Skip to main content

Structural, morphological, and electrical properties of doped ceria as a solid electrolyte for intermediate-temperature solid oxide fuel cells

Journal of Materials Science volume 50, pages 3781–3794 (2015)Cite this article

Abstract

The solid solutions of CeO2 with one or more rare-earth oxides among Yb2O3, Sm2O3, and Gd2O3 are synthesized by either modified glycine nitrate procedure (MGNP) or self-propagating reaction at room temperature (SPRT). The overall mole fraction of rare-earth oxide dopants was x = 0.2. The characterization was committed by XRPD, TEM, BET, and Raman Spectroscopy methods. According to XRPD and Raman spectroscopy, the obtained products presented the single-phase solid solutions with basic fluorite-type CeO2 structure, regardless on the number and the concentration of dopants. Both XRPD and TEM analysis evidenced the nanometer particle dimensions. The defect model was applied to calculate lattice parameters of single-, co-, and multi-doped solids. The sintering of the sample nanopowders was performed at 1550 °C, in air atmosphere. The sintered samples were characterized by XRPD, SEM, and complex impedance methods. The sintering did not affect the concentration ratios of the constituents. The highest conductivity at 700 °C amounting to 2.14 × 10−2 and 1.92 × 10−2 Ω−1 cm−1 was measured for the sample Ce0.8Sm0.08Gd0.12O2−δ, synthesized by SPRT and MGNP methods, respectively. The corresponding activation energies of conductivity, measured in the temperature range 500–700 °C, amounted to 0.24 and 0.23 eV.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

References

  1. Alves HJ, Junior CB, Niklevicz RR, Frigo EP, Frigo MS, Coimbra-Araújo CH (2013) Overview of hydrogen production technologies from biogas and the applications in fuel cells. Int J Hydrog Energy 38:5215–5225

    Article  Google Scholar 

  2. Galvagno A, Chiodo V, Urbani F, Freni F (2013) Biogas as hydrogen source for fuel cell applications. Int J Hydrog Energy 38:3913–3920

    Article  Google Scholar 

  3. Liu J, Zhang S, Wang W, Gao J, Liu W, Chen C (2012) Partial oxidation of methane in a Zr0.84Y0.16O1.92eLa0.8Sr0.2Cr0.5Fe0.5O3-δ hollow fiber membrane reactor targeting solid oxide fuel cell applications. J Power Sour 217:287–290

  4. Takagi Y, Kerman K, Ko C, Ramanathan S (2011) Operational characteristics of thin film solid oxide fuel cells with ruthenium anode in natural gas. J Power Sour 243:1–9

  5. Hertz JL, Tuller HL (2004) Electrochemical characterization of thin films for a micro-solid oxide fuel cell. J Electroceram 13:663–668

    Article  Google Scholar 

  6. Hütter AB, Hertz JL, Tuller HL (2008) Fabrication and electrochemical characterization of planar Pt-CGO microstructures. Acta Mater 56:177–187

    Article  Google Scholar 

  7. Litzelman SJ, Hertz JL, Jung W, Tuller HL (2008) Opportunities and challenges in materials development for thin film solid oxide fuel cells. Fuel Cells 08:294–302

    Article  Google Scholar 

  8. Dudek M (2012) Ceramic electrolytes in the CeO2–Gd2O3–SrO system-preparation, properties and application for solid oxide fuel cells. Int J Electrochem Sci 7:2874–2889

    Google Scholar 

  9. Zahir MH, Suzuki T, Funahashi Y, Yamaguchi T, Fujishiro Y, Awano M (2009) Wet atomisation of Gd-doped CeO2 electrolyte slurries for intermediate temperatures’ microtubular SOFC applications. Fuel Cells 9:164–169

    Article  Google Scholar 

  10. Pikalova EYu, Murashkina AA, Maragou VI, Demin AK, Strekalovsky VN, Tsiakaras PE (2011) CeO2 based materials doped with lanthanides for applications in intermediate temperature electrochemical devices. Int J Hydrog Energy 36:6175–6183

    Article  Google Scholar 

  11. Stojmenović M, Bošković S, Žunić M, Varela JA, Prekajski M, Matović B, Mentus S (2014) Electrical properties of multidoped ceria. Ceram Int 40:9285–9292

    Article  Google Scholar 

  12. Tsunekawa S, Fukuda T, Kasuya A (2000) X-ray photoelectron spectroscopy of monodisperse CeO2−x nanoparticles. Surf Sci Lett 457:437–440

    Article  Google Scholar 

  13. Steele BCH (2000) Appraisal of Ce1-yGdyO2-y/2 electrolytes for IT-SOFC operation at 500 & #xB0;C. Solid State Ion 129:95–110

    Article  Google Scholar 

  14. Inaba H, Tagawa H (1996) Ceria-based solid electrolytes. Solid State Ion 83:1–16

    Article  Google Scholar 

  15. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 32:751–767

    Article  Google Scholar 

  16. Liu W, Li B, Liu H, Pan W (2011) Electrical conductivity of textured Sm3+ and Nd3+ Co-doped CeO2 thin-film electrolyte. Electrochim Acta 56:3334–3337

    Article  Google Scholar 

  17. Pérez-Coll D, Núñez P, Frade JR (2011) The role of SiO2 and sintering temperature on the grain boundary properties of Ce0.8Sm0.2O2−δ. J Power Sour 196:8383–8390

    Article  Google Scholar 

  18. Siqueira Júnior JM, Brum Malta LF, Garrido FMS, Ogasawara T, Medeiros ME (2012) Raman and Rietveld structural characterization of sintered alkaline earth doped ceria. Mater Chem Phys 135:957–964

  19. Bae H, Choi J, Choi GM (2013) Electrical conductivity of Gd-doped ceria film fabricated by aerosol deposition method. Solid State Ion 236:16–21

    Article  Google Scholar 

  20. Wright J, Virkar AV (2011) Conductivity of porous Sm2O3-doped CeO2 as a function of temperature and oxygen partial pressure. J Power Sour 196:6118–6124

    Article  Google Scholar 

  21. Jiang J, Shen W, Hertz JL (2013) Structure and ionic conductivity of nanoscale gadolinia-doped ceria thin films. Solid State Ion 249–250:139–143

    Article  Google Scholar 

  22. Kosinski MR, Baker RT (2011) Preparation and property-performance relationships in samarium-doped ceria nanopowders for solid oxide fuel cell electrolytes. J Power Sour 196:2498–2512

    Article  Google Scholar 

  23. Kahlaoui M, Chefi S, Inoubli A, Madani A, Chefi C (2013) Synthesis and electrical properties of co-doping with La3+, Nd3+, Y3+, and Eu3+ citric acid-nitrate prepared samarium-doped ceria ceramics. Ceram Int 39:3873–3879

    Article  Google Scholar 

  24. Tadokoro SK, Muccillo ENS (2007) Effect of Y and Dy co-doping on electrical conductivity of ceria ceramics. J Eur Ceram Soc 27:4261–4264

    Article  Google Scholar 

  25. Ye F, Mori T, Ou DR, Takahashi M, Zou J, Drennan J (2007) Ionic conductivities and microstructures of Ytterbium-doped ceria. J Electrochem Soc 154:B180–B185

    Article  Google Scholar 

  26. Mori T, Drennan J, Wang Y, Auchterlonie G, Li JG, Yago A (2003) Influence of nano-structural feature on electrolytic properties in Y2O3 doped CeO2 system. J Sci Technol Adv Mater 4:213–220

    Article  Google Scholar 

  27. West AR (1991) Solid state chemistry and its applications. Wiley, New York, pp 36–64

    Google Scholar 

  28. Dann SE (2000) Reactions and characterization of solids. Wiley, New York, pp 141–148

    Google Scholar 

  29. Wang S, Maeda K, Awano M (2002) Direct formation of crystalline gadolinium-doped ceria powder via polymerized precursor solution. J Am Ceram Soc 85:1750–1752

    Article  Google Scholar 

  30. Bošković SB, Matović BZ, Vlajić MD, Kristić VD (2007) Modified glycine nitrate procedure (MGNP) for the synthesis of SOFC nanopowders. Ceram Int 33(1):89–93

    Article  Google Scholar 

  31. Bošković S, Đurović D, Dohčević-Mitrović Z, Popović Z, Zinkevich M, Aldinger A (2005) Self-propagating room temperature synthesis of nanopowders for solid oxide fuel cells (SOFC). J Power Sour 145:237–242

    Article  Google Scholar 

  32. Hong SJ, Virkar AV (1995) Lattice parameters and densities of rare-earth oxide doped ceria electrolytes. J Am Ceram Soc 78:433–439

    Article  Google Scholar 

  33. Moraisa EA, Scalvib LVA, Geraldoa V, Ribeiroc SJL, Santilli CV (2003) Er Rare-earth Ion Incorporation in Sol–Gel SnO2. Mater Res 6:445–449

    Article  Google Scholar 

  34. Mentus S, Jelić D, Grudić V (2007) Lanthanum nitrate decomposition by both temperature programmed heating and by citrate gel combustion. Comparative study. J Therm Anal Calorim 90:393–397

  35. Suryanarayana C, Grant Norton M (1998) X-ray diffraction: a practical approach. Springer, New York

  36. Barrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc 73:373–380

    Article  Google Scholar 

  37. Kaneko K, Ishii C, Ruike M, Kuwabara H (1992) Origin of superhigh surface area and microcrystalline graphitic structures of activated carbons. Carbon 30:1075–1088

    Article  Google Scholar 

  38. Kruk M, Jaroniec M, Gadkaree KP (1997) Nitrogen adsorption studies of novel synthetic active carbons. J Colloid Interface Sci 192:250–256

    Article  Google Scholar 

  39. Kaneko K, Ishii C, Kanoh H, Hanzawa Y, Setoyama N, Suzuki T (1998) Characterization of porous carbons with high resolution α s -analysis and low temperature magnetic susceptibility. Adv Colloid Interface Sci 76–77:295–320

    Article  Google Scholar 

  40. Stojmenović M, Bošković S, Zec S, Babić B, Matović B, Bučevac D, Dohčević-Mitrović Z, Aldinger F (2010) Characterization of nanometric multidoped ceria powders. J Alloy Compd 507:279–285

    Article  Google Scholar 

  41. Tsunekawa S, Wang J-T, Kawazoe Y (2006) J Alloy Compd 408–412:1145–1148

    Article  Google Scholar 

  42. Tsunekawa S, Ishikawa K, Li Z-Q, Kawazoe Y, Kasuya A (2000) Phys Rev Lett 85:3440–3443

    Article  Google Scholar 

  43. Zhang F, Chan S-W, Spanier JE, Apak E, Jin Q (2002) Appl Phys Lett 80:127–129

    Article  Google Scholar 

  44. Weber WH, Hass KC, Mcbride JR (1993) Phys Rev B 48:178–185

    Article  Google Scholar 

  45. Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619

    Article  Google Scholar 

  46. da Silva CA, Ribeiro NFP, Souza MMVM (2009) Effect of the fuel type on the synthesis of yttria stabilized zirconia by combustion method. Ceram Int 35:3441–3446

  47. Gregg SJ, Sing KSW (1982) Adsorption, surface area and porosity. pp 21–38, 112–132

  48. Phoka S, Laokul P, Swatsitang E, Promarack V (2009) Mater. Synthesis, structural and optical properties of CeO2 nanoparticles synthesized by a simple polyvinyl pyrrolidone (PVP) solution route. Chem Phys 115:423–428

    Google Scholar 

  49. Doroftei C, Popa PD, Iacomi F, Leontie L (2014) The influence of Zn2+ ions on the microstructure, electrical and gas sensing properties of La0.8Pb0.2FeO3 perovskite. Sens Actuators B 191:239–245

  50. Evans AG, Hsueh CH (1986) Behavior of large pores during sintering and hot isostatic pressing. J Am Ceram Soc 69:444–448

    Article  Google Scholar 

  51. Kim G, Lee N, Kim K-B, Kim B-K, Chang H, Song S-J, Park J-Y (2013) Various synthesis methods of aliovalent-doped ceria and their electrical properties for intermediate temperature solid oxide electrolytes. Int J Hydrog Energy 38:1571–1587

  52. Moure A, Moure C, Tartaj J (2011) A significant improvement of the processing and electric properties of CeO2 co-doped with Ca and Sm by mechanosynthesis. J Power Sour 196:10543–10549

    Article  Google Scholar 

  53. Prado-Gonjal J, Schmidt R, Espindola-Canuto J, Ramos-Alvarez P, Moran E (2012) Increased ionic conductivity in microwave hydrothermally synthesized rare-earth doped ceria Ce1-xRExO2-(x/2). J Power Sour 209:163–171

  54. Jaiswal N, Kumar D, Upadhyay S, Parkash O (2013) Effect of Mg and Sr co-doping on the electrical properties of ceria-based electrolyte materials for intermediate temperature solid oxide fuel cells. J Alloy Compd 577:456–462

    Article  Google Scholar 

  55. Waster R, Hagenbeck R (2000) Grain boundaries in dielectric and mixed-conducting ceramics. Acta Mater 48:797–825

    Article  Google Scholar 

  56. Chen XJ, Khor KA, Chan SH, Yu LG (2003) Preparation yttria-stabilized zirconia electrolyte by spark-plasma sintering. Mater Sci Eng A 341:43–48

    Article  Google Scholar 

  57. Stojmenović M, Bošković S, Bučevac D, Prekajski M, Babić B, Matović B, Mentus S (2013) Electrical characterization of multidoped ceria ceramics. Ceram Int 39:1249–1255

  58. Pérez-Coll D, Núñez P, Frade JR (2006) Improved conductivity of Ce1−x Sm x O2−δ ceramics with submicrometer grain sizes. J Electrochem Soc 153:A478–A483

    Article  Google Scholar 

  59. Jensen SH, Hauch A, Hendriksen PV, Mogensen M, Bonanos N, Jacobsen T (2007) A method to separate process contributions in impedance spectra by variation of test conditions. J Electrochem Soc 154:B1325–B1330

    Article  Google Scholar 

  60. Kingery WD, Bowen HK, Uhlmann DR (1975) Introduction to ceramics. Wiley, New York, pp. 61–70, 853–863

Download references

Acknowledgements

This work has been supported by the Ministry of Education and Science of Serbia (project number: III 45012, III 45014 and III 45007).

Author information

Authors and Affiliations

  1. Institute of Nuclear Sciences “Vinča”, Belgrade University of Belgrade, Mihaila Petrovića Alasa 12-14, Vinča, 11000, Serbia

    M. Stojmenović, J. Gulicovski & V. Dodevski

  2. Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia

    M. Žunić

  3. Faculty of Physical Chemistry, University of Belgrade, Studenski trg 12-16, 11158, Belgrade, Serbia

    D. Bajuk-Bogdanović, I. Holclajtner-Antunović & S. Mentus

  4. Serbian Academy of Science and Arts, Knez Mihajlova 35, 11000, Belgrade, Serbia

    S. Mentus

Authors
  1. M. Stojmenović
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Žunić
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. Gulicovski
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. D. Bajuk-Bogdanović
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. I. Holclajtner-Antunović
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. V. Dodevski
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. S. Mentus
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. Stojmenović.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Stojmenović, M., Žunić, M., Gulicovski, J. et al. Structural, morphological, and electrical properties of doped ceria as a solid electrolyte for intermediate-temperature solid oxide fuel cells. J Mater Sci 50, 3781–3794 (2015). https://doi.org/10.1007/s10853-015-8943-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-015-8943-y

Keywords

  • Ceria
  • CeO2
  • Sintered Sample
  • Pure CeO2
  • Pure Ceria