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Abstract:

We present molecular dynamics simulation results pertaining to the solvation of Li+ in dimethyl sulfoxide-acetonitrile binary mixtures. The results are potentially relevant in the design of Li-air batteries that rely on aprotic mixtures as solvent media. To analyze effects derived from differences in ionic size and charge sign, the solvation of Li+ is compared to the ones observed for infinitely diluted K+ and Cl- species, in similar solutions. At all compositions, the cations are preferentially solvated by dimethyl sulfoxide. Contrasting, the first solvation shell of Cl- shows a gradual modification in its composition, which varies linearly with the global concentrations of the two solvents in the mixtures. Moreover, the energetics of the solvation, described in terms of the corresponding solute-solvent coupling, presents a clear non-ideal concentration dependence. Similar nonlinear trends were found for the stabilization of different ionic species in solution, compared to the ones exhibited by their electrically neutral counterparts. These tendencies account for the characteristics of the free energy associated to the stabilization of Li+Cl-, contact-ion-pairs in these solutions. Ionic transport is also analyzed. Dynamical results show concentration trends similar to those recently obtained from direct experimental measurements. © 2014 AIP Publishing LLC.

Registro:

Documento: Artículo
Título:Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures
Autor:Semino, R.; Zaldívar, G.; Calvo, E.J.; Laria, D.
Filiación:Departamento de Quimica Inorganica Analitica y Quimica-Fisica e INQUIMAe, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Pabellón II, Buenos Aires, 1428, Argentina
Departamento de Física de la Materia Condensada, Comisión Nacional de Energía Atómica, Avenida Libertador 8250, Buenos Aires, 1429, Argentina
Palabras clave:Acetonitrile; Dimethyl sulfoxide; Free energy; Lithium; Molecular dynamics; Solvation; Solvents; Stabilization; Acetonitrile binary mixtures; Concentration dependence; Concentration trends; Gradual modifications; Ionic transports; Li-air batteries; Molecular dynamics simulations; Non-linear trends; Binary mixtures
Año:2014
Volumen:141
Número:21
DOI: http://dx.doi.org/10.1063/1.4902837
Título revista:Journal of Chemical Physics
Título revista abreviado:J Chem Phys
ISSN:00219606
CODEN:JCPSA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n21_p_Semino

Referencias:

  • Scrosati, B., Garche, J., (2010) J. Power Sources, 195, p. 2419
  • Kraytsberg, A., Ein-Eli, Y., (2011) J. Power Sources, 196, p. 886
  • Girishkumar, G., McCloskey, B., Luntz, A.C., Swanson, S., Wilcke, W., (2010) J. Phys. Chem. Lett., 1, p. 2193
  • Abraham, K.M., Jiang, Z.A., (1996) J. Electrochem. Soc., 143, p. 1
  • Xu, K., (2004) Chem. Rev., 104, p. 4303
  • Kwabi, D.G., Ortiz-Vitoriano, N., Freunberger, S.A., Chen, Y., Imanishi, N., Bruce, P.G., Shao-Horn, Y., (2014) MRS Bull., 39, p. 443
  • Garcia-Araez, N., Novák, P., (2013) J. Solid State Electrochem., 17, p. 1793
  • Bhatt, M.D., Geaney, H., Nolan, M., O'Dwyer, C., (2014) Phys. Chem. Chem. Phys., 16, p. 12093
  • Khetan, A., Pitsch, H., Viswanathan, V., (2014) J. Phys. Chem. Lett., 5, p. 1318
  • Khetan, A., Pitsch, H., Viswanathan, V., (2014) J. Phys. Chem. Lett., 5, p. 2419
  • Bryantsev, V.S., Uddin, J., Giordani, V., Walker, W., Addison, D., Chase, G.V., (2013) J. Electrochem. Soc., 160, p. A160
  • Bryantsev, V.S., Giordani, V., Walker, W., Blanco, M., Zecevic, S., Sasaki, K., Uddin, J., Chase, G.V., (2011) J. Phys. Chem. A, 115, p. 12399
  • Lu, J., Li, L., Park, J.-B., Sun, Y.-K., Wu, F., Amine, K., (2014) Chem. Rev., 114, p. 5611
  • Imanishi, N., Yamamoto, O., (2014) Mater. Today, 17, p. 24
  • Xu, D., Wang, Z., Xu, J., Zhang, L., Zhang, X., (2012) Chem. Commun., 48, p. 6948
  • Peng, Z., Freunberger, S.A., Chen, Y., Bruce, P.G., (2012) Science, 337, p. 563
  • Sharon, D., Afri, M., Noked, M., Garsuch, A., Frimer, A.A., Aurbach, D., (2013) J. Phys. Chem. Lett., 4, p. 3115
  • McCloskey, B.D., Valery, A., Luntz, A.C., Gowda, S.R., Wallraff, G.M., Garcia, J.M., Mori, T., Krupp, L.E., (2011) J. Phys. Chem. Lett., 2, p. 1161
  • Calvo, E.J., Mozhzhukhina, N., (2013) Electrochem. Commun., 31, p. 56
  • Pasgreta, E., Puchta, R., Galle, M., Van Eikema Hommes, N., Zahl, A., Van Eldik, R., (2007) ChemPhysChem., 8, p. 1315
  • Pasgreta, E., Puchta, R., Zahl, A., Van Eldik, R., (2007) Eur. J. Inorg. Chem., 2007, p. 1815
  • Megyes, T., Bakó, I., Radnai, T., Gróz, T., Kosztolányi, T., Mroz, B., Probst, M., (2006) Chem. Phys., 321, p. 100
  • Seo, D.M., Boyle, P.D., Borodin, O., Henderson, W.A., (2012) RSC Adv., 2, p. 8014
  • Barthel, J., Deser, R., (1994) J. Sol. Chem., 23, p. 1133
  • Kalugin, O.N., Adya, A.K., Volobuev, M.N., Kolesnik, Y.V., (2003) Phys. Chem. Chem. Phys., 5, p. 1536
  • Onthong, U., Megyes, T., Bakó, I., Radnai, T., Hermansson, K., Probst, M., (2005) Chem. Phys. Lett., 401, p. 217
  • Kunz, W., Barthel, J., Klein, L., Cartailler, T., Turq, P., Reindl, B., (1991) J. Sol. Chem., 20, p. 875
  • Spångbeg, D., Hermansson, K., (2004) Chem. Phys., 300, p. 165
  • Seo, D.M., Borodin, O., Han, S.-D., Boyle, P.D., Henderson, W.A., (2012) J. Electrochem. Soc., 159, p. A1489
  • Mozhzhukhina, N., Longinotti, M.P., Corti, H.R., Calvo, E.J., A conductivity study of preferential solvation of lithium ion in acetonitrile-dimethyl sulfoxide mixtures Electrochim. Acta, , (in press)
  • Fort, R.J., Moore, W.R., (1965) Trans. Faraday Soc., 61, p. 2102
  • Martínez, L., Andrade, R., Birgin, E.G., Martínez, J.M., (2009) J. Comput. Chem., 30, p. 2157
  • Darden, T.A., York, D.M., Pedersen, L.G., (1993) J. Chem. Phys., 98, p. 10089
  • Essmann, U., Perera, L., Berkowitz, M.L., Darden, T.A., Lee, H., Pedersen, L.G., (1995) J. Chem. Phys., 103, p. 8577
  • Phillips, J.C., Braun, R., Wang, W., Gumbart, J., Tajkhorshid, E., Villa, E., Chipot, C., Schulten, K., (2005) J. Comput. Chem., 26, p. 1781
  • Luzar, A., Chandler, D., (1993) J. Chem. Phys., 98, p. 8160
  • Liu, H., Müller-Plathe, F., Van Gunsteren, W.F., (1995) J. Am. Chem. Soc., 117, p. 4363
  • Skaf, M., (1997) J. Chem. Phys., 107, p. 7996
  • Benjamin, I., (1999) J. Chem. Phys., 110, p. 8070
  • Strader, M., Feller, S.E., (2002) J. Phys. Chem. A, 106, p. 1074
  • Grabuleda, X., Jaime, C., Kollman, P.A., (2000) J. Comput. Chem., 21, p. 901
  • Guàrdia, E., Pinzón, R., Casulleras, J., Orozco, M., Luque, F.J., (2001) Mol. Simul., 26, p. 287
  • Nikitin, A.M., Lyubartsev, A.P., (2007) J. Comput. Chem., 28, p. 2020
  • Bernardi, E., Stassen, H., (2004) J. Chem. Phys., 120, p. 4860
  • Dang, L.X., (1992) J. Chem. Phys., 96, p. 6970
  • Allen, M.P., Tildesley, D.J., (1987) Computer Simulation of Liquids, , (Clarendon, Oxford)
  • Guàrdia, E., Laria, D., Martí, J., (2006) J. Phys. Chem. B, 110, p. 6332
  • Richardi, J., Fries, P.H., Krienke, H., (1998) J. Chem. Phys., 108, p. 4079
  • Guàrdia, E., Pinzón, R., (2000) J. Mol. Liq., 85, p. 33
  • Fischer, R., Richardi, J., Fries, P.H., Krienke, H., (2002) J. Chem. Phys., 117, p. 8467
  • Chandler, D., (1987) Introduction to Modern Statistical Mechanics, , (Oxford University Press, Oxford), Cha 7
  • Dixit, S.B., Chipot, C., (2001) J. Phys. Chem. A, 105, p. 9795
  • Chipot, C., Pearlman, D.A., (2002) Mol. Simul., 28, p. 1
  • Chipot, C., Pohorille, A., (2007) Free Energy Calculations: Theory and Applications in Chemistry and Biology, , (Springer Verlag, Berlin)
  • Darve, E., Pohorille, A., (2001) J. Chem. Phys., 115, p. 9169
  • Rodriguez-Gomez, D., Darve, E., Pohorille, A., (2004) J. Chem. Phys., 120, p. 3563
  • Hénin, J., Chipot, C., (2004) J. Chem. Phys., 121, p. 2904
  • Kolthodd, I.M., Bruchenstein, S., Chantooni, M.K., Jr., (1961) J. Am. Chem. Soc., 83, p. 3927
  • Cooke, C., McCallum, C., Pethybridge, A.D., Prue, J.E., (1975) Electrochim. Acta, 20, p. 591
  • Laria, D., Kapral, R., Estrin, D., Ciccotti, G., (1996) J. Chem. Phys., 104, p. 6560
  • Goldfarb, D.L., Longinotti, M.P., Corti, H.R., (2001) J. Sol. Chem., 30, p. 307
  • Tsierkezos, N.G., Philippopoulos, A.I., (2009) Fluid Phase Equilib., 277, p. 20

Citas:

---------- APA ----------
Semino, R., Zaldívar, G., Calvo, E.J. & Laria, D. (2014) . Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures. Journal of Chemical Physics, 141(21).
http://dx.doi.org/10.1063/1.4902837
---------- CHICAGO ----------
Semino, R., Zaldívar, G., Calvo, E.J., Laria, D. "Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures" . Journal of Chemical Physics 141, no. 21 (2014).
http://dx.doi.org/10.1063/1.4902837
---------- MLA ----------
Semino, R., Zaldívar, G., Calvo, E.J., Laria, D. "Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures" . Journal of Chemical Physics, vol. 141, no. 21, 2014.
http://dx.doi.org/10.1063/1.4902837
---------- VANCOUVER ----------
Semino, R., Zaldívar, G., Calvo, E.J., Laria, D. Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures. J Chem Phys. 2014;141(21).
http://dx.doi.org/10.1063/1.4902837