Thermodynamic Database for Hydrogen Storage Materials



In order to be used for applications, the thermodynamic stability of a candidate hydrogen storage material should be suitable for hydrogen sorption at room conditions. By mixing different hydrides, it is possible to promote the hydrogenation/dehydrogenation processes. On the other hand, small changes in composition allow a tailoring of thermodynamic stability of hydrides. Knowledge of thermodynamic stability of hydrides is thus fundamental to study the hydrogenation/dehydrogenation processes and useful to rationalize synthesis reactions and to suggest possible alternative reaction routes. The purpose of this work is to develop a consistent thermodynamic database for hydrogen storage systems by the CALPHAD approach. Experimental data have been collected from the literature. When experimental measurements were scarce or completely lacking, estimations of the energy of formation of hydrides have been obtained by ab initio calculations performed with the CRYSTAL code. Several systems of interest for hydrogen storage have been investigated, including metallic hydrides (M-H) and complex hydrides. The effect on thermodynamic properties of fluorine-to-hydrogen substitution in some simple hydrides is also considered. Calculated and experimental thermodynamic properties of various hydrides have been compared and a satisfactory agreement has been achieved.







M. Baricco et al., "Thermodynamic Database for Hydrogen Storage Materials", Advances in Science and Technology, Vol. 72, pp. 213-218, 2010


October 2010


[1] A. Züttel: Naturwissenschaften Vol. 91 (2004), p.157.

[2] B. Sundman, S.G. Fries and H.L. Lukas: Computational Thermodynamics (Cambridge 2007 ).

[3] P.E.A. Turchi, I.A. Abrikosov, B. Burton, S.G. Fries, G. Grimvall, L. Kaufman, P. Korzhavyi, V.R. Manga, M. Ohno, A. Pisch, A. Scott and W. Zhang: CALPHAD Vol. 31 (2007), p.4.


[4] J. Urgnani, F.J. Torres, M. Palumbo and M. Baricco: Int. J. Hydr. Energy Vol. 33 (2008), p.3111.

[5] M. Zinkevich, N. Mattern, A. Handstein and O. Gutfleisch: J. Alloys Compd Vol. 339 (2002), p.118.

[6] A.T. Dinsdale: CALPHAD Vol. 15 (1991), p.317.

[7] M.W. Chase Jr., NIST-JANAF Thermochemical Tables, fourth ed., J. Phys. Chem. Ref. Data Monograph No. 9.

[8] R. Dovesi, V. R. Saunders, C. Roetti, R Orlando, C. M. Zicovich-Wilson, F. Pascale, B. Civalleri, K. Doll, N.M. Harrison, I.J. Bush, P. D'Arco, M. Llunell, CRYSTAL2006 User's Manual; http: /www. crystal. unito. it, University of Torino: Torino, (2006).

[9] R. Dovesi, R. Orlando, B. Civalleri, C. Roetti, V.R. Saunders and C.M. Zicovich-Wilson: Z.  Kristallogr. Vol. 220 (2005), p.571.

[10] C. Qiu, G.B. Olson, S.M. Opalka and D.L. Anton: Int. J. Mat. Res. Vol. 97 (2006), p.845.

[11] A.D. Pelton: Z. Melallkde. Vol. 84 (1993), p.767.

[12] K. Zeng, T. Klassen, W. Oelerich and R. Bormann: Int. J. Hydrogen Energy Vol. 24 (1999), p.989.

[13] C. Qiu, G.B. Olson, S.M. Opalka and D.L. Anton: J. Phase Equilib. Diff. Vol. 25 (2004), p.520.

[14] W. Huang, S.M. Opalka, D. Wang and T.B. Flanagan: CALPHAD Vol. 31 (2007), p.315.

[15] E. Konigsberger , G. Eriksson and W.A. Oates: JALCOM Vol. 299 (2000), p.148.

[16] J. -M Joubert and S. Thiébaut: Journal of Nuclear Materials Vol. 395 (2009), p.79.

[17] M. Palumbo, J. Urgnani, D. Baldissin, L. Battezzati and M. Baricco: CALPHAD Vol. 33 (2009), p.162.


[18] K. Zeng, T. Klassen, W. Oelerich and R. Bormann: JALCOM Vol. 299 (1999), p.213.

[19] B. -M. Lee, J. -W. Jang, J. -H. Shimb, Y.W. Cho and B. -J. Lee: JALCOM Vol. 424 (2006), p.370.

[20] J. -W. Jang, J. -H. Shimb, Y. W. Cho and B. -J. Lee: JALCOM Vol. 420 (2006), p.286.

[21] M. Palumbo, F.J. Torres, J.R. Ares, C. Pisani, J.F. Fernandez and M. Baricco, CALPHAD Vol. 31 (2007), p.457.

[22] J. Vajo, S.L. Skeith and F. Mertens: J Phys. Chem. B Lett. Vol. 109 (2005), p.3719.

[23] D. Pottmaier, E. Groppo, S. Bordiga, G. Spoto and M. Baricco: Proc. HYSYDAYS 2009, Turin, Italy, Oct. (2009).

[24] K. Ikeda, S. Kato, Y. Shinzato, N. Okuda, Y. Nakamori, A. Kitano, H. Yukawa, M. Morinaga and S. Orimo: Journal of Alloys and Compounds Vol. 446–447 (2007), p.162.


[25] P. Wang, X.D. Kang and H.M. Cheng: ChemPhysChem Vol. 6 (2005), p.2488.

[26] L. Yin, P. Wang, X. Kang, C. Sun and H. Cheng: Phys. Chem. Chem. Phys. Vol. 9 (2007), p.1499.

[27] J.J. Vajo and G.L. Olson : Scripta Mat. Vol. 56 (2007), p.829.

[28] J.J. Vajo, T.T. Salguero, A.F. Gross, S.L. Skeith and G.L. Olson, J. All. Comp. Vol. 446–447 (2007) p.409.

[29] A. Meyer, P. D'Arco, R. Orlando and R. Dovesi: J. Phys. Chem. C Vol. 113(2009), p.14507.