Skip to main content
Log in

An insight into the electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction

  • Original Paper
  • Published:
Journal of Solid State Electrochemistry Aims and scope Submit manuscript

Abstract

The electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction were investigated as a function of temperature, applied cathodic voltage, and electrode thickness by means of electrochemical impedance spectroscopy technique. The impedance spectra were deconvoluted with the aid of an analysis on the distribution function of relaxation times. The electrode polarization was related to the contribution coming from the elementary steps of surface oxygen exchange process. The electrode reaction was appreciably activated by applying cathodic voltage, attributable to reduction of partial transition metal cations in the electrodes accompanied by creation of oxygen vacancies. The electrocatalytic properties displayed a significant dependence on the electrode thickness, which was explained considering the impact of changing electrode thickness on the kinetics of the reaction steps involved. The lengths of electrocatalytically active region were estimated to be 6–12 μm at temperatures from 700 to 800 °C, while the optimum electrode thickness was ascertained to be around 35 μm at the temperatures. The ~ 35-μm-thick electrode showed a polarization resistance of 0.086 Ω cm2 at 800 °C. The present study demonstrates that oxygen adsorption and disassociation is the key step dictating the kinetics of the overall electrode reaction.

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

Access this article

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. Adler SB (2004) Factors governing oxygen reduction in solid oxide fuel cell cathodes. Chem Rev 104(10):4791–4843

    Article  CAS  PubMed  Google Scholar 

  2. Chen YB, Zhou W, Ding D, Liu ML, Ciucci F, Tade M, Shao ZP (2015) Advances in cathode materials for solid oxide fuel cells: complex oxides without alkaline earth metal elements. Adv Energy Mater 5(18):1500537

    Article  CAS  Google Scholar 

  3. Gao Z, Mogni LV, Miller EC, Railsback JG, Barnett SA (2016) A perspective on low-temperature solid oxide fuel cells. Energy Environ Sci 9(5):1602–1644

    Article  CAS  Google Scholar 

  4. Li MR, Zhao MW, Li F, Zhou W, Peterson VK, Xu XY, Shao ZP, Gentle I, Zhu ZH (2017) A niobium and tantalum co-doped perovskite cathode for solid oxide fuel cells operating below 500 °C. Nat Commun 8(1):13990

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Adler SB, Lane JA, Steele BCH (1996) Electrode kinetics of porous mixed-conducting oxygen electrodes. J Electrochem Soc 143(11):3554–3564

    Article  CAS  Google Scholar 

  6. Yokokawa H, Tu H, Iwanschitz B, Mai A (2008) Fundamental mechanisms limiting solid oxide fuel cell durability. J Power Sources 182(2):400–412

    Article  CAS  Google Scholar 

  7. Kuklja MM, Kotomin EA, Merkle R, Mastrikov YA, Maier J (2013) Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells. Phys Chem Chem Phys 15(15):5443–5471

    Article  CAS  PubMed  Google Scholar 

  8. Niu YJ, Zhou W, Sunarso J, Ge L, Zhu ZH, Shao ZP (2010) High performance cobalt-free perovskite cathode for intermediate temperature solid oxide fuel cells. J Mater Chem 20(43):9619–9622

    Article  CAS  Google Scholar 

  9. Wei B, Lü Z, Huang XQ, Liu ZG, Miao JP, Li N, Su WH (2007) Ba0.5Sr0.5Zn0.2Fe0.8O3 perovskite oxide as a novel cathode for intermediate-temperature solid-oxide fuel cells. J Am Ceram Soc 90(10):3364–3366

    Article  CAS  Google Scholar 

  10. Zhou Q, Xu L, Guo YJ, Jia D, Li Y, Wei WCJ (2012) La0.6Sr0.4Fe0.8Cu0.2O3-δ perovskite oxide as cathode for IT-SOFC. Int J Hydrog Energy 37(16):11963–11968

    Article  CAS  Google Scholar 

  11. Chen M, Paulson S, Thangadurai V, Birss V (2013) Sr-rich chromium ferrites as symmetrical solid oxide fuel cell electrodes. J Power Sources 236:68–79

    Article  CAS  Google Scholar 

  12. Chen M, Paulson S, Kan WH, Thangadurai V, Birss V (2015) Surface and bulk study of strontium-rich chromium ferrite oxide as a robust solid oxide fuel cell cathode. J Mater Chem A 3(45):22614–22626

    Article  CAS  Google Scholar 

  13. Pang SL, Wang WZ, Chen T, Shen XQ, Wang YG, Xu KJ, Xi XM (2016) Systematic evaluation of cobalt-free Ln0.5Sr0.5Fe0.8Cu0.2O3-δ (Ln=La, Pr, and Nd) as cathode materials for intermediate-temperature solid oxide fuel cells. J Power Sources 326:176–181

    Article  CAS  Google Scholar 

  14. Bian LZ, Duan CC, Wang LJ, Zhu LZ, O'Hayre R, Chou KC (2018) Electrochemical performance and stability of La0·5Sr0·5Fe0·9Nb0·1O3-δ symmetric electrode for solid oxide fuel cells. J Power Sources 399:398–405

    Article  CAS  Google Scholar 

  15. Nie LF, Liu MF, Zhang YJ, Liu ML (2010) La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes infiltrated with samarium-doped cerium oxide for solid oxide fuel cells. J Power Sources 195(15):4704–4708

    Article  CAS  Google Scholar 

  16. Pan ZH, Liu QL, Lyu RZ, Li P, Chan SH (2018) Effect of La0.6Sr0.4Co0.2Fe0.8O3−δ air electrode-electrolyte interface on the short-term stability under high-current electrolysis in solid oxide electrolyzer cells. J Power Sources 378:571–578

    Article  CAS  Google Scholar 

  17. Muhammed Ali SA, Anwar M, Baharuddin NA, Somalu MR, Muchtar A (2018) Enhanced electrochemical performance of LSCF cathode through selection of optimum fabrication parameters. J Solid State Electrochem 22(1):263–273

    Article  CAS  Google Scholar 

  18. Baumann FS, Fleig J, Habermeier HU, Maier J (2006) Impedance spectroscopic study on well-defined (La,Sr)(Co,Fe)O3-δ model electrodes. Solid State Ionics 177(11-12):1071–1081

    Article  CAS  Google Scholar 

  19. Molero-Sánchez B, Addo P, Buyukaksoy A, Paulson S, Birss V (2015) Electrochemistry of La0.3Sr0.7Fe0.7Cr0.3O3-δ as an oxygen and fuel electrode for RSOFCs. Faraday Discuss 182:159–175

    Article  PubMed  CAS  Google Scholar 

  20. Lin L, Xu Q, Wang YP, Chen M, Xiao J, Huang DP, Zhang F (2018) Property optimization for strontium-rich lanthanum chromium ferrite cathodes: a demonstration of lanthanide replacement effect. Mater Res Bull 106:263–270

    Article  CAS  Google Scholar 

  21. Xu Q, Huang DP, Zhao K, Chen W, Chen M, Kim BH (2011) Powder morphology modification and sinterability improvement of Ce0.8Sm0.2O1.9 derived from solution combustion process. Ceram Int 37(3):913–920

    Article  CAS  Google Scholar 

  22. Zhao K, Xu Q, Huang DP, Chen M, Kim BH (2012) Electrochemical evaluation of La2NiO4+δ -based composite electrodes screen-printed on Ce0.8Sm0.2O1.9 electrolyte. J Solid State Electrochem 16(8):2797–2804

    Article  CAS  Google Scholar 

  23. Baumann FS, Fleig J, Konuma M, Starke U, Habermeier HU, Maier J (2005) Strong performance improvement of La0.6Sr0.4Co0.8Fe0.2O3-δ SOFC cathodes by electrochemical activation. J Electrochem Soc 152(10):A2074–A2079

    Article  CAS  Google Scholar 

  24. Wang YP, Xu Q, Huang DP, Zhao K, Chen M, Kim BH (2016) Evaluation of La1.8Sr0.2NiO4+δ as cathode for intermediate temperature solid oxide fuel cells. Int J Hydrog Energy 41(15):6476–6485

    Article  CAS  Google Scholar 

  25. Küngas R, Kivi I, Lust K, Nurk G, Lust E (2009) Statistical method to optimize the medium temperature solid oxide fuel cell electrode materials. J Electroanal Chem 629(1-2):94–101

    Article  CAS  Google Scholar 

  26. Shao J, Hansen KK (2013) Enhancement of NOx removal performance for (La0.85Sr0.15)0.99MnO3/Ce0.9Gd0.1O1.95 electrochemical cells by NOx storage/reduction adsorption layers. Electrochim Acta 90:482–491

    Article  CAS  Google Scholar 

  27. Boukamp B (1995) A linear Kronig-Kramers transform test for immittance data validation. J Electrochem Soc 142(6):1885–1894

    Article  CAS  Google Scholar 

  28. Leonide A, Sonn V, Weber A, Ivers-Tiffée E (2008) Evaluation and modeling of the cell resistance in anode-supported solid oxide fuel cells. J Electrochem Soc 155(1):B36–B41

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  30. Boulfrad S, Cassidy M, Irvine JTS (2010) Adhesion and percolation parameters in two dimensional Pd-LSCM composites for SOFC anode current collection. Adv Funct Mater 20(5):861–866

    Article  CAS  Google Scholar 

  31. Horovistiz AL, Muccillo ENS (2011) Quantification of microstructural features in gadolinia-doped ceria containing co-additives by digital image analysis. J Eur Ceram Soc 31(8):1431–1438

    Article  CAS  Google Scholar 

  32. Hoomans BPB, Kuipers JAM, Briels WJ, van Swaaij WPM (1996) Discrete particle simulation of bubble and slug formation in a two-dimensional gas-fluidised bed: a hard-sphere approach. Chem Eng Sci 51(1):99–118

    Article  CAS  Google Scholar 

  33. Yang XH, Lu TJ, Kim T (2013) A simplistic model for the tortuosity in two-phase close-celled porous media. J Phys D Appl Phys 46(12):125305

    Article  CAS  Google Scholar 

  34. Li JG, Ikegami T, Mori T (2004) Low temperature processing of dense samarium-doped CeO2 ceramics: sintering and grain growth behaviors. Acta Mater 52(8):2221–2228

    Article  CAS  Google Scholar 

  35. Wang YP, Zhao K, Xu Q, Huang DP, Chen M, Kim BH (2018) Optimization on the electrochemical properties of La2NiO4+δ cathodes by tuning the cathode thickness. Int J Hydrog Energy 43(9):4482–4491

    Article  CAS  Google Scholar 

  36. Mauvy F, Bassat JM, Boehm E, Manaud JP, Dordor P, Grenier JC (2003) Oxygen electrode reaction on Nd2NiO4+δ cathode materials: impedance spectroscopy study. Solid State Ionics 158(1-2):17–28

    Article  CAS  Google Scholar 

  37. Hildenbrand N, Nammensma P, Blank DHA, Bouwmeester HJM, Boukamp BA (2013) Influence of configuration and microstructure on performance of La2NiO4+δ intermediate-temperature solid oxide fuel cells cathodes. J Power Sources 238:442–453

    Article  CAS  Google Scholar 

  38. Wan TH, Saccoccio M, Chen C, Ciucci F (2015) Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim Acta 184:483–499

    Article  CAS  Google Scholar 

  39. Boukamp BA, Rolle A (2017) Analysis and application of distribution of relaxation times in solid state ionics. Solid State Ionics 302:12–18

    Article  CAS  Google Scholar 

  40. Escudero MJ, Aguadero A, Alonso JA, Daza L (2007) A kinetic study of oxygen reduction reaction on La2NiO4 cathodes by means of impedance spectroscopy. J Electroanal Chem 611(1-2):107–116

    Article  CAS  Google Scholar 

  41. Kharton VV, Tsipisa EV, Yaremchenkoa AA, Frade JR (2004) Surface-limited oxygen transport and electrode properties of La2Ni0.8Cu0.2O4+δ. Solid State Ionics 166(3-4):327–337

    Article  CAS  Google Scholar 

  42. Chen XJ, Khor KA, Chan SH (2004) Electrochemical behavior of La(Sr)MnO3 electrode under cathodic and anodic polarization. Solid State Ionics 167(3-4):379–387

    Article  CAS  Google Scholar 

  43. Huber AK, Falk M, Rohnke M, Luerßen B, Gregoratti L, Amati M, Janek J (2012) In situ study of electrochemical activation and surface segregation of the SOFC electrode material La0.75Sr0.25Cr0.5Mn0.5O3±δ. Phys Chem Chem Phys 14(2):751–758

    Article  CAS  PubMed  Google Scholar 

  44. Mauvy F, Lalanne C, Bassat JM, Grenier JC, Zhao H, Huo LH, Stevens P (2006) Electrode properties of Ln2NiO4+δ (Ln=La, Nd, Pr) AC impedance and DC polarization studies. J Electrochem Soc 153(8):A1547–A1553

    Article  CAS  Google Scholar 

  45. Read MSD, Islam MS, Watson GW, Hancock FE (2001) Surface structures and defect properties of pure and doped La2NiO4. J Mater Chem 11(10):2597–2602

    Article  CAS  Google Scholar 

  46. Xu XY, Xia CR, Xiao GL, Peng DK (2005) Fabrication and performance of functionally graded cathodes for IT-SOFCs based on doped ceria electrolytes. Solid State Ionics 176(17-18):1513–1520

    Article  CAS  Google Scholar 

  47. Adler SB, Chen XY, Wilson JR (2007) Mechanisms and rate laws for oxygen exchange on mixed-conducting oxide surfaces. J Catal 245(1):91–109

    Article  CAS  Google Scholar 

  48. Cao YP, Gadre MJ, Ngo AT, Adler SB, Morgan DD (2019) Factors controlling surface oxygen exchange in oxides. Nat Commun 10(1):1346

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  49. Liu Z, Liu MF, Nie LF, Liu ML (2013) Fabrication and characterization of functionally-graded LSCF cathodes by tape casting. Int J Hydrog Energy 38(2):1082–1087

    Article  CAS  Google Scholar 

  50. Xie XB, Xu Q, Xiao J, Chen M, Chen DC, Huang DP, Zhang F (2020) Improved electrocatalytic properties of La0.3Ca0.7Fe0.7Cr0.3O3-δ electrodes for oxygen reduction reaction: the effect of electrode thickness. Mater Res Bull 131:110967

    Article  CAS  Google Scholar 

  51. Yoon SP, Nam SW, Han JH, Lim TH, Hong SA, Hyun SH (2004) Effect of electrode microstructure on gas-phase diffusion in solid oxide fuel cells. Solid State Ionics 166(1-2):1–11

    Article  CAS  Google Scholar 

  52. Pajot M, Duffort V, Capoen E, Mamede AS, Vannier RN (2020) Influence of the strontium content on the performance of La1-xSrxMnO3/Bi1.5Er0.5O3 composite electrodes for low temperature solid oxide fuel cells. J Power Sources 450:227049

    Article  CAS  Google Scholar 

  53. Merkle R, Maier J (2002) Oxygen incorporation into Fe-doped SrTiO3: mechanistic interpretation of the surface reaction. Phys Chem Chem Phys 4(17):4140–4148

    Article  CAS  Google Scholar 

  54. Adler SB (1998) Mechanism and kinetics of oxygen reduction on porous La1-xSrxCoO3-δ electrodes. Solid State Ionics 111(1-2):125–134

    Article  CAS  Google Scholar 

  55. Qiang F, Sun KN, Zhang NQ, Le SR, Zhu XD, Piao JH (2009) Optimization on fabrication and performance of A-site-deficient La0.58Sr0.4Co0.2Fe0.8O3-δ cathode for SOFC. J Solid State Electrochem 13(3):455–467

    Article  CAS  Google Scholar 

Download references

Funding

This research was financially supported by the National Natural Science Foundation of China (Nos. 51572204 and 51872047), Nature Science Foundation of Guangdong Province (No. 2018A030313779), Key Project of Guangdong Provincial Department of Education (No. 2019KZDXM039), and Fundamental Research Funds for the Central Universities (WUT: 2016-III-036).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Qing Xu or Min Chen.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

ESM 1

(DOC 5144 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Xie, XB., Xu, Q., Huang, DP. et al. An insight into the electrocatalytic properties of porous La0.3Sr0.7Fe0.7Cr0.3O3−δ electrodes towards oxygen reduction reaction. J Solid State Electrochem 25, 1007–1018 (2021). https://doi.org/10.1007/s10008-020-04875-w

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10008-020-04875-w

Keywords

Navigation