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

Journal Article · · Journal of the Electrochemical Society
OSTI ID:1050692

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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
Environmental Energy Technologies Division; Materials Sciences Division
DOE Contract Number:
DE-AC02-05CH11231
OSTI ID:
1050692
Report Number(s):
LBNL-4883E; JESOAN; TRN: US201218%%897
Journal Information:
Journal of the Electrochemical Society, Vol. 157, Issue 12; Related Information: Journal Publication Date: 2010; ISSN 0013-4651
Country of Publication:
United States
Language:
English