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Title: The structure and ordering of {epsilon}-MnO{sub 2}

Abstract

The presence of {epsilon}-MnO{sub 2} as a major component of electrolytic manganese dioxide (EMD) has been demonstrated by a combined X-ray diffraction/transmission electron microscopy (TEM) study. {epsilon}-MnO{sub 2} usually has a partially ordered defect NiAs structure containing 50% cation vacancies; these vacancies can be fully ordered by a low temperature (200 deg. C) heat treatment to form a pseudohexagonal but monoclinic superlattice. Numerous fine-scale anti-phase domain boundaries are present in ordered {epsilon}-MnO{sub 2} and cause extensive peak broadening and a massive shift of a very intense, 0.37 nm superlattice peak. This suggests a radically different explanation of the ubiquitous, very broad {approx}0.42 nm peak ({approx}21-22 deg. 2{theta}, CuK{alpha} radiation) in EMDs, which heretofore has been attributed to Ramsdellite containing numerous planar defects. This work confirms the multi-phase model of equiaxed EMDs proposed by Heuer et al. [ITE Lett. 1(6) (2000) B50; Proc. Seventh Int. Symp. Adv. Phys. Fields 92 (2001)], rather than the defective single-phase model of Chabre and Pannetier [Prog. Solid State Chem. 23 (1995) 1] and Bowden et al. [ITE Lett. 4(1) (2003) B1].

Authors:
 [1];  [1];  [1];  [2];  [3];  [4]
  1. Department of Materials Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106-7204 (United States)
  2. Department of Materials Science and Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106-7204 (United States). E-mail: heuer@case.edu
  3. Physical Sciences Inc., 20 New England Business Center, Andover, MA 01810 (United States)
  4. Energizer Battery Manufacturing, 25225 Detroit Rd., Westlake, OH 44145 (United States)
Publication Date:
OSTI Identifier:
20784919
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2005.11.042; PII: S0022-4596(05)00573-6; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; HEAT TREATMENTS; MANGANESE OXIDES; MONOCLINIC LATTICES; SUPERLATTICES; TEMPERATURE RANGE 0400-1000 K; TRANSMISSION ELECTRON MICROSCOPY; VACANCIES; X-RAY DIFFRACTION

Citation Formats

Kim, Chang-Hoon, Akase, Zentaro, Zhang Lichun, Heuer, Arthur H., Newman, Aron E., and Hughes, Paula J. The structure and ordering of {epsilon}-MnO{sub 2}. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.11.042.
Kim, Chang-Hoon, Akase, Zentaro, Zhang Lichun, Heuer, Arthur H., Newman, Aron E., & Hughes, Paula J. The structure and ordering of {epsilon}-MnO{sub 2}. United States. doi:10.1016/j.jssc.2005.11.042.
Kim, Chang-Hoon, Akase, Zentaro, Zhang Lichun, Heuer, Arthur H., Newman, Aron E., and Hughes, Paula J. Wed . "The structure and ordering of {epsilon}-MnO{sub 2}". United States. doi:10.1016/j.jssc.2005.11.042.
@article{osti_20784919,
title = {The structure and ordering of {epsilon}-MnO{sub 2}},
author = {Kim, Chang-Hoon and Akase, Zentaro and Zhang Lichun and Heuer, Arthur H. and Newman, Aron E. and Hughes, Paula J.},
abstractNote = {The presence of {epsilon}-MnO{sub 2} as a major component of electrolytic manganese dioxide (EMD) has been demonstrated by a combined X-ray diffraction/transmission electron microscopy (TEM) study. {epsilon}-MnO{sub 2} usually has a partially ordered defect NiAs structure containing 50% cation vacancies; these vacancies can be fully ordered by a low temperature (200 deg. C) heat treatment to form a pseudohexagonal but monoclinic superlattice. Numerous fine-scale anti-phase domain boundaries are present in ordered {epsilon}-MnO{sub 2} and cause extensive peak broadening and a massive shift of a very intense, 0.37 nm superlattice peak. This suggests a radically different explanation of the ubiquitous, very broad {approx}0.42 nm peak ({approx}21-22 deg. 2{theta}, CuK{alpha} radiation) in EMDs, which heretofore has been attributed to Ramsdellite containing numerous planar defects. This work confirms the multi-phase model of equiaxed EMDs proposed by Heuer et al. [ITE Lett. 1(6) (2000) B50; Proc. Seventh Int. Symp. Adv. Phys. Fields 92 (2001)], rather than the defective single-phase model of Chabre and Pannetier [Prog. Solid State Chem. 23 (1995) 1] and Bowden et al. [ITE Lett. 4(1) (2003) B1].},
doi = {10.1016/j.jssc.2005.11.042},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 179,
place = {United States},
year = {Wed Mar 15 00:00:00 EST 2006},
month = {Wed Mar 15 00:00:00 EST 2006}
}