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J. Aust. Ceram. Soc. 44 [1] (2008) 34-38

Preparation of Zinc- Doped Lanthanum Strontium Gallate Solid Electrolyte Using a Reaction-Sintering Process
Y. C. LIOU*, C. C. LAN, and S. L. YANG
Department of Electronic Engineering, Kun Shan University, Tainan 71003, Taiwan, R.O.C. *email: ycliou@mail.ksu.edu.tw ABSTRACT La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics prepared using a reaction-sintering process was investigated in this study. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. SrLaGa3O7 is the major phase in 1150C sintered pellets and decreased at higher sintering temperature 1250C. La0.8Sr0.2Ga0.8Zn0.2O2.8 became the major phase in pellets sintered at 1250oC/2 h. Density of La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics increases with sintering temperature and reaches a maximum 6.71 g/cm3 at 1230oC for 6 h. The reaction-sintering process has proven a simple and effective method in preparing La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics for solid electrolyte applications in solid oxide fuel cells. KEYWORDS: La0.8Sr0.2Ga0.8Zn0.2O2.8, electrolyte, reaction-sintering process 1. INTRODUCTION Sr- and Mg-doped LaGaO3 (LSGM) ceramics have received increasing attention since Goodenough and co-workers [1-3], Ishihara et al. [4, 5], and Huang and Petric [6] discovered their superior oxygen ion conducting properties as compared with yttriastabilized zirconia electrolytes. LSGM was found with an oxide-ion conductivity o>0.10 S/cm at 800oC, a very low electronic conduction at T<1000oC, and a stable performance [1-6]. LSGM ceramics were typically synthesized by the conventional mixed oxide method [7-16]. Other methods such as combustion synthesis [17, 18], and the technique of spray pyrolysis were also used to prepare sub-micrometer LSGM powders [19, 20]. Tas et al. prepared La0.8Sr0.2Ga0.8Zn0.2O2.8 (LSGZ) using aqueous chemical precipitation method and obtained single-phase LSGZ after calcination at about 1300oC for 6 h in an air atmosphere [21]. Few years ago, Liou and co-workers prepared Pb(Mg1/3Nb2/3)O3 (PMN) and Pb(Fe1/2Nb1/2)O3 (PFN) ceramics via a simple and effective reaction-sintering process [22, 23]. PbO and Nb2O5 were mixed with Mg(NO3)2 or Fe(NO3)3 then pressed and sintered directly into PMN and PFN ceramics with the calcination step bypassed. These are the first successful synthesis of perovskite relaxor ferroelectric ceramics without having to go through the calcination step in the conventional solid state route or in the columbite/wolframite route (two calcination steps were involved). PMN ceramics with a density 8.09 g/cm3 and dielectric constant 19,900 (1 kHz) were obtained. Other Pb-based complex perovskite ceramics were also produced by this reaction-sintering process successfully. In their recent studies, some microwave dielectric ceramics such as BaTi4O9, (BaxSr1-x)(Zn1/3Nb2/3)O3, Ba5Nb4O15, Sr5Nb4O15, CaNb2O6 and NiNb2O6 were also prepared successfully via this reaction-sintering process [24-28]. In this study, synthesis of La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics by a reaction-sintering process was investigated. 2. EXPERIMENTAL PROCEDURES All samples in this study were prepared from reagent-grade powders: La2O3 (99.99%), SrCO3 (99%), Ga2O3 (99.998%) and ZnO (99%). Appropriate amounts of raw materials for La0.8Sr0.2Ga0.8Zn0.2O2.8 (LSGZ) were milled in acetone with zirconia balls for 12 h. After they had been dried and pulverized, they were formed into pellets 12 mm in diameter and 2-3 mm thick. The pellets were then heated at a rate 10C/min and sintered in a covered alumina crucible at temperatures ranging between 1150C and 1250C for 2-6 h in air. We analyzed the sintered pellets using X-ray diffraction (XRD) to check the reflections of the phases. Microstructures were analyzed using scanning electron microscopy (SEM). The density of the sintered pellets was measured using the Archimedes method. 3. RESULTS AND DISCUSSION The XRD patterns of LSGZ sintered at 1150oC and 1250C for 2 h are shown in Fig. 1. It can be seen reflections of SrLaGa3O7, LSGZ, SrLaGaO4 and La4Ga2O9 were detected. SrLaGa3O7 is the major phase in 1150C sintered pellets and decreased at higher sintering temperature 1250C. LSGZ became the major phase in pellets sintered at 1250oC/2 h. Therefore, reaction-sintering process can efficiently transform the mixture of raw materials into LSGZ phase. La4Ga2O9 phase decreased obviously at 1250oC. Using a Pechini-type process, Tas et al. reported that SrLaGaO4 and SrLaGa3O7 phases appeared in the calcined La0.9Sr0.1GaO2.95 at 1200oC and disappeared at 1340oC/6 h calcination. SrLaGa3O7 phase appeared after 6 h calcined at 700oC and about 4-5 wt% of a mixture of the undesired SrLaGaO4 and SrLaGa3O7 phases still remained even after calcined at 1400oC for 6 h [29]. They also found SrLaGa3O7 as a major phase in LSGZ calcined at 1000oC via aqueous chemical precipitation and almost pure LSGZ at 1200oC [21].

Y. C. Liou, C. C. Lan, S. L. Yang

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Fig. 1 XRD patterns of LSGZ sintered at (A) 1150oC and (B) 1250oC for 2 h. (1: LaGaO3 ICDD PDF # 00-054-0870; 2: SrLaGaO4 ICDD PDF # 01-080-1806; 3: SrLaGa3O7 ICDD PDF # 00-045-0637; 4: La4Ga2O9 ICDD PDF # 00-037-1433)

Fig. 2 SEM photographs of as-fired LSGZ ceramics sintered at (A) 1150oC, (B) 1170oC, (C) 1200oC, (D) 1230oC, and (E) 1250oC for 2 h.

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J. Aust. Ceram. Soc. 44 [1] (2008) 34-38

Fig. 3 SEM photographs of as-fired LSGZ ceramics sintered at (A) 1150oC, (B) 1170oC, (C) 1200oC, (D) 1230oC, and (E) 1250oC for 4 h. SEM photographs of as-fired LSGZ ceramics sintered at 1150-1250oC/2 h are shown in Fig. 2. Porous pellet with fine grains of about 2 m formed at 1150oC and 1170oC. This means 1150-1170oC sintering is not high enough for grain growth and densification in LSGZ ceramics prepared using the reaction-sintering process. It can be easily observed that pores decreased at 1200oC and grain size increased at temperatures 1200-1250oC. The amount of pores decreased in LSGZ ceramics sintered for 4 h as
30 28 26 24 22 20 18 16 14 12 10 1140 1160 1180 1200 1220

shown in Fig. 3. Dense LSGZ could be obtained at sintering temperatures above 1230oC. Dense structure is needed in electrolyte of SOFC to avoid mixing and reaction between fuel and oxygen gas. Tas et al. reported LSGZ powders consisted of round particles with an average diameter of 0.25 m after calcined at 1000oC for 6 h. The non-compacted LSGZ powder body consisted of dense 20 to 30 m chunks was observed at 1300oC 6 h calcination [21].

Shrinkage (%)

2h 4h 6h

1240

1260

Sintering Temperature ()

Fig. 4 Shrinkage percentage of LSGZ ceramics sintered at various temperatures for 2-6 h.

Y. C. Liou, C. C. Lan, S. L. Yang Fig. 4 shows the shrinkage percentage of LSGZ ceramics sintered at various temperatures for 2-6 h. It increases from about 19-22% at 1150oC to 24-25% at 1250oC. In our study of La0.8Sr0.2Ga0.83Mg0.17O2.815 ceramics via reactionsintering process, shrinkage of 17-20% at 1300oC and 26-28% at 1400oC were found. It implies a
8.0

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lower temperature is needed in Zn-doped than in Mg-doped LaSrGaO3- ceramics prepared via reaction-sintering process. In Fig. 5, density of LSGZ ceramics increases with sintering temperature and reaches a maximum 6.71 g/cm3 at 1230oC for 6 h.

Density (g/cm )

7.0 6.0
2h

5.0 4.0 1140 1160 1180 1200 1220

4h 6h

1240

1260

Sintering Temperature ()
Fig. 5 Density of LSGZ ceramics sintered at various temperatures for 2-6 h. 4. CONCLUSIONS Reaction-sintering process can efficiently transform the mixture of raw materials into La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics even if the calcination stage is bypassed. SrLaGa3O7 is the major phase in 1150C sintered pellets and decreased at higher sintering temperature 1250C. La0.8Sr0.2Ga0.8Zn0.2O2.8 became the major phase in pellets 5. REFERENCES 1. K. Huang, M. Feng, J.B. Goodenough, and M. Schmerling, Charaterisation of Sr-Doped LaMnO3 and LaCoO3 as Cathode Materials for Doped LaGaO3 Ceramic Full Cell, J. Electrochem. Soc., Vol. [143], (1996), 3630-3636. 2. K. Huang, M. Feng, and J.B. Goodenough, Sol-Gel Synthesis of a New Oxide-Ion Conductor Sr- and Mg-Doped LaGaO3 Perovskite, J. Am. Ceram. Soc., Vol. [79], (1996), 1100-1104. 3. M. Feng and J.B. Goodenough, A Superior Oxide-Ion Electrolyte, Eur. J. Solid State Inorg. Chem., Vol. [31], (1994), 663-672. 4. T. Ishihara, H Matsuda, and Y. Takita, Effects of Rare Earth Cations Doped for La sit on the Oxide Ionic Conductivity of LaGaO3-Based Perovskite-Type Oxide, Solid Stste Ionic, Vol. [79], (1995), 147-151. 5. T. Ishihara, H Matsuda, and Y. Takita, Doped LaGaO3 Perovskite Type Oxide as a New Oxide Ionic Conductor, J. Am. Chem. Soc., Vol. [116], (1994), 3801-3803. 6. P. Huang and A. Petric, Superior Oxygen Ion Conductivity of Lathanum Gallate Doped with Strotium and Magnesium, J. Electrochem. Soc., Vol. [143], (1996), 1644-1648. 7. K.Q. Huang, M. Feng, J.B. Goodenough, and C. Milliken, Electrode Performance Test on Single Ceramic Fuel Cells Using as Electrolyte Sr- and Mg-Doped LaGaO3, J. Electrochem. Soc., Vol. [144], sintered at 1250oC/2 h. Density of La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics increases with sintering temperature and reaches a maximum 6.71 g/cm3 at 1230oC for 6 h. The reaction-sintering process has proven a simple and effective method in preparing La0.8Sr0.2Ga0.8Zn0.2O2.8 ceramics for solid electrolyte applications in solid oxide fuel cells.

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