXAFS results during cycling show that the Ni-O changes the most, followed by Co-O, and Mn-O varies the least. These measurements on this cathode material confirmed that the material retains its symmetry and good structural short-range order leading to the superior cycling reported earlier.},
doi = {},
url = {https://www.osti.gov/biblio/1050692}, journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 12,
volume = 157,
place = {United States},
year = {Mon Jun 14 00:00:00 EDT 2010},
month = {Mon Jun 14 00:00:00 EDT 2010}
}