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Title: Structural characterization of layered LiMnO{sub 2} electrodes by electron diffraction and lattice imaging

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/1.1391949· OSTI ID:680038
;  [1]; ; ;  [2]; ;  [3]
  1. Michigan Technological Univ., Houghton, MI (United States). Dept. of Metallurgical and Materials Engineering
  2. Univ. of St. Andrews, Fife (United Kingdom). School of Chemistry
  3. Argonne National Lab., IL (United States). Chemical Technology Div.

Electrode materials of the formula LiMnO{sub 2} were prepared by an ion-exchange process from {alpha}-NaMnO{sub 2} and were examined by X-ray diffraction and convergent-beam electron diffraction to determine crystal structure and phase purity. Electron diffraction data showed that a typical parent LiMnO{sub 2} sample consisted predominantly of layered LiMnO{sub 2} (C2/m) with lithiated-spinel Li{sub 2}[Mn{sub 2}]O{sub 4} (F4{sub 1}/ddm) present in minor concentration; orthorhombic LiMnO{sub 2} (Pmmm) was detected in trace quantity. An orientation relationship between the monoclinic layered LiMnO{sub 2} and tetragonal lithiated-spinel Li{sub 2}[Mn{sub 2}]O{sub 4} was obtained from an analysis of single-crystal electron diffraction data. Electron diffraction analyses of three electrochemically cycled Li{sub x}MnO{sub 2} (0 < x < 1) samples showed that the parent compound was unstable to repeated lithium intercalation/deintercalation and transformed to a spinel-type structure, consistent with previous reports. These Li{sub x}MnO{sub 2} electrodes, like those derived from orthorhombic-LiMnO{sub 2}, show greater stability compared to standard Li{sub y}[Mn{sub 2}]O{sub 4} spinel electrodes, when cycled between 4.6 and 2.0 V. The unexpected stability of the Li{sub x}MnO{sub 2} electrodes (0.5 {le} x < 1.0) at 3 V is attributed to the presence of Li{sub 1+z}Mn{sub 2{minus}z}O{sub 4} spinel domains (0 < z < 0.33) in a composite electrode structure.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE, Washington, DC (United States)
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
680038
Journal Information:
Journal of the Electrochemical Society, Vol. 146, Issue 7; Other Information: PBD: Jul 1999
Country of Publication:
United States
Language:
English

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