Proteic sol–gel synthesis of Gd-doped ceria: a comprehensive structural, chemical, microstructural and electrical analysis
Source abstract
Abstract
Gd-doped ceria (Ce1−xGdxO2-δ; x = 0, 0.1 and 0.2) is one of the best ceramic electrolytes for application in solid oxide electrochemical devices. This work reports an innovative and environmentally friendly route known as “proteic sol–gel synthesis” using gelatin for their preparation. Materials are characterized via thermogravimetric analysis, X-ray diffractometry, scanning electron microscopy, Raman and X-ray photoelectron spectroscopies, and electrochemical impedance spectroscopy. The proposed method allows to produce pure phase nanosized powders at 400 °C that exhibit excellent sinterability at 1350 °C. Significant differences are found in the bulk at lower temperatures, with estimated defect association enthalpies of 0.45 and 0.56 eV for the compositions containing 10 and 20 mol% Gd, respectively, leading to an increased bulk conductivity in the first case. In contrast, identical grain boundary Schottky barrier height values of around 0.2 V are a possible result of the relatively low sintering temperature, decreasing the extent of the acceptor dopant segregation to the grain boundaries due to insufficient cation mobility. This leads to similar specific grain boundary characteristics in both doped compositions. Overall, this work provides a rational understanding of a novel route for the synthesis of CGO ceramics with competitive performance and decreased sintering temperature.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advancements in Solid Oxide Fuel Cells · Electronic and Structural Properties of Oxides · Catalytic Processes in Materials Science
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (55)
Show source-provided references
1. Huijsmans JPP, van Berkel FPF, Christie GM (1998) Intermediate temperature SOFC—a promise for the 21st century. J Power Sources 71:107–110. https://doi.org/10.1016/S0378-7753(97)02789-410.1016/S0378-7753(97)02789-4 ↗
2. Nechache A, Cassir M, Ringuedé A (2014) Solid oxide electrolysis cell analysis by means of electrochemical impedance spectroscopy: a review. J Power Sources 258:164–181. https://doi.org/10.1016/j.jpowsour.2014.01.11010.1016/j.jpowsour.2014.01.110 ↗
3. Steele BCH, Heinzel A (2001) Materials for fuel-cell technologies. Nature 414:345–352. https://doi.org/10.1142/9789814317665_003110.1142/9789814317665_0031 ↗
4. Dönmez G, Sarıboğa V, Gürkaynak Altinçekiç T, Öksüzömer MAF (2014) Polyol synthesis and investigation of Ce1−xRExO2−x/2 (RE = Sm, Gd, Nd, La, 0 ≤ x ≤ 0.25) eElectrolytes for IT-SOFCs. J Am Ceram Soc 98:501–509. https://doi.org/10.1111/jace.1330010.1111/jace.13300 ↗
5. Kharton VV, Marques FMB, Atkinson A (2004) Transport properties of solid oxide electrolyte ceramics: a brief review. Solid State Ionics 174:135–149. https://doi.org/10.1016/j.ssi.2004.06.01510.1016/j.ssi.2004.06.015 ↗
6. Zhou Y, Rahaman MN (1997) Effect of redox reaction on the sintering behavior of cerium oxide. Acta Mater 45:3635–3639. https://doi.org/10.1016/S1359-6454(97)00052-910.1016/S1359-6454(97)00052-9 ↗
7. Jadhav LD, Chourashiya MG, Subhedar KM et al (2009) Synthesis of nanocrystalline Gd doped ceria by combustion technique. J Alloys Compd 470:383–386. https://doi.org/10.1016/j.jallcom.2008.02.07710.1016/j.jallcom.2008.02.077 ↗
8. Lima CGM, Santos TH, Grilo JPF et al (2015) Synthesis and properties of CuO-doped Ce0.9Gd0.1O2-δ electrolytes for SOFCs. Ceram Int 41:4161–4168. https://doi.org/10.1016/j.ceramint.2014.12.09310.1016/j.ceramint.2014.12.093 ↗
9. Fagg DP, Kharton VV, Frade JR (2002) P-type electronic transport in Ce0.8Gd0.2O2-δ: The effect of transition metal oxide sintering aids. J Electroceramics 9:199–207. https://doi.org/10.1023/A:102326932665110.1023/A:1023269326651 ↗
10. Grilo JPF, Macedo DA, Nascimento RM, Marques FMB (2019) Electronic conductivity in Gd-doped ceria with salt additions. Electrochim Acta 318:977–988. https://doi.org/10.1016/j.electacta.2019.06.14810.1016/j.electacta.2019.06.148 ↗
11. Loureiro FJA, Souza GS, Graça VCD et al (2019) Nickel-copper based anodes for solid oxide fuel cells running on hydrogen and biogas: Study using ceria-based electrolytes with electronic short-circuiting correction. J Power Sources 438:227041–227049. https://doi.org/10.1016/j.jpowsour.2019.22704110.1016/j.jpowsour.2019.227041 ↗
12. Zarkov A, Stanulis A, Salkus T et al (2016) Synthesis of nanocrystalline gadolinium doped ceria via sol–gel combustion and sol–gel synthesis routes. Ceram Int 42:3972–3988. https://doi.org/10.1016/j.ceramint.2015.11.06610.1016/j.ceramint.2015.11.066 ↗
13. Santos JRD, Loureiro FJA, Grilo JPF et al (2018) Understanding the cathodic polarisation behaviour of the misfit [Ca2CoO3-δ]q[CoO2] (C349) as oxygen electrode for IT-SOFC. Electrochim Acta 285:214–220. https://doi.org/10.1016/j.electacta.2018.08.01810.1016/j.electacta.2018.08.018 ↗
14. Emerenciano AA, Araújo AJM, Grilo JPF et al (2019) Environmentally friendly synthesis methods to obtain the misfit [Ca2CoO3-δ]0.62[CoO2] thermoelectric material. Mater Lett 254:286–289. https://doi.org/10.1016/j.matlet.2019.07.05310.1016/j.matlet.2019.07.053 ↗
15. Pechini MP (1967) Method of preparing lead and alkaline earth titanates and niobates and coating method using the same to form a capacitor. https://patents.google.com/patent/US3330697A/en
16. Silva RM, Raimundo RA, Fernandes WV et al (2018) Proteic sol-gel synthesis, structure and magnetic properties of Ni/NiO core-shell powders. Ceram Int 44:6152–6156. https://doi.org/10.1016/j.ceramint.2017.12.24810.1016/j.ceramint.2017.12.248 ↗
17. Cela B, Macedo DA, Souza GL et al (2011) NiO-CGO in situ nanocomposite attainment: One step synthesis. J Power Sources 196:2539–2544. https://doi.org/10.1016/j.jpowsour.2010.11.02610.1016/j.jpowsour.2010.11.026 ↗
18. Araujo AJM, Sousa ARO, Grilo JPF et al (2016) Preparation of one-step NiO/Ni-CGO composites using factorial design. Ceram Int 42:18166–18172. https://doi.org/10.1016/j.ceramint.2016.08.13110.1016/j.ceramint.2016.08.131 ↗
19. Grilo JPF, Moura CG, Macedo DA et al (2017) Effect of composition on the structural development and electrical conductivity of NiO-GDC composites obtained by one-step synthesis. Ceram Int 43:8905–8911. https://doi.org/10.1016/j.ceramint.2017.04.02710.1016/j.ceramint.2017.04.027 ↗
20. Silva TR, Silva VD, Ferreira LS et al (2020) Role of oxygen vacancies on the energy storage performance of battery-type NiO electrodes. Ceram Int 46:9233–9239. https://doi.org/10.1016/j.ceramint.2019.12.17610.1016/j.ceramint.2019.12.176 ↗
21. Ferreira LS, Silva TR, Silva VD et al (2020) Proteic sol-gel synthesis, structure and battery-type behavior of Fe-based spinels (MFe2O4, M = Cu Co, Ni). Adv Powder Technol 31:604–613. https://doi.org/10.1016/j.apt.2019.11.01510.1016/j.apt.2019.11.015 ↗
22. Lima CGM, Silva RM, de Aquino FM et al (2017) Proteic sol-gel synthesis of copper doped misfit Ca-cobaltites with potential SOFC application. Mater Chem Phys 187:177–182. https://doi.org/10.1016/j.matchemphys.2016.11.06310.1016/j.matchemphys.2016.11.063 ↗
23. Ferreira LS, Silva TR, Santos JRD et al (2019) Structure, magnetic behavior and OER activity of CoFe2O4 powders obtained using agar-agar from red seaweed (Rhodophyta). Mater Chem Phys 237:121847. https://doi.org/10.1016/j.matchemphys.2019.12184710.1016/j.matchemphys.2019.121847 ↗
24. (2004) ISO 19318:2004, Surface chemical analysis—X-ray photoelectron spectroscopy—reporting of methods used for charge control and charge correction. https://www.iso.org/standard/33783.html
25. (2015) ASTM E1523–15, Standard guide to charge control and charge referencing techniques in X-ray photoelectron spectroscopy. ASTM International, West Conshohocken, PA. www.astm.org
26. Yeh JJ, Lindau I (1985) Atomic subshell photoionization cross sections and asymmetry parameters: 1 ⩽ Z ⩽ 103. At Data Nucl Data Tables 32:1–155. https://doi.org/10.1016/0092-640X(85)90016-610.1016/0092-640X(85)90016-6 ↗
27. Braga TP, Dias DF, de Sousa MF et al (2015) Synthesis of air stable FeCo alloy nanocrystallite by proteic sol-gel method using a rotary oven. J Alloys Compd 622:408–417. https://doi.org/10.1016/j.jallcom.2014.10.07410.1016/j.jallcom.2014.10.074 ↗
28. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 32:751–767. https://doi.org/10.1107/S056773947600155110.1107/S0567739476001551 ↗
29. Rietveld HM (1969) A profile refinement method for nuclear and magnetic structures. J Appl Crystallogr 2:65–71. https://doi.org/10.1107/S002188986900655810.1107/S0021889869006558 ↗
30. Guo M, Lu J, Wu Y et al (2011) UV and visible Raman studies of oxygen vacancies in rare-earth-doped ceria. Langmuir 27:3872–3877. https://doi.org/10.1021/la200292f10.1021/la200292f ↗
31. He D, Hao H, Chen D et al (2017) Synthesis and application of rare-earth elements (Gd, Sm, and Nd) doped ceria-based solid solutions for methyl mercaptan catalytic decomposition. Catal Today 281:559–565. https://doi.org/10.1016/j.cattod.2016.06.02210.1016/j.cattod.2016.06.022 ↗
32. Banerji A, Grover V, Sathe V et al (2009) CeO2-Gd2O3 system: unraveling of microscopic features by Raman spectroscopy. Solid State Commun 149:1689–1692. https://doi.org/10.1016/j.ssc.2009.06.04510.1016/j.ssc.2009.06.045 ↗
33. Araújo AJM, Silva VD, Sousa ARO et al (2019) Battery-like behavior of Ni-ceria based systems: Synthesis, surface defects and electrochemical assessment. Ceram Int 45:7157–7165. https://doi.org/10.1016/j.ceramint.2018.12.22210.1016/j.ceramint.2018.12.222 ↗
34. Upadhyaya DD, Bhat R, Ramanathan S et al (1994) Solute effect on grain growth in ceria ceramics. J Eur Ceram Soc 14:337–341. https://doi.org/10.1016/0955-2219(94)90070-110.1016/0955-2219(94)90070-1 ↗
35. Inaba H, Nakajima T, Tagawa H (1998) Sintering behaviors of ceria and gadolinia-doped ceria. Solid State Ionics 106:263–268. https://doi.org/10.1016/s0167-2738(97)00496-710.1016/s0167-2738(97)00496-7 ↗
36. Peng R, Xia C, Peng D, Meng G (2004) Effect of powder preparation on (CeO2)0.8(Sm2O3)0.1 thin film properties by screen-printing. Mater Lett 58:604–608. https://doi.org/10.1016/S0167-577X(03)00578-010.1016/S0167-577X(03)00578-0 ↗
37. Xia C, Liu M (2002) Microstructures, conductivities, and electrochemical properties of Ce0.9Gd0.1O2 and GDC–Ni anodes for low-temperature SOFCs. Solid State Ionics 152–153:423–430. https://doi.org/10.1016/S0167-2738(02)00381-810.1016/S0167-2738(02)00381-8 ↗
38. Arabac A, Öksüzömer MF (2012) Preparation and characterization of 10 mol% Gd doped CeO2 (GDC) electrolyte for SOFC applications. Ceram Int 38:6509–6515. https://doi.org/10.1016/j.ceramint.2012.05.03010.1016/j.ceramint.2012.05.030 ↗
39. Tian R, Zhao F, Chen F, Xia C (2011) Sintering of Samarium-doped ceria powders prepared by a glycine-nitrate process. Solid State Ionics 192:580–583. https://doi.org/10.1016/j.ssi.2010.08.00310.1016/j.ssi.2010.08.003 ↗
40. Sındıraç C, Büyükaksoy A, Akkurt S (2019) Electrical properties of gadolinia doped ceria electrolytes fabricated by infiltration aided sintering. Solid State Ionics 340:115020. https://doi.org/10.1016/j.ssi.2019.11502010.1016/j.ssi.2019.115020 ↗
41. Cheng J, Zha S, Fang X et al (2002) On the green density, sintering behavior and electrical property of tape cast Ce0.9Gd0.1O1.95 electrolyte. Mater Res Bull 37:2437–2446. https://doi.org/10.1016/S0025-5408(02)00931-510.1016/S0025-5408(02)00931-5 ↗
42. Gondolini A, Mercadelli E, Sanson A et al (2011) Microwave-assisted synthesis of gadolinia-doped ceria powders for solid oxide fuel cells. Ceram Int 37:1423–1426. https://doi.org/10.1016/j.ceramint.2011.01.01010.1016/j.ceramint.2011.01.010 ↗
43. Chen M, Zhang H, Fan L et al (2014) Ceria-carbonate composite for low temperature solid oxide fuel cell: Sintering aid and composite effect. Int J Hydrogen Energy 39:12309–12316. https://doi.org/10.1016/j.ijhydene.2014.04.00410.1016/j.ijhydene.2014.04.004 ↗
44. Fuentes RO, Baker RT (2008) Synthesis and properties of Gadolinium-doped ceria solid solutions for IT-SOFC electrolytes. Int J Hydrogen Energy 33:3480–3484. https://doi.org/10.1016/j.ijhydene.2007.10.02610.1016/j.ijhydene.2007.10.026 ↗
45. Suda E, Pacaud B, Mori M (2006) Sintering characteristics, electrical conductivity and thermal properties of La-doped ceria powders. J Alloys Compd 408–412:1161–1164. https://doi.org/10.1016/j.jallcom.2004.12.13510.1016/j.jallcom.2004.12.135 ↗
46. Kang YJ, Choi GM (2009) The effect of alumina and Cu addition on the electrical properties and the SOFC performance of Gd-doped CeO2 electrolyte. Solid State Ionics 180:886–890. https://doi.org/10.1016/j.ssi.2009.02.02110.1016/j.ssi.2009.02.021 ↗
47. Sánchez-Bautista C, Dos Santos-García AJ, Peña-Martínez J, Canales-Vázquez J (2010) Processing of samarium doped ceria for IT-SOFC. Grain boundary effect on the electrical conductivity. Bol la Soc Española Ceram y Vidr 49:7–14
48. Santos TH, Grilo JPF, Loureiro FJA et al (2018) Structure, densification and electrical properties of Gd3+ and Cu2+ co-doped ceria solid electrolytes for SOFC applications: effects of Gd2O3 content. Ceram Int 44:2745–2751. https://doi.org/10.1016/j.ceramint.2017.11.00910.1016/j.ceramint.2017.11.009 ↗
49. Guo X, Waser R (2006) Electrical properties of the grain boundaries of oxygen ion conductors: acceptor-doped zirconia and ceria. Prog Mater Sci 51:151–210. https://doi.org/10.1016/j.pmatsci.2005.07.00110.1016/j.pmatsci.2005.07.001 ↗
50. Pérez-Coll D, Núñez P, Ruiz-Morales JC et al (2007) Re-examination of bulk and grain boundary conductivities of Ce1-xGdxO2-δ ceramics. Electrochim Acta 52:2001–2008. https://doi.org/10.1016/j.electacta.2006.08.00910.1016/j.electacta.2006.08.009 ↗
51. Zhang TS, Ma J, Huang HT et al (2003) Effects of dopant concentration and aging on the electrical properties of Y-doped ceria electrolytes. Solid State Sci 5:1505–1511. https://doi.org/10.1016/j.solidstatesciences.2003.10.00110.1016/j.solidstatesciences.2003.10.001 ↗
52. Guo X, Maier J (2001) Grain boundary blocking effect in Zirconia: a Schottky barrier analysis. J Electrochem Soc 148:E121–E126. https://doi.org/10.1149/1.134826710.1149/1.1348267 ↗
53. 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 Sources 196:8383–8390. https://doi.org/10.1016/j.jpowsour.2011.06.07510.1016/j.jpowsour.2011.06.075 ↗
54. Shirpour M, Rahmati B, Sigle W et al (2012) Dopant segregation and space charge effects in proton-conducting BaZrO3 perovskites. J Phys Chem C 116:2453–2461. https://doi.org/10.1021/jp208213x10.1021/jp208213x ↗
55. Esposito V, Traversa E (2008) Design of electroceramics for solid oxides fuel cell applications: playing with Ceria. J Am Ceram Soc 91:1037–1051. https://doi.org/10.1111/j.1551-2916.2008.02347.x10.1111/j.1551-2916.2008.02347.x ↗