Highest Ionic Conductivity of BIMEVOX (ME = 10% Cu, 10% Ga, 20% Ta): Computational Modeling and Simulation


Akram La Kilo(1*), Alberto Costanzo(2), Daniele Mazza(3), Muhamad Abdulkadir Martoprawiro(4), Bambang Prijamboedi(5), Ismunandar Ismunandar(6)

(1) Department of Chemistry, Universitas Negeri Gorontalo, Jl. Jenderal Soedirman No. 6 Gorontalo 96126, Indonesia
(2) Dipartimento di Scienza dei Materiali e’ Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
(3) Dipartimento di Scienza dei Materiali e’ Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
(4) Inorganic and Physical Chemistry Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia
(5) Inorganic and Physical Chemistry Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia
(6) Inorganic and Physical Chemistry Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung 40132, Indonesia
(*) Corresponding Author


BIMEVOX had the potential to play an important role in solid oxide fuel cell, especially as the electrolyte due to their high ionic conductivity. In this work, oxide ion migrations of γ-Bi2VO5.5 and BIMEVOX were simulated using density function theory (DFT), Mott-Littleton method, and molecular dynamic simulation. In γ-Bi2VO5.5, there were oxygen vacancies at the equatorial position in the vanadate layers. These vacancies could facilitate oxide ions migration. The Enthalpy of the oxide migration for γ-Bi2VO5.5 based on DFT calculation was 0.38 eV, which was in a good agreement with experimental results. The γ-Bi2VO5.5 can be stabilized by partial substitution of V5+ with Cu2+, Ga3+, and Ta5+. Defect simulation results using the Mott-Littleton method showed that the total maximum energies of region II were achieved at concentrations of 10, 10, and 20%, respectively for Cu2+, Ga3+, and Ta5+. The calculated concentration of Cu2+, Ga3+, and Ta5+ were in a good agreement with those of experiment results, where the highest ionic conductivity obtained. The results of the molecular dynamics simulation showed that the activation energies of oxide ion migration in γ-Bi2VO5.5 and BIMEVOX (ME = Cu and Ta) respectively were 0.19, 0.21, and 0.10 eV, close to experimental values.


simulation; vacancy defect; γ-Bi2VO5.5 and BIMEVOX; ionic migration

Full Text:

Full Text PDF


[1] Cho, H.S., Sakai, G., Shimanoe, K., and Yamazoe, N., 2005, Preparation of BiMeVOx (Me= Cu, Ti, Zr, Nb, Ta) compounds as solid electrolyte and behavior of their oxygen concentration cells, Sens. Actuators, B, 109 (2), 307–314.

[2] Chmielowiec, J., Paściak, G., and Bujło, P., 2008, Ionic conductivity and thermodynamic stability of La-doped BIMEVOX, J. Alloys Compd., 451 (1-2), 676–678.

[3] Khaerudini, D.S., Guan, G., Zhang, P., Hao, X., and Abudula, A., 2014, Prospects of oxide ionic conductivity bismuth vanadate-based solid electrolytes, Rev. Chem. Eng., 30 (6), 539–551.

[4] Tripathy, D., Saikia, A., and Pandey, A.C., 2019, Effect of simultaneous Ti and Nb doping on structure and ionic conductivity of Bi2V1xTix/2Nbx/2O5.5−δ (0.1≤ x≤ 0.25) ceramics, Ionics, 25 (5), 2221–2230.

[5] Tripathy, D., and Pandey, A., 2018, Structural and impedance studies of TiIV and NbV co-doped bismuth vanadate system, J. Alloys Compd., 737, 136–143.

[6] Pernot, E., Anne, M., Bacmann, M., Strobel, P., Fouletier, J., Vannier, R.N., Mairesse, V.G., Abraham, F., and Nowogrocki, G., 1994, Structure and conductivity of Cu and Ni-substituted Bi4V2O11 compounds, Solid State Ionics, 70-71, 259–263.

[7] Abrahams, I., Krok, F., Malys, M., and Bush, A.J., 2001, Defect structure and ionic conductivity as a function of thermal history in BIMGVOX solid electrolytes, J. Mater. Sci., 36 (5), 1099–1104.

[8] Rusli, R., Abrahams, I., Patah, A., Prijamboedi, B., and Ismunandar, 2014, Ionic conductivity of Bi2NixV1−xO5.5−3x/2 (0.1 ≤ x ≤ 0.2) oxides prepared by a low temperature sol-gel route, AIP Conf. Proc., 1589 (1), 178.

[9] Abraham, F., Boivin, J.C., Mairesse, G., and Nowogrocki, G., 1990, The BIMEVOX series: A new family of high performances oxide ion conductors, Solid State Ionics, 40-41, 934–937.

[10] Abrahams, I., and Krok, F., 2002, Defect chemistry of the BIMEVOXes, J. Mater. Chem., 12 (12), 3351–3362.

[11] Khaerudini, D.S., Guan, G., Zhang, P., Hao, X., Kasai, Y., Kusakabe, K., and Abudula, A., 2014, Structural and conductivity characteristics of Bi4MgxV2−xO11−δ (0⩽ x ⩽ 0.3) as solid electrolyte for intermediate temperature SOFC application, J. Alloys Compd., 589, 29–36.

[12] Kant, R., Singh, K., and Pandey, O.P., 2010, Structural, thermal and transport properties of Bi4V2_xGaxO11_δ (0 ≤ x ≤ 0.4), Ionics, 16 (3), 277–282.

[13] Dereeper, E., Briois, P., and Billard, A., 2017, BITAVOX coatings obtained by reactive magnetron sputtering: Influence of thickness and composition, Solid State Ionics, 304, 7–12.

[14] Kant, R., Singh, K., and Pandey, O.P., 2008, Synthesis and characterization of bismuth vanadate electrolyte material with aluminium doping for SOFC application, Int. J. Hydrogen Energy, 33 (1), 455–462.

[15] Krok, F., Abrahams, I., Zadrożna, A., Małys, M., Bogusz, W., Nelstrop, J.A.G., and Bush, A.J., 1999, Electrical conductivity and structure correlation in BIZNVOX, Solid State Ionics, 119 (1-4), 139–144.

[16] Mairesse, G., 1999, Advances in oxygen pumping concept with BIMEVOX, C. R. Acad. Sci. IIC: Chim., 2 (11-13), 651–660.

[17] Mairesse, G., Roussel, P., Vannier, R.N., Anne, M., Pirovano, C., and Nowogrocki, G.L., 2003, Crystal structure determination of α, β and γ-Bi4V2O11 polymorphs. Part I: γ and β-Bi4V2O11, Solid State Sci., 5 (6), 851–859.

[18] Payne M.C., and TCM group in Cambridge, 2005, CASTEP of Material Studio Modeling from Accerys, series number 3.2.00, with consumer is Politecnico di Torino.

[19] Gale, J.D., 1997, GULP: A computer program for the symmetry-adapted simulation of solids, J. Chem. Soc., Faraday Trans., 93 (4), 629-637.

[20] Todorov, I.T., Smith, W., Trachenko, K., and Dove, M.T., 2006, DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism, J. Mater. Chem., 16 (20), 1911–1918.

[21] Voronkova, V.I., Yanovskii, V.K., Kharitonova, E.P., and Rudnitskaya, O.G., 2005, Superionic conductors in the Bi2WO6-Bi2VO5.5 system, Inorg. Mater., 41 (7), 760–765.

[22] Kant, R., Singh, K., and Pandey, O.P., 2009, Microstructural and electrical behavior of Bi4V2-xCuxO11-δ (0 ≤ x ≤ 0.4), Ceram. Int., 35 (1), 221–227.

[23] Lazure, S., Vernochet, C., Vannier, R.N., Nowogrocki, G., and Mairesse, G., 1996, Composition dependence of oxide anion conduction in the BIMEVOX family, Solid State Ionics, 90 (1-4), 117–123.

[24] Murasheva, V.V., Fortalnova, E.A., Politova, E.A., Politova, E.D., Safronenko, M.G., Stefanovich, S.Y., and Venskovskii, N.U., 2008, Phase transitions in the BIMEVOX solid solutions with Me = Ga, Zr, Mater. Sci. Forum, 587-588, 114–117.

[25] Joubert, O., Jouanneaux, A., Ganne, M., Vannier, R.N., and Mairesse, G., 1994, Solid phase synthesis and characterization of new BIMEVOX series: Bi4V2−xMxO11 (M = Sbv, Nbv), Solid State Ionics, 73 (3-4), 309–318.

[26] Ramsahye, N.A., and Bell, R.G., 2005, Cation mobility and the sorption of chloroform in zeolite NaY: Molecular dynamics study, J. Phys. Chem. B, 109 (10), 4738–4747.

[27] Guillodo, M., Bassat, J.M., Fouletier, J., Dessemond, L., and Del Gallo, P., 2003, Oxygen diffusion coefficient and oxygen exchange coefficient of BIMEVOX.10 (ME = Cu, Co) ceramic membranes, Solid State Ionics, 164 (1-2), 87–96.

[28] Krok, F., Bogusz, W., Kurek, P., Wasiucionek, M., Jakubowski, W., and Dygas, J., 1993, Influence of preparation procedure on some physical properties of BICUVOX, Mater. Sci. Eng., B, 21 (1), 70–76.

[29] Simner, S.P., Suarez‐Sandoval, D., Mackenzie, J.D., and Dunn, B., 1997, Synthesis, densification, and conductivity characteristics of BICUVOX oxygen‐ion‐conducting ceramics, J. Am. Ceram. Soc., 80 (10), 2563–2568.

DOI: https://doi.org/10.22146/ijc.42635

Article Metrics

Abstract views : 3593 | views : 3784

Copyright (c) 2019 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.