Hostname: page-component-cd9895bd7-jkksz Total loading time: 0 Render date: 2024-12-23T04:15:30.589Z Has data issue: false hasContentIssue false
  • English
  • Français

Disorder in Layered Hydroxides: DIFFaX Simulation of the X-ray Powder Diffraction Patterns of Nickel Hydroxide

Published online by Cambridge University Press:  01 January 2024

T. N. Ramesh ,
R. S. Jayashree  and
P. Vishnu Kamath
T. N. Ramesh
Affiliation:
Department of Chemistry, Central College, Bangalore University, Bangalore 560 001, India
R. S. Jayashree
Affiliation:
Department of Chemistry, Central College, Bangalore University, Bangalore 560 001, India
P. Vishnu Kamath*
Affiliation:
Department of Chemistry, Central College, Bangalore University, Bangalore 560 001, India
*
*E-mail address of corresponding author: vishnu@sscu.iisc.ernet.in
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Layered metal hydroxides exhibit non-uniform broadening of lines in their X-ray powder diffraction (XRPD) patterns, which cannot always be explained on the basis of crystallite size effects. In the case of hexagonal solids such as nickel hydroxide, DIFFaX simulations of the XRPD patterns show that: (1) stacking faults and turbostratic disorder at low (<30%) incidence selectively broaden the h0l reflections; (2) turbostratic disorder at high (>40%) incidence causes asymmetric broadening of the hk0 reflections and a complete extinction of the hkl reflections while leaving 00l unchanged; (3) interstratification selectively broadens the non-hk0 reflections; and (4) cation vacancies reduce the relative intensity of the 100 reflection. In contrast, a reduction in the thickness of the crystallites along the stacking direction of the layers selectively broadens the 00l reflections while a reduction in the disc diameter causes the progressive broadening and extinction of the hk0 reflections. Comparison with experimental data shows that several kinds of disorders have to be invoked to account for the observed broadening. DIFFaX simulations enable the quantification of the different kinds of disorder.

Keywords

Cation VacanciesCrystallite SizeDIFFaXInterstratificationNickel HydroxideStacking FaultsTurbostraticity
Type
Research Article
Information
Clays and Clay Minerals , Volume 51 , Issue 5 , October 2003 , pp. 570 - 576
Copyright
Copyright © 2003, The Clay Minerals Society

References

Andreev, Y.G. and Lundstrom, T., (1994) In-plane lattice-parameter and crystallite-size determination in a turbostratic graphite-like structure Journal of Applied Crystallography 27 767–771 10.1107/S0021889894003249.Google Scholar
Artioli, G. Bellotto, M. Gualtieri, A. and Pavese, A., (1995) Nature of structural disorder in natural kaolinites: A new model based on computer simulation of powder diffraction data and electrostatic energy calculation Clays and Clay Minerals 43 438–445 10.1346/CCMN.1995.0430407.Google Scholar
Barnard, R. Randell, C.F. and Tye, F.L., (1981) Studies concerning the ageing of α and β-Ni(OH)2 in relation to nickel-cadmium cells Power Sources London Academic Press 401–425 vol. 8 .Google Scholar
Bernard, M.C. Cortes, R. Keddam, M. Takenouti, H. Bernard, P. and Senyarich, S., (1996) Structural defects and electrochemical reactivity of β-Ni(OH)2 Journal of Power Sources 63 247–254 10.1016/S0378-7753(96)02482-2.Google Scholar
Cornilsen, B.C. Karjala, P.J. and Loyselle, P.L., (1988) Structural models for nickel hydroxide electrode active mass Journal of Power Sources 22 351–357 10.1016/0378-7753(88)80029-6.Google Scholar
Cornilsen, B.C. Shan, X. and Loyselle, L., (1990) Structural comparison of nickel electrodes and precursor phases Journal of Power Sources 29 453–456 10.1016/0378-7753(90)85018-8.Google Scholar
Delmas, C. and Tessier, C., (1997) Stacking faults in the structure of nickel hydroxide: a rationale of its high electrochemical activity Journal of Materials Chemistry 7 1439–1443 10.1039/a701037k.Google Scholar
Dittrich, H. and Wohlfahrt-Mehrens, M., (2001) Stacking fault analysis in layered materials International Journal of Inorganic Materials 3 1137–1142 10.1016/S1466-6049(01)00143-X.Google Scholar
Dixit, M. Subbanna, G.N. and Kamath, P.V., (1996) Homogeneous precipitation from solution by urea hydrolysis: a novel chemical route to the α-hydroxides of nickel and cobalt Journal of Materials Chemistry 6 1429–1432 10.1039/JM9960601429.Google Scholar
Dixit, M. Kamath, P.V. and Gopalkrishnan, J., (1999) Zinc-substituted a-Nickel hydroxide as an electrode material for alkaline secondary cells Journal of the Electrochemical Society 146 79–82 10.1149/1.1391567.Google Scholar
Greaves, C. and Thomas, M.A., (1986) Refinement of the structure of deuterated nickel hydroxide, Ni(OD)2, by powder neutron diffraction and evidence for structural disorder in samples with high surface area Acta Crystallographica B42 51–55 10.1107/S0108768186098592.Google Scholar
Guggenheim, S. Bain, D.C. Bergaya, F. Brigatti, M.F. Drits, V.A. Eberl, D.D. Formoso, M.L.L. Galán, E. Merriman, R.J. Peacor, D.R. Stanjek, H. and Watanabe, T., (2002) Report of the Association Internationale pour l’Etude des Argiles (AIPEA) nomenclature committe for 2001: order, disorder and crystallinity in phyllosilicates and the use of the ‘crystallinity index’ Clays and Clay Minerals 50 406–409 10.1346/000986002760833783.Google Scholar
Jayashree, R.S. Kamath, P.V. and Subbanna, G.N., (2000) The effect of crystallinity on the reversible discharge capacity of ni ckel hydroxide Journal of the Electrochemical Society 147 2029–2032 10.1149/1.1393480.Google Scholar
Kamath, P.V. Dixit, M. Indira, L. Shukla, A.K. Ganesh Kumar, V. and Munichandraiah, N., (1994) Stabilized a-Ni(OH)2 as electrode material for alkaline secondary cells Journal of the Electrochemical Society 141 2956–2959 10.1149/1.2059264.Google Scholar
Lu, Z. and Dahn, J.R., (2001) Effects of stacking fault defects on the X-ray diffraction patterns of T2, O2, and O6 structure Li2/3[CoxNi1/3-xMn2/3]O2 Chemistry of Materials 13 2078–2083 10.1021/cm000885d.Google Scholar
McBreen, J., White, R.E. Bockris, J.O.M. and Conway, B.E., (1990) The nickel oxide electrodes Modern Aspects ofElectrochemistry New York Plenum Press 28 63.Google Scholar
Oliva, P. Leonardi, J. Laurent, J.F. Delmas, C. Braconnier, J.J. Figlarz, M. Fievet, F. and de Guibert, A., (1982) Review of the structure and the electrochemistry of nickel hydroxides and oxy-hydroxides Journal of Power Sources 8 229–255 10.1016/0378-7753(82)80057-8.Google Scholar
Oswald, H.R. Asper, R. and Lieth, R.M.A., (1977) Bivalent metal hydroxides Preparation and Crystal Growth of Materials with Layered Structures Dordrecht, The Netherlands Reidel Publishing Company.Google Scholar
Rajamathi, M. Kamath, P.V. and Seshadri, R., (2000) Polymorphism in nickel hydroxide: role of interstratification Journal of Materials Chemistry 10 503–506 10.1039/a905651c.Google Scholar
Tessier, C. Haumesser, P.H. Bernard, P. and Delmas, C., (1999) The structure of Ni(OH)2: From the ideal material to the electrochemically active one Journal of the Electrochemical Society 146 2059 10.1149/1.1391892.Google Scholar
Treacy, M.M.J., Deem, M.W. and Newsam, J.M. (2000) Computer code DIFFaX, Version 1.807.Google Scholar
Treacy, M.M.J. Newsam, J.M. and Deem, M.W., (1991) A general recursion method for calculating diffracted intensities from crystals containing planar faults Proceedings of the Royal Society, London A433 499–520 10.1098/rspa.1991.0062.Google Scholar
Viani, A. Gualtieri, A.F. and Artioli, G., (2002) The nature of disorder in montmorillonite by simulation of X-ray powder patterns American Mineralogist 87 966–975 10.2138/am-2002-0720.Google Scholar
Warren, B.E. and Bodenstein, P., (1966) The shape of two-dimensional carbon black reflections Acta Crystallographica 20 602–605 10.1107/S0365110X66001464.Google Scholar
West, A.R., (1987) Slid State Chemistry and its Applications Singapore John Wiley and Sons.Google Scholar