Abstract
Increasing Sr2+ and Ti4+ concentrations in perovskite-type \( {\left( {{\hbox{L}}{{\hbox{a}}_{0.{75} - x}}{\hbox{S}}{{\hbox{r}}_{0.{25} + x}}} \right)_{0.{95}}}{\hbox{M}}{{\hbox{n}}_{0.{5}}}{\hbox{C}}{{\hbox{r}}_{0.{5} - x}}{\hbox{T}}{{\hbox{i}}_x}{{\hbox{O}}_{{3} - }}_\delta \left( {x = 0 - 0.{5}} \right) \) results in slightly higher thermal and chemical expansion, whereas the total conductivity activation energy tends to decrease. The average thermal expansion coefficients determined by controlled-atmosphere dilatometry vary in the range (10.8–14.5) × 10−6 K−1 at 373–1,373 K, being almost independent of the oxygen partial pressure. Variations of the conductivity and Seebeck coefficient, studied in the oxygen pressure range 10−18–0.5 atm, suggest that the electronic transport under oxidizing and moderately reducing conditions is dominated by p-type charge carriers and occurs via a small-polaron mechanism. Contrary to the hole concentration changes, the hole mobility decreases with increasing x. The oxygen permeation fluxes through dense ceramic membranes are quite similar for all compositions due to very low level of oxygen nonstoichiometry and are strongly affected by the grain-boundary diffusion and surface exchange kinetics. The porous electrodes applied onto lanthanum gallate-based solid electrolyte exhibit a considerably better electrochemical performance compared to the apatite-type La10Si5AlO26.5 electrolyte at atmospheric oxygen pressure, while Sr2+ and Ti4+ additions have no essential influence on the polarization resistance. In H2-containing gases where the electronic transport in \( {\left( {{\hbox{L}}{{\hbox{a}}_{0.{75} - x}}{\hbox{S}}{{\hbox{r}}_{0.{25} + x}}} \right)_{0.{95}}}{\hbox{M}}{{\hbox{n}}_{0.{5}}}{\hbox{C}}{{\hbox{r}}_{0.{5} - x}}{\hbox{T}}{{\hbox{i}}_x}{{\hbox{O}}_{{3} - }}_\delta \) perovskites becomes low, co-doping deteriorates the anode performance, which can be however improved by infiltrating Ni and \( {\hbox{Ce}}{{\hbox{O}}_{{\rm{2}} - }}_\delta \)v into the porous oxide electrode matrix.
Similar content being viewed by others
References
Fuel Cell Handbook (2004) EG&G technical services, 7th edn. Morgantown, West Virginia
Möbius H-H (1997) J Solid State Electrochem 1:2
Tsipis EV, Kharton VV (2008) J Solid State Electrochem 12:1367
Gorte RJ, Park S, Vohs JM, Wang C (2000) Adv Mater 12:1465
Tsipis EV, Kharton VV, Frade JR (2005) J Eur Ceram Soc 25:2623
Marina OA, Canfield NL, Stevenson JW (2002) Solid State Ionics 149:21
Canales-Vásques J, Tao SW, Irvine JTS (2003) Solid State Ionics 159:159
Primdahl S, Hansen JR, Grahl-Madsen L, Larsen PH (2001) J Electrochem Soc 148:A74
Tao S, Irvine JTS (2004) J Electrochem Soc 151:A252
Zha S, Tsang P, Cheng Z, Liu M (2005) J Solid State Chem 178:1844
Ruiz-Moralez JC, Canales-Vazquez J, Peña-Martínez J, Marrero-López D, Núñez P (2006) Electrochim Acta 52:278
Lu XC, Zhu JH (2007) Solid State Ionics 178:1467
Chen XJ, Liu QL, Khor KA, Chan SH (2007) J Power Sources 165:34
Wan J, Zhu JH, Goodenough JB (2006) Solid State Ionics 177:1211
Kharton VV, Tsipis EV, Marozau IP, Viskup AP, Frade JR, Irvine JTS (2007) Solid State Ionics 178:101
Jiang SP, Zhang L, Zhang Y (2007) J Mater Chem 17:2627
Shaula AL, Kharton VV, Marques FMB (2005) J Solid State Chem 178:2050
Kharton VV, Shaula AL, Vyshatko NP, Marques FMB (2003) Electrochim Acta 48:1817
Tsipis EV, Kharton VV, Frade JR (2007) Electrochim Acta 52:4428
Marozau IP, Kharton VV, Viskup AP, Frade JR, Samakhval VV (2006) J Eur Ceram Soc 26:1371
Plint SM, Connor PA, Tao S, Irvine JTS (2006) Solid State Ionics 177:2005
Oishi M, Yashiro K, Sato K, Mizusaki J, Kawada T (2008) J Solid State Chem 181:3177
Tsipis EV, Kharton VV (2008) J Solid State Electrochem 12:1039
Okamura T, Shimizu S, Nogi M, Tanimura M, Furuya K, Munakata F (2004) J Power Sources 130:38
Mizusaki J (1992) Solid State Ionics 52:79
Anderson HU, Kuo JH, Sparlin DM (1989) In: Singhal SC (ed) SOFC I. The Electrochemical Society, Pennington, p 111, PV89-11
Hahn WC Jr, Muan A (1960) Am J Sci 258:66
Nakamura T, Petzow G, Gauckler LJ (1979) Mater Res Bull 14:649
Yasuda I, Hishinuma M (1996) J Solid State Chem 123:382
Kofstad P (1972) Nonstoichiometry, diffusion and electrical conductivity in binary metal oxides. Wiley, New York
Raffaelle R, Anderson HU, Sparlin DM, Parris PE (1991) Phys Rev B 43:7991
Kawada T, Horita T, Sakai N, Yokokawa H, Dokiya M (1995) Solid State Ionics 79:201
Suzuki M, Sasaki H, Kajimura A (1997) Solid State Ionics 96:83
Lee DK, Yoo HI (2000) J Electrochem Soc 147:2835
Berenov AV, MacManus-Driscoll JL, Kilner JA (1999) Solid State Ionics 122:41
Jiang SP (2002) Solid State Ionics 146:1
Takeda Y, Kanno R, Noda M, Tomida Y, Yamamoto O (1987) ci 134:2656
Crank J (1975) The mathematics of diffusion, 2nd edn. Oxford Univ Press, Oxford
Acknowledgements
This work was partially supported by the FCT, Portugal (projects PTDC/CTM/64357/2006, SFRH/BD/45227/2008, SFRH/BPD/28629/2006, and SFRH/BPD/28913/2006), by the European Commission (project STRP 033410-MatSILC), and by the Ministry of Education and Science of the Russian Federation (state contract 02.740.11.5214).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Kolotygin, V.A., Tsipis, E.V., Shaula, A.L. et al. Transport, thermomechanical, and electrode properties of perovskite-type \( {\left( {{\hbox{L}}{{\hbox{a}}_{0.{75} - x}}{\hbox{S}}{{\hbox{r}}_{0.{25} + x}}} \right)_{0.{95}}}{\hbox{M}}{{\hbox{n}}_{0.{5}}}{\hbox{C}}{{\hbox{r}}_{0.{5} - x}}{\hbox{T}}{{\hbox{i}}_x}{{\hbox{O}}_{{3} - }}_\delta \left( {x = 0 - 0.{5}} \right) \) . J Solid State Electrochem 15, 313–327 (2011). https://doi.org/10.1007/s10008-010-1203-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10008-010-1203-9