Skip to main content
SpringerLink
Log in

Ionic conductivity in single-crystal LiAlSi2O6: influence of structure on lithium mobility

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

With the increased interest in application of Li aluminosilicate materials as solid electrolytes, this study focuses on investigating the influence of structure on conductivity properties in single-crystal LiAlSi2O6 which is characterized by three crystal polymorphs where only structural arrangements differ while the amount of mobile carriers is identical. Two single-crystal polymorphic phases produced at ambient pressure are with tetragonal P41212 symmetry and hexagonal P6222 symmetry, also referred to as β- and γ-spodumene in the older literature. For this study, flux-grown hexagonal spodumene single-crystals were measured for conductivity parallel to the crystallographic c-axis and the results were compared with previously published results for tetragonal spodumene, both as single-crystal and polycrystalline aggregate, monoclinic spodumene (α-spodumene) and LiAlSi2O6 glass. The activation energy E a of 79.69 ± 0.38 kJ/mol for hexagonal phase is very similar to the other crystalline polymorphs with the same orientation. However, the σ DC in hexagonal spodumene was determined to be higher than other crystalline phases and about 1.5 orders of magnitude lower than the conductivity in glass LiAlSi2O6 phase. Additionally, the densities of atomic packing were compared between phases, and the differences in the openness of the structures indicate that the more dominant effect on the Li mobility lies with the actual spatial arrangement of Li sites and the Si/Al sublattice.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Alekseeva I, Dymshits O, Tsenter M, Zhilin A, Golubkov V, Denisov I, Skoptsov N, Malyarevich A, Yumashev K (2010) Optical applications of glass-ceramics. J Non-Cryst Solids 356:3042–3058

    Article  Google Scholar 

  • Baum E, Treutmann W, Lottermoser W, Amthauer G (1997) Magnetic properties of the clinopyroxenes aegirine and hedenbergite: a magnetic susceptibility study on single crystals. Phys Chem Miner 24:294–300

    Article  Google Scholar 

  • Beall GH, Pinckney LR (1999) Nanophase glass-ceramics. J Am Ceram Soc 82:5–16

    Article  Google Scholar 

  • Clarke PT, Spink JM (1969) The crystal structure of β-spodumene, LiAlSi2O6-II. Z Kristallogr 130:420–426

    Article  Google Scholar 

  • Deer WA, Howie RA, Zussman J (1992) An introduction to the rock-forming minerals, 2nd edn. Pearson Education Ltd, Harlow

    Google Scholar 

  • Dowty E (1980) Crystal-chemical factors affecting the mobility of ions in minerals. Am Miner 65:174–182

    Google Scholar 

  • Drysdale DJ (1975) Hydrothermal synthesis of various spodumenes. Am Miner 60:105–110

    Google Scholar 

  • Fortier SM, Giletti BJ (1989) An empirical model for predicting diffusion coefficients in silicate minerals. Science 245:1481–1484

    Article  Google Scholar 

  • Imre AW, Voss S, Staesche H, Ingram MD, Funke K, Mehrer H (2007) Pressure-dependent diffusion coefficients and haven ratios in cation-conducting glasses. J. Phys. Chem. B 111:5301–5307

    Article  Google Scholar 

  • Knauth P (2009) Inorganic solid Li ion conductors: an overview. Solid State Ion 180:911–916

    Article  Google Scholar 

  • Kuhn A, Wilkening M, Heitjans P (2009) Mechanically induced decrease of the Li conductivity in an alumosilicate glass. Solid State Ion 180:302–307

    Article  Google Scholar 

  • Li CT (1968) The crystal structure of LiAlSi2O6-III (high-quartz solid solution). Z Kristallogr 127:327–348

    Article  Google Scholar 

  • Li CT (1973) The role of lithium in stabilizing some high-temperature silica phases. Z Kristallogr 138:216–236

    Article  Google Scholar 

  • Li CT, Peacor DR (1968) The crystal structure of LiAlSi2O6-II ("β-spodumene”). Z Kristallogr 126:46–65

    Article  Google Scholar 

  • Liebau F (1985) Structural chemistry of silicates. Springer, Berlin

    Book  Google Scholar 

  • McMillan PW (1979) Glass-ceramics, 2nd edn. Academic Press, London

    Google Scholar 

  • Mehrer H (2007) Diffusion in solids—fundamentals, methods, materials, diffusion-controlled processes, Springer Series in Solid-State Sci, vol 155. Springer, New York, pp 185; pp 650

  • Nordmann A, Cheng YB (1997) Crystallization behaviour and microstructural evolution of a Li2O–Al2O3–SiO2 glass derived from spodumene mineral. J Mater Sci 32:83–89

    Article  Google Scholar 

  • Pouchou JL, Pichoir F (1991) Electron probe quantitation. Plenum Press Div Plenum Publishing Corp, New York

    Google Scholar 

  • Qi F, Rier C, Böhmer R, Franke W, Heitjans P (2005) Ion hopping in crystalline and glassy spodumene LiAlSi2O6: 7Li spin-lattice relaxation and 7Li echo NMR spectroscopy. Phys Rev B 72:104301-1–10430111

    Article  Google Scholar 

  • Redhammer GJ, Roth G (2004) Structural variation and crystal chemistry of LiMe3 +Si2O6 clinopyroxenes Me3 + = AI, Ga, Cr, V, Fe, Sc and In. Z Kristallogr 219:278–294

    Article  Google Scholar 

  • Roth G, Boehm H (1987) Ionic conductivity of β-spodumene (LiAlSi2O6). Solid State Ion 22:253–256

    Article  Google Scholar 

  • Scheidler H, Rodek E (1989) Li2O–Al2O3–SiO2 glass-ceramics. Am Ceram Soc Bull 68:1926–1930

    Google Scholar 

  • Schlechter E, Stalder R, Behrens H (2012) Electrical conductivity of H-bearing orthopyroxene single crystals measured with impedance spectroscopy. Phys Chem Miner 39:531–541

    Article  Google Scholar 

  • Shannon RD, Prewitt CD (1969) Effective Ionic Radii in Oxides and Fluorides. Acta Cryst B 25:925–946

    Article  Google Scholar 

  • Sharma SK, Simons B (1981) Raman study of crystalline polymorphs and glasses of spodumene composition quenched from various pressures. Am Mineral 66:118–126

    Google Scholar 

  • Voss S, Divinski S, Imre AW, Mehrer H, Mundy JN (2005) Towards a universal behaviour of ion dynamics in Na- and Rb-oxide glasses. Solid State Ion 176:1383–1391

    Article  Google Scholar 

  • Welsch A-M, Behrens H, Ross S, Murawski D (2012a) Structural control of ionic conductivity in LiAlSi2O6 and LiAlSi4O10 glasses and single crystals. Z Phys Chem 226:491–511

    Article  Google Scholar 

  • Welsch A-M, Behrens H, Horn I, Ross S, Heitjans P (2012b) Self-diffusion of lithium in LiAlSi2O6 glasses studied using mass spectrometry. J Phys Chem A 116:309–318

    Article  Google Scholar 

  • Wilke, K-Th(1988) Kristallzüchtung, VEB – Deutscher Verlag der Wissenschaften, Berlin

  • Wilkening M, Kuhn A, Heitjans P (2008) Atomic-scale measurement of ultraslow Li motions in glassy LiAlSi2O6 by two-time 6Li spin-alignment echo NMR correlation spectroscopy. Phys Rev B 78:054303-1–054303-9

    Article  Google Scholar 

  • Zhao ZF, Zheng YF (2007) Diffusion compensation for argon, hydrogen, lead, and strontium in minerals: empirical relationships to crystal chemistry. Am Mineral 92:289–308

    Article  Google Scholar 

Download references

Acknowledgments

Great appreciation of the effort invested by Dr Biljana Krüger (née Lazic) for high-temperature X-ray single-crystal diffractometry is hereby acknowledged. The authors would also like to thank Otto Diedrich and Julian Feige for sample preparation.

Author information

Authors and Affiliations

  1. Institut für Mineralogie, Leibniz Universität Hannover, Callinstraße 3, 30167, Hannover, Germany

    A-M. Welsch & D. Murawski

  2. Materials Science Laboratory, Institute of Nuclear Sciences, 170 Vinča, P.O. Box 522, 11001, Belgrade, Serbia

    M. Prekajski

  3. Laboratory of Crystallography, Faculty of Mining and Geology, University of Belgrade, Ðusina 7, 11000, Belgrade, Serbia

    P. Vulic & A. Kremenovic

Authors
  1. A-M. Welsch
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. Murawski
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Prekajski
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. P. Vulic
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A. Kremenovic
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A-M. Welsch.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Welsch, AM., Murawski, D., Prekajski, M. et al. Ionic conductivity in single-crystal LiAlSi2O6: influence of structure on lithium mobility. Phys Chem Minerals 42, 413–420 (2015). https://doi.org/10.1007/s00269-015-0732-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00269-015-0732-2

Keywords

Search

Navigation