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 CalculationPreview
Unable to display preview. Download preview PDF.
References
- 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.Schøning, C. and T. Grande, The stability of refractory oxides in sodium-rich environments. JOM, 2006. 58(2): p. 58–61.CrossRefGoogle Scholar
- 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.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.Sørlie, M. and H.A. Øye, Cathodes in Aluminium Electrolysis. 3rd. ed. 2010, Germany: Aluminium-Verlag Marketing & Kommunikation GmbH.Google Scholar
- 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.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.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.Mikhalev, Y. and H.A. Øye, Absorption of metallic sodium in carbon cathode materials. Carbon, 1996. 34(1): p. 37–41.CrossRefGoogle Scholar
- 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.Sangster, J., C-Na (carbon — sodium) system. Journal of Phase Equilibria and Diffusion, 2007. 28(6): p. 571–579.CrossRefGoogle Scholar
- 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.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.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.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.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.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.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.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.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.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