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

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Li(Ni{sub 0.4}Co{sub 0.2-y}Al{sub y}Mn{sub 0.4})O{sub 2} with y=0.05 was investigated to understand the effect of replacement of the cobalt by aluminum on the structural and electrochemical properties. The effect of the substitution was studied by in-situ X-ray absorption spectroscopy (XAS), 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 ... continued below

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Rumble, C.; Conry, T.E.; Doeff, Marca; Cairns, Elton J.; Penner-Hahn, James. E. & Deb, Aniruddha February 2, 2010.

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Li(Ni{sub 0.4}Co{sub 0.2-y}Al{sub y}Mn{sub 0.4})O{sub 2} with y=0.05 was investigated to understand the effect of replacement of the cobalt by aluminum on the structural and electrochemical properties. The effect of the substitution was studied by in-situ X-ray absorption spectroscopy (XAS), 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 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 towards Co{sup 4+} and Mn was found to be electrochemically inactive and remains 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.

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  • Journal Name: Electrochemical Society

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  • Report No.: LBNL-3582E
  • Grant Number: DE-AC02-05CH11231
  • DOI: 10.1149/1.3494211 | External Link
  • Office of Scientific & Technical Information Report Number: 984355
  • Archival Resource Key: ark:/67531/metadc1012365

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  • February 2, 2010

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  • Oct. 14, 2017, 8:36 a.m.

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  • Oct. 17, 2017, 6:59 p.m.

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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, article, February 2, 2010; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc1012365/: accessed July 19, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.