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Electronic Structure and Bonding in Energy Storage Materials


Miao, Shu (2007) Electronic Structure and Bonding in Energy Storage Materials. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/FD8F-2H41.


LixNi0.5Mn0.5O2 and LixNi1/3Mn1/3Co1/3O2 are cathode materials in Li-ion batteries. The changes in their electronic structure during charging/discharging processes were studied by using electron energy loss spectrometry (EELS) in a transmission electron microscope (TEM) and first-principles calculations. Significant growth was observed at O K-edge upon the removal of lithium, indicating a depletion of O 2p electrons. Only small changes were observed on Ni absorption edges. Our results indicate that the widely believed Ni2+ -> Ni4+ oxidation does not occur during delithiation, and O is mainly responsible for the charge compensation in these materials. Following similar procedure, the olivine phases of LixFePO4 were studied. It was found that about half electron was donated by Fe atoms during delithiation, while the rest of the charge was contributed by O atoms. We also studied the bonding in Mg2Si. The Mg-Si bond was found to be very ionic. An ionicity of 74% was found via Bader analysis.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Bonding; EELS; Electronic structure; Li-ion batteries; Valence
Degree Grantor:California Institute of Technology
Division:Engineering and Applied Science
Major Option:Materials Science
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Fultz, Brent T.
Thesis Committee:
  • Fultz, Brent T. (chair)
  • Atwater, Harry Albert
  • Bockrath, Marc William
  • Yazami, Rachid
  • Haile, Sossina M.
Defense Date:30 January 2007
Record Number:CaltechETD:etd-02052007-090808
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:500
Deposited By: Imported from ETD-db
Deposited On:05 Feb 2007
Last Modified:18 Mar 2020 19:08

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