Document Detail

Characterization of Novel Lithium Battery Cathode Materials by Spectroscopic Methods: The Li5+xFeO4 System.
MedLine Citation:
PMID:  23876729     Owner:  NLM     Status:  In-Data-Review    
The novel, lithium-rich oxide-phase Li5FeO4 (LFO) could, in theory, deliver a specific capacity >900 mAh/g when deployed as a cathode or cathode precursor in a battery with a lithium-based anode. However, research results to date on LFO indicate that less than one of the five Li(+) cations can be reversibly de-intercalated/re-intercalated during repetitive charging and discharging cycles. In the present research, the system Li5+xFeO4 with x values in the range of 0.0-2.0 was investigated by a combination of Raman and X-ray absorption spectroscopic methods supported by X-ray diffraction (XRD) analysis in order to determine if the Li5FeO4 lattice would accommodate additional Li(+) ions, with concomitant lowering of the valence on the Fe(III) cations. Both the Raman phonon spectra and the XRD patterns were invariant for all values of x, strongly indicating that additional Li(+) did not enter the Li5FeO4 lattice. Also, Raman spectral results and high-resolution synchrotron XRD data revealed the presence of second-phase Li2O in all samples with x greater than 0.0. Synchrotron X-ray absorption spectroscopy at the Fe kα edge performed on the sample with a Li-Fe ratio of 7.0 (i.e., x = 2.0) showed no evidence for the presence of Fe(II). This resistance to accepting more lithium into the Li5FeO4 structure is attributed to the exceedingly stable nature of high-spin Fe(III) in tetrahedral "Fe(III)O4" structural units of Li5FeO4. Partial substitution of the Fe(III) with other cations could provide a path toward increasing the reversible Li(+) content of Li5xFeO4-type phases.
Victor A Maroni; Christopher S Johnson; Shawn C M Rood; A Jeremy Kropf; Dean A Bass
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Applied spectroscopy     Volume:  67     ISSN:  1943-3530     ISO Abbreviation:  Appl Spectrosc     Publication Date:  2013 Aug 
Date Detail:
Created Date:  2013-07-23     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0372406     Medline TA:  Appl Spectrosc     Country:  United States    
Other Details:
Languages:  eng     Pagination:  903-12     Citation Subset:  IM    
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
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