June 2011, Volume 2, No.

3 International Journal of Chemical and Environmental Engineering

Fabrication of Macroporous NiO-YSZ Anode using Template-assisted Method

Kai-Hsing Chang-a,, Kuan-Zong Fung -,b Kung University, Tainan City 701, Taiwan a Department of Materials Science and Engineering National Cheng b Corresponding Author E-mail: z8702009@email.ncku.edu.tw
Abstract To increase the area of the triple phase boundaries to promote the efficiency of SOFCs, macroporous NiO-YSZ structure with ordered pores is needed. Monodisperse PMMA spheres prepared by emulsifier-free emulsion polymerization with micron-range diameters were used as the template. The diameters of PMMA spheres are dependent upon the reaction time, initiator concentration and monomer concentration. The compacts of PMMA spheres were impregnated with NiO-YSZ precursors. The removal of PMMA spheres was conducted by heat treatment in air. Consequently, the macroporous NiO-YSZ structure with minimal pore size about 800nm was obtained after heat treatment at 800~1000oC. Keywords: Macroporous; electrode structure; PMMA; Fuel Cell, NiO-YSZ, template

1.

Introduction

Solid oxide fuel cell (SOFC) has been recognized as one of highly efficient and clean technologies for chemical-to-electrical energy conversion. At present, yttria-stabilized zirconia (YSZ) is the most commonly used electrolyte in SOFCs because it possesses an adequate level of oxygen-ion conductivity and exhibits desirable stability in both oxidizing and reducing atmospheres[1,2]. NiO-YSZ mixture is the starting material for preparation of Ni-YSZ cermet anode. In order to extend the active electrochemical reaction sites from the traditional triple phase boundaries (TPBs) at the interface between an electronic-conducting electrode and the electrolyte[3], NiO-YSZ with porous structure is needed. In this work, the monodisperse PMMA spheres prepared by emulsifier-free emulsion polymerization [4] were used as the template. Metal salts were precipitated in the interstices of the template from the precursors. Calcination temperatures as high as 1100 were used to remove the polymer and convert the inorganic precursors into a macroporous skeleton of YSZ. The objective of this study was (1)to obtain the macroporous structure after removal of microsphere template (2)to examine the effect of calcinations temperature on the evolution of macroporous structure.

conducted at 80 for 1h to prepare fine PMMA spheres as shown in Fig.1. To prepare the macroporous NiO-YSZ structure, zirconium acetate, yttrium acetate and nickel acetate were dissolved in methanol as the precursors. Then the precursor solution was permeated into the PMMA microspheres on YSZ substrate. After drying, the PMMA microspheres were removed by thermal decomposition at 400 for 2h. As shown in Fig. 2, the subsequent heat treatment was conducted to obtain
MMA + D.I water K2S2O8 + D.I

Through N2

Heating

Washing

Deposition &

SEM
Figure 1. Procedures for preparation of PMMA spheres

2.

Material and Method

The monodisperse PMMA spheres were synthesized by emulsifier-free emulsion polymerization with methyl methacrylate (MMA) as the monomer. The reaction was

desired NiO-YSZ structure at 800~1000 for 4h[5]. The macroporous structure of NiO-YSZ was examined by SEM (SEM Hitachi 3000). The crystal structure of

Fabrication of Macroporous NiO-YSZ Anode using Template-assisted Method derived NiO-YSZ from the precursors was examined using XRD. spheres at this temperature range. According to the result of TG curve shown in Fig.4, the PMMA spheres also showed significant loss of weight starting at about 260. The loss of weight for PMMA spheres continued with the temperature arising. Finally, the weight loss was not detected at 380. Based on this result, it is important to heat up the samples slowly below 380since the large amount of gases was generated during thermal decomposition. Moreover, the porous structure formed after PMMA spheres were removed from the samples.

PMM A

Y(NO3)
3

Ni(CH3COO)2

Deposition ZrO(NO3)2/ ZrOCl2 Heat treatment D.I Water Filled with YSZ precursor NiO/YSZ precursor

Calcining

SE M

Figure 4. DTA/TG curves of PMMA spheres analyzed with a heating rate of 5 /min at air

Figure 2. Flow chart for preparation of macroporous NIO-YSZ

(a)

u
(a) (b)
Figure 3. SEM pictures of as-deposited PMMA spheres with diameters 1.6m (a)Low-magnification; (b)High-magnification

(b)

(c)

3.

ResultsandDiscussion

Figure 5. The SEM pictures of macroporous NiO/YSZ prepared by 1.6m PMMA spheres sintered at (a) 800 (b) 900 (c)1000 for 4hrs.

Fig. 3 shows the monodisperse PMMA spheres with uniform diameters prepared by emulsifier-free emulsion polymerization. Very uniform PMMA microspheres were observed although few slightly larger spheres were present as well. According to the result of DTA curve shown in Fig.4, the PMMA spheres showed exothermic reaction between the 260 and 380. This exothermic reaction was caused by the thermal oxidation of PMMA

Fig. 5 shows the SEM micrographs of macroporous NiO-YSZ fabricated from NiO-YSZ precursor solution at different temperatures. Figure 5(a) shows the macroporous NiO-YSZ fabricated on YSZ substrate using 0.3M precursor solution after heat-treatment at 800oC. The formation of pores clearly was due to the thermal decomposition of PMMA spheres. In additions, the precursors also converted to oxides and formed 3D

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Fabrication of Macroporous NiO-YSZ Anode using Template-assisted Method network after high temperature heat treatment. As the temperature increased from 800 oC to 900 oC and 1000 oC, the macroporous structure was not changed significantly because the sintering temperature was not reached yet. In this micrograph, the macroporous structure was not continuous and few large pores were observed. The polymer microspheres were entirely surrounded by precursor. After the heat treatment at 400 the polymer PMMA spheres was removed and the macroporous structure NiO-YSZ was formed. As seen in Fig.6(c) NiOYSZ formed a 3-D network structure with numerous pores (~800nm). To verify the structure of NiO-YSZ, the X-ray diffraction analysis was used. Fig.7 shows that crystallized NiO-YSZ formed after calcining at 1100 for 4h. From the XRD analysis, YSZ showed cubic fluorite-type structure and NiO showed cubic rock-salt type structure.
(a)

4.

Conclusions

(b)

(c)

Figure 6. SEM photographs of macroporous NiO-YSZ fabricated from (a) 0.3M (b) 0.4M (c) 0.5M NiO-YSZ precursor solution

The macroporous NiO-YSZ structure has been successfully fabricated by a template-assisted method employing the monodisperse PMMA spheres prepared by emulsifier-free emulsion polymerization with diameters about 1m as template. According to the analysis of TG/DTA, it was found that the PMMA spheres had obvious exothermic curve between the 260~380 and weight loss starting at about 260. No further weight loss was observed at temperatures higher than 380. In order to maintain the framework and prevent from collapse, the concentration of NiO-YSZ precursor solution needs to be higher than 0.4M. The calcinations temperature must be higher than 800oC. The resulting pore size after heat treatment was about 800nm formed by the removal of PMMA spheres. Finally, fluorite and rock-salt structures of YSZ and NiO were confirmed from the XRD analysis.. ACKNOWLEDGMENT This work is financially supported by the National Science Council under Grant NSC 98-3114-E-006-005 REFERENCES
[1] F.J. Rorh, in : P. Hagenmuller, W. Vangool, (Eds.), Solid Electrolytes, Academic Press, New York, 1978, p.431.

Figure 7. The XRD pattern of macroporous NiO-YSZ calcining at 1100 for 4h.

Thus, this result indicates that the amount of NiOYSZ is not enough to fill into the space between polymer spheres. Figure 6 shows the SEM micrographs of macroporous NiO-YSZ fabricated from NiO-YSZ precursor solution with different concentration.. When the concentration of precursor solution increased to 0.4M, the framework of macroporous NiOYSZ was established. However, the bottom of few pores was still not completely filled. Finally, when the concentration of precursor solution increased to 0.5M, the oxide obtained after heat treatment.

[2] F.J. Rorh, in : H.S. Isaacs, S. Srinivasan, I.L. Harry (Eds.), Proc. Workshop on High Temperature Solid Oxide Fuel Cells, Brookhaven National Laboratory, Upton, NY, 1978, p.122. [3] Y. Zhang, S. Zha, M. Liu, Adv. Mater., 4, 487(2005). [4] S.M. Klein, V.N. Manoharan, D.J. Pine, F.F. Lange, Colloid Polym. Sci., 282, 7-13(2003). [5] K. Sasahara, T. Hyodo, Y. Shimizu, M. Egashira, Euro. Soi., 24, 1961-1967(2004). Ceram.

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