Skip to main content
SpringerLink
Log in

Mechanochemical synthesis and electrical properties of Gd2Hf2−xZrxO7 solid electrolytes for their use in SOFC’s

  • Research Article
  • Published:
Journal of Applied Electrochemistry Aims and scope Submit manuscript

Abstract

Lanthanides hafnates Ln2Hf2O7 (Ln = lanthanides) are known by their interesting electrical properties; many of them are good oxygen ion conductors at high temperatures and can be used as solid electrolytes in solid oxide fuel cells. Properties of these materials are significantly affected by the presence of defects such as vacancies and structural disorder which can be generated by single or multiple chemical substitutions or even by processing. This work analyzes the effect of Hf substitution by Zr on the electrical properties of gadolinium hafnate, starting by the synthesis of solid solutions with general formula Gd2Hf2−xZrxO7 (x = 0, 0.8, 1.2, 1.6 and 2) by mechanical milling, a powder processing method which allows obtaining metastable phases at room temperature. These phases include a large number of structural defects, which will have an interesting effect on their properties. Results show that all proposed compositions with a disordered fluorite-type arrangement can be obtained after a mechanical milling process of 30 h, by using a planetary ball mill and Yttria Stabilized Zirconia vials and balls. Post-milling thermal treatments at 1500 °C facilitates the evolution to ordered pyrochlore structures for all analyzed compositions. Their electrical properties, analyzed by impedance spectroscopy, reveal that activation energy for ionic migration increases as Zr content increases and dc conductivity, one important property for solid electrolytes application, reaches a maximum for x = 1.6 at 750 °C. This degree of doping would represent the optimal degree of disorder in the system Gd2Hf2−xZrxO7 to obtain the higher ionic conductivity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Labrincha JA, Frade JR, Marques FM (1993) La2Zr2O7 formed at ceramic electrode/YSZ contacts. J Mater Sci 28:3809–3815

    Article  CAS  Google Scholar 

  2. Mitterdorfer A, Gauckler AJ (1997) La2Zr2O7 formation between yttria stabilized zirconia and La0.85Sr0.15MnO3 at 1773 K. J Solid State Chem Inorg Mater 453:425–430

    Google Scholar 

  3. Yokokawa H, Sakai N, Kawada T, Dokiya M (1991) Thermodynamic analysis of reaction profiles between LaMO3 (M = Ni, Co, Mn) and ZrO2. J Electrochem Soc 138:2719–2727

    Article  CAS  Google Scholar 

  4. Takeda Y, Sakaki Y, Tu HY, Phillipps MB, Imanishi N, Yamamoto O (2000) Perovskite oxides for the cathode in solid oxide fuel cells. Electrochemistry 68:764–770

    CAS  Google Scholar 

  5. Díaz-Guillén JA, Fuentes AF, Díaz-Guillén MR, Almanza JM, Santamaría J, León C (2009) The effect of homovalent A-site substitutions on the ionic conductivity of pyrochlore-type Gd2Zr2O7. J Power Sources 186:349–352

    Article  Google Scholar 

  6. Shlyakhtina AV, Shcherbakova LG (2011) Polymorphism and high-temperature conductivity of Ln2M2O7 (Ln = Sm–Lu; M = Ti, Zr, Hf) pyrochlores. Solid State Ionics 192:200–204

    Article  CAS  Google Scholar 

  7. Shlyakhtina AV, Belov DA, Stefanovich YS, Kolbanev IV, Karyagina OK, Egorov AV, Savilov SV, Shcherbakova LG (2011) d-Phase-to-defect fluorite (order–disorder) transition in the R2O3–MO2 (R = Sc, Tm, Lu; M = Zr, Hf) systems. Mater Res Bull 46:512–517

    Article  CAS  Google Scholar 

  8. Subramanian MA, Aravamudan G, Subba Rao GV (1985) Oxide pyrochlore, a review. Prog Solid State Chem 15:55–143

    Article  Google Scholar 

  9. Mandal BP, Garg N, Sharma SM, Tyagi AK (2006) Preparation, XRD and raman spectroscopic studies on new compounds RE2Hf2O7 (RE = Dy, Ho, Er, Tm, Lu, Y): pyrochlores or defect-fluorite. J Solid State Chem 179:1990–1994

    Article  CAS  Google Scholar 

  10. Liu ZG, Ouyang JH, Zhou Y, Xia XL (2010) Coprecipitation synthesis and sintering property of (YbxSm1−x)2Zr2O7 ceramic powders. Adv Appl Ceram 109:12–17

    Article  CAS  Google Scholar 

  11. Kumara BV, Velchuria R, Prasadb G, Sreedharc B, Ravikumard K, Vithala M (2010) Preparation, characterization, photoactivity and XPS studies of Ln2ZrTiO7 (Ln = Sm and Nd). Ceram Int 36(4):1347–1355

    Article  Google Scholar 

  12. Díaz-Guillén JA, Díaz-Guillén MR, Almanza JM, Fuentes AF, Santamaría J, León C (2007) Effect of La substitution for Gd in the ionic conductivity and oxygen dynamics of fluorite-type Gd2Zr2O7. J Phys Condens Matter 19:356212

    Google Scholar 

  13. Moreno KJ, Mendoza G, Fuentes AF, García-Barriocanal J, León C, Santamaría J (2005) Cooperative oxygen dynamics in fuel cell materials Gd2Ti2−yZryO7. Phys Rev B 71:132301

    Article  Google Scholar 

  14. Fuentes AF, Takacs L (2013) Preparation of multicomponent oxides by mechanochemical methods. J Mater Sci 48(2):598–611

    Article  CAS  Google Scholar 

  15. Van Dijk MP, Burggraaf AJ, Cormack AN, Catlow CR (1985) Defect structures and migration mechanisms in oxide pyrochlores. Solid State Ionics 17:159–167

    Article  Google Scholar 

  16. Moon PK, Tuller HL (1989) Fast ion conduction in the Gd2(ZrxTi1−x)2O7 pyrochlore system. Mater Res Soc Symp  Proc 135:149–155

    Article  CAS  Google Scholar 

  17. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A A32:751–767

    Article  CAS  Google Scholar 

  18. Jonscher AK (1983) Dielectric relaxation in solids. Chelsea Dielectric, London

    Google Scholar 

Download references

Acknowledgments

This work has been carried out with the financial support of TECNOLÓGICO NACIONAL DE MEXICO and CONSEJO NACIONAL DE CIENCIA Y TECNOLOGÍA (Grants CB-2011-01-166995 and CB-2013-01-221701).

Author information

Authors and Affiliations

  1. Cinvestav Unidad Saltillo, Apartado Postal 663, 25000, Saltillo, Coahuila, Mexico

    N. M. Cepeda-Sánchez, A. F. Fuentes & F. A. López-Cota

  2. División de Estudios de Posgrado e Investigación, Instituto Tecnológico de Saltillo, 25280, Saltillo, Coahuila, Mexico

    F. A. López-Cota, M. Rodríguez-Reyes & J. A. Díaz-Guillén

Authors
  1. N. M. Cepeda-Sánchez
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. F. Fuentes
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F. A. López-Cota
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Rodríguez-Reyes
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. J. A. Díaz-Guillén
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to J. A. Díaz-Guillén.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cepeda-Sánchez, N.M., Fuentes, A.F., López-Cota, F.A. et al. Mechanochemical synthesis and electrical properties of Gd2Hf2−xZrxO7 solid electrolytes for their use in SOFC’s. J Appl Electrochem 45, 1231–1237 (2015). https://doi.org/10.1007/s10800-015-0828-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10800-015-0828-x

Keywords

Search

Navigation