Light Metals 2014 pp 1239-1244 | Cite as

Interaction of Sodium Vapor and Graphite Studied by Thermogravimetric Analysis

Abstract

Intercalation of sodium in carbon materials is of paramount importance for the Hall-Héroult process. The interaction of sodium and graphite has been investigated for decades, but despite considerable efforts, the transport and nature of sodium in carbon materials are still poorly understood. Here we report on a study of the interaction between graphite and sodium vapor by thermogravimetric analysis. A graphitized carbon material was exposed to sodium vapor, and the equilibration of sodium uptake in the carbon material was monitored. The kinetics of the sodium uptake is discussed with respect to surface adsorption, bulk diffusion and the solid solubility of sodium in graphite. The kinetics of the reaction was analyzed with support from finite element method simulations. Finally, recent density functional theory simulations of sodium intercalation compounds are presented, demonstrating the low thermodynamic stability of such sodium intercalation compounds reflecting the low reactivity of sodium with carbon.

Keywords

Aluminum Electrolysis Graphite Thermogravimetry Sodium Diffusion DFT Calculation 

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References

  1. 1.
    Siljan, O.J., C. Schørning, and T. Grande, State-of-the-art alumino-silicate refractories for aluminium electrolysis cell. JOM, 2002. 54(5): p. 46–54;63.CrossRefGoogle Scholar
  2. 2.
    Schøning, C. and T. Grande, The stability of refractory oxides in sodium-rich environments. JOM, 2006. 58(2): p. 58–61.CrossRefGoogle Scholar
  3. 3.
    Wang, Z., E. Skybakmoen, and T. Grande, Spent Si 3 N 4 bonded SiC sidelining materials in aluminium electrolysis cells. Light Metals (TMS), 2009: p. 353–358.Google Scholar
  4. 4.
    Wang, Z., E. Skybakmoen, and T. Grande, Chemical degradation of Si3N4 bonded SiC sidelining materials in aluminum electrolysis cells. J. Am. Ceram. Soc., 2009. 92(6): p. 1296–1302.CrossRefGoogle Scholar
  5. 5.
    Sørlie, M. and H.A. Øye, Cathodes in Aluminium Electrolysis. 3rd. ed. 2010, Germany: Aluminium-Verlag Marketing & Kommunikation GmbH.Google Scholar
  6. 6.
    Solheim, A. and C. Schøning, Deterioration of the bottom lining in aluminium reduction cells — Part I: Chemical equilibria at 1100 K, in Aluminium of Siberia. 2008: Knrasnoyarsk, Russia. p. 69–75.Google Scholar
  7. 7.
    Hop, J.G., Sodium expansion and creep of cathode carbon, in Department of Material Science and Engineering. 2003, Norwegian University of Science and Technology. p. 176.Google Scholar
  8. 8.
    Ratvik, A.P., et al., The effect of current density on cathode expansion during start-up. Light Metals (TMS), 2008: p. 973–978.Google Scholar
  9. 9.
    Mikhalev, Y. and H.A. Øye, Absorption of metallic sodium in carbon cathode materials. Carbon, 1996. 34(1): p. 37–41.CrossRefGoogle Scholar
  10. 10.
    Brisson, P.Y., et al., The effect of sodium on the carbon lining of the aluminum electrolysis cell — a review. Canadian Metallurgical Quarterly, 2005. 44(2): p. 265–280.CrossRefGoogle Scholar
  11. 11.
    Sangster, J., C-Na (carbon — sodium) system. Journal of Phase Equilibria and Diffusion, 2007. 28(6): p. 571–579.CrossRefGoogle Scholar
  12. 12.
    Rapoport, M.B. and V.N. Samoilenko, Deformation of cathode blocks in aluminium baths during process of electrolysis. Tsvetnye Metally, 1957. 30(2): p. 44–51.Google Scholar
  13. 13.
    Kozlov, F.A., et al., Study of the behavior of the graphitesodium system for the central rotating column in a BN-600 reactor. Atomic Energy, 2006. 101(6): p. 887–893.CrossRefGoogle Scholar
  14. 14.
    Zolochevsky, A., et al., Rapoport—Samoilenko test for cathode carbon materials: I. Experimental results and constitutive modelling. Carbon, 2003. 41(3): p. 497–505.CrossRefGoogle Scholar
  15. 15.
    Naas, T., Interactions of alkali metals and electrolyte with cathode carbons, in Institutt for uorganisk kjemi. 1997, Norwegion University of Science and Technology.Google Scholar
  16. 16.
    Houston, G.J., B.J. Welch, and D.J. Young, Uptake of electrochemically generated forms of sodium by various carbons. Light Metals (TMS), 1981: p. 529–540.Google Scholar
  17. 17.
    Wang, Z., S.M. Selbach, and T. Grande, Van der Waals density functional studay of the energetics of alkali metal intercalation in graphite. PCCP, to be submitted, 2013.Google Scholar
  18. 18.
    Browning, P. and P.E. Potter, An assessment of the experimentally determined vapour pressures of the liquid alkali metals, chapter 6.2 in Handbook of Thermodynamic and Transport Properties of Alkali Metals. 1985.Google Scholar
  19. 19.
    Brunauer, S., P.H. Emmett, and E. Teller, Adsorption of gases in multimolecular layers. J. Am. Ceram. Soc., 1938. 60(2): p. 309–319.Google Scholar
  20. 20.
    Asher, R.C., A lamellar compound of sodium and graphite. Journal of Inorganic and Nuclear Chemistry, 1959. 10(3–4): p. 238–249.CrossRefGoogle Scholar
  21. 21.
    Wang, Z., J. Rutlin, and T. Grande, Sodium diffusion in cathode lining in aluminium electrolysis cells. Light Metals (TMS), 2010: p. 841–847.Google Scholar

Copyright information

© TMS (The Minerals, Metals & Materials Society) 2014

Authors and Affiliations

  • Z. Wang
    • 1
  • A. P. Ratvik
    • 2
  • E. Skybakmoen
    • 2
  • T. Grande
    • 1
  1. 1.Department of Materials Science and EngineeringNorwegian University of Science and TechnologyTrondheimNorway
  2. 2.SINTEF Materials and ChemistryTrondheimNorway

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