Electrochemistry Communications 13 (2011) 570573

Contents lists available at ScienceDirect

Electrochemistry Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e l e c o m

Preparation and characterization of nano-tube and nano-rod structured La0.8Sr0.2MnO3-/Zr0.92Y0.08O2 composite cathodes for solid oxide fuel cells
Naiqing Zhang a,, Juan Li b, Zhilong He b, Kening Sun a,
a b

Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150001, PR China Department of Chemistry, Harbin Institute of Technology, Harbin 150001, PR China

a r t i c l e

i n f o

a b s t r a c t
In this work, La0.8Sr0.2MnO3-/Zr0.92Y0.08O2 (LSM/YSZ) composite nano-tubes are co-synthesized by a pore wetting technique as a cathode material for solid oxide fuel cells (SOFCs). A fast-ring method is introduced to improve the contact between the composite cathode and the YSZ electrolyte, as well as to retain the original nano-tube structure. The morphology and structure studies indicate that the LSM/YSZ composite cathodes which undergo a 1100 C heat treatment present nano-tube and nano-rod structure (with heating and cooling rates of 200 and 100 C min1). Area specic resistance (ASR) of the composite cathodes is characterized by electrochemical impedance spectroscopy. The as-prepared nanostructured composite cathode shows low ASR values, which is mainly due to small grain size, homogeneous particle distribution and ne pore structure of the material. 2011 Elsevier B.V. All rights reserved.

Article history: Received 29 January 2011 Received in revised form 9 March 2011 Accepted 9 March 2011 Available online 17 March 2011 Keywords: Solid oxide fuel cells Composite cathodes Nano-tube Nano-rod

1. Introduction Research on novel electrode materials [13] and/or unique microstructure [46] is one of the critical issues in the development of new generation solid oxide fuel cells (SOFCs). Nanomaterials, including nano-wires, nano-tubes, nano-rods and nano-belts, have great potential to increase the triple phase boundary (TPB, where the gas, electrode, and electrolyte are in contact) length and dramatically enhance the SOFC performance. Recently, Bellino et al. [5,7] reported the synthesis of cobaltite nano-tubes and a new architecture based on these materials as cathodes for SOFCs, which show impressively low polarization resistance. So far, cobaltite nano-tubes have been used to fabricate cathodes for SOFCs. However, the fabrication of composite cathodes showing nano-tube structure has not yet been reported. It is well known that the addition of an ionically conductive phase to the electronic or mixed ionic and electronic conductive (MIEC) oxides signicantly reduces the interfacial resistance compared to that of single-phase oxides [813]. Thus, it is of great signicance to develop nano-tube structured composite cathodes which will combine the above mentioned advantages. In this study, La0.8Sr0.2MnO3-/Zr0.92Y0.08O2 (LSM/YSZ) composite nano-tubes were co-synthesized by pore

wetting technique as cathode materials for SOFCs. Fast-ring method was used to attach the composite cathode to the electrolyte. When used as cathode in SOFCs, the as-prepared nanostructured composites of LSM/YSZ show low area specic resistance (ASR) values.

2. Experimental Commercial polycarbonate (PC) membranes (Whatman, UK) with pore size of 400 nm were used as templates. The mixture (0.15 mol L1) of La(NO3)36H2O, Sr(NO3)2, Mn(NO3)24H2O, Y(NO3)36H2O and ZrO (NO3)22H2O in de-ionized water was stirred for 20 min to make the precursor solution of La0.8Sr0.2MnO3- and Zr0.92Y0.08O2 (weight ratio 1:1). A few drops of the precursor solution were spread on a glass slide and covered with the PC membranes. The membranes would be lled with the solution due to capillary force. After having been kept at 30 C in a vacuum for 12 h, the lled PC membranes were calcined in a furnace at 800 C for 10 min with the heating rate of 2 C min1 and cooled to room temperature naturally in the furnace. The resulting powder was a collection of LSM/YSZ composite nano-tubes. The resulting samples were characterized by means of X-ray diffraction (XRD, Rigaku D/max-B) using Cu K radiation. The crystalline size was calculated based on Scherrer's equation. The morphology and microstructure of the samples were examined by scanning electron microscope (SEM, FEI Quanta 200f, Holland) and transmission electron microscope (TEM, FEI Tecnai G2, Holland) operating at 300 kV.

Corresponding authors. Tel./fax: +86 451 8641 2153. E-mail addresses: znqmww@163.com (N. Zhang), keningsun@yahoo.com.cn (K. Sun). 1388-2481/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2011.03.012

N. Zhang et al. / Electrochemistry Communications 13 (2011) 570573

571

A three-electrode cell was fabricated for electrochemical impedance spectroscopy (EIS) measurements, as described in our previous paper [8]. Measurements were taken in air over a temperature range of 700850 C, at zero bias. A screen printed layer of LSM/YSZ composites on the YSZ electrolyte was sintered through a fast-ring technique at 1100 C for 1 min with heating and cooling rates of 100 and 200 C min1, respectively. The cathode area was 0.25 cm2. The Ni/YSZ anode-supported YSZ electrolyte was prepared by tape-casting for fuel cell tests, as introduced in our previous paper [14]. 3. Results and discussion The SEM micrograph of LSM/YSZ composite nano-tubes fabricated with template-directed synthesis method is shown in Fig. 1a. The nano-tubes were found to be 46 m in length and 260 10 nm in outer diameter. Furthermore, the microstructures of the composite nano-tubes were investigated directly by taking the TEM image (Fig. 1b), indicating that the composites consist of nanometer sized LSM and YSZ particles (1015 nm). The XRD pattern of the LSM/YSZ nano-tubes after calcination at 800 C is presented in the inset of Fig. 1a. We can see that all peaks agree well with the uorite YSZ and perovskite LSM phases. The mean crystalline size estimated with Scherrer's equation is approximately 17.6 nm and 10.3 nm for LSM and YSZ, which agrees well with the TEM image shown in Fig. 1b. It is well known that signicant grain growth leads to severe agglomeration of nanomaterial at temperatures 1000 C [5]. In this report, a fast-ring process with fast heating and cooling rates as well as a short dwell time was carefully chosen, aiming to suppress the

grain growth and retain the nano-tube structure simultaneously. The as-prepared LSM/YSZ composite nano-tubes were screen-printed onto solid YSZ electrolytes, followed by heating at 1100 C for 1 min with heating and cooling rates of 200 and 100 C min1 (coded as L/Y200 and L/Y100). Fig. 1c and d compared the micrographs of different cathodes. It can be observed that the L/Y100 composite cathode turns into dense nano-rods while the hollow nano-tube structure is retained for L/Y200 cathode. The inset in Fig. 1c shows the cross-section SEM micrograph of the L/Y200 sample. The 12 m thick cathode lm has good contact with the electrolyte membrane. The fast ring prole recommended to maintain the nanostructures will put thermal stresses on the SOFCs during preparation. In order to validate the application of fast ring in the state-of-the-art SOFC architecture, the power output test on a real SOFC device has been conducted. The IV curve of the fuel cell is shown in the inset of Fig. 2a. The OCVs which are very close to the cell theoretical voltage in the testing temperature range from 650 to 800 C certify the high quality of YSZ electrolyte lm. Thus, the YSZ electrolyte thin lm could endure the thermal stresses. To understand the inuence of heating rate on the electrochemical performance of SOFC cathodes, the two types of cathodes (L/Y200 and L/Y100) were investigated by EIS measurements at 700850 C in air atmosphere. Fig. 2a displays the evolution of the Nyquist plots with temperature for the L/Y200 cathode. The resistances were obtained by tting EIS data with the equivalent circuit model LRel(QRH)(QRL). The intercept of the semicircle on the real axis in the high frequency represents the ohmic resistance (Rel), and (RHQ), (RLQ) represent the high frequency and low frequency arc, respectively. The radius

Fig. 1. (a) SEM and (b) TEM micrographs of LSM/YSZ composite nano-tubes, the inset in (a) is the XRD pattern of the nano-tubes; Surface SEM micrographs of LSM/YSZ composite cathodes sintered at 1100 C for 1 min with heating and cooling rates of (c) 200 C min1 and (d) 100 C min1, the inset in (c) is the corresponding cross-section SEM micrograph.

572

N. Zhang et al. / Electrochemistry Communications 13 (2011) 570573

difference of the arc between the intercepts in the high- and lowfrequency region on the real axis corresponds to the ASR of the cathode. Fig. 2b shows the resistances of L/Y200 and L/Y100 composite cathodes as a function of temperature. The L/Y200 composite cathode was found to have ASR values of 0.17, 0.25, 0.39 and 0.52 cm2 at 850, 800, 750 and 700 C, respectively, which are lower than that of the L/Y100 composite cathode, reaching correspondingly 0.37, 0.49, 0.73 and 1.18 cm2. Since the cathode composition and the test conditions are identical, the decrease in the ASR values can be ascribed to the microstructure difference of the cathodes. It is well known that the oxygen reduction reaction (ORR) on a SOFC cathode takes place at the TPB region. In composite cathodes, it is generally recognized that the TPB region expands from the limits of the two-dimensional interface between cathode and electrolyte to the entire cathode. A schematic diagram was used to explain the ORR on the nano-tube and nano-rod LSM/YSZ composite cathodes, as shown in Fig. 2c. Due to the hollow structure of L/Y200 composite cathodes, the ORR takes place at both inner and outer surfaces of the nano-tubes, while only on the outer surface for the nano-rod structure in L/Y100 cathodes. Moreover, pores of submicron and nanometer scale were found in L/Y200 composite cathodes. Such architecture facilitates the gas-phase diffusion processes [15], which contributes a low ASR value. Up to now, various approaches have been suggested to fabricate LSM/YSZ composite cathodes for SOFCs. These reported ASR values of cathodes are summarized in Table 1. It is worth noting that the ASRs reported in this study are substantially lower than those reported in the literature [4,813]. Especially, the as-prepared composite cathode is favorable for a relatively low temperature, e.g. 700 C. Several groups have pointed out that electrode microstructure (i.e., particle size, pore size, and porosity) has a strong inuence on the value of ASR [46]. Thus, the promising performance of the nanostructured L/Y200 composite cathodes is attributed to the optimized microstructure, i.e., small grain size, uniform size distribution, ne pore structure, and good inter-connectivity between LSM and YSZ particles. Although the L/Y200 composite cathode was found to have ASR value of 0.17 cm2 at 850 C, grain growth of the nanoparticles at such high temperature is inevitable for extended periods of time. However, LSM nanoparticles proved to be stable at 650 C [16], indicating that the durability of the nanostructures at a relatively low temperature is acceptable. Based on these considerations, the resultant microstructure proposed herein is more applicable for intermediate temperatures SOFCs. The durability of the resultant microstructure at intermediate temperatures will be tested further.
Fig. 2. (a) Nyquist plots of the L/Y200 composite cathode at 700850 C, symbols correspond to experimental data, solid lines correspond to tted results using the equivalent circuit LRel(QRH)(QRL), the numbers indicate the frequency (logarithm), and the inset shows the IV curve of the real SOFC device; (b) RH, RL and ASRs of L/Y200 and L/Y100 composite cathodes as a function of temperature; (c) Schematic illustration of the ORR on the nano-tube and nano-rod LSM/YSZ composite cathodes.

4. Conclusions Nanostructures of LSM/YSZ composite have been co-synthesized by using the pore wetting technique. SEM micrographs suggest that the

Table 1 Comparative ASR values and experimental parameters of LSM/YSZ composite cathodes based on YSZ electrolytes. Cathode La0.8Sr0.2MnO3--YSZ La0.7Sr0.3MnO3-YSZ La0.8Sr0.2MnO3--YSZ La0.8Sr0.2MnO3--YSZ La0.8Sr0.2MnO3--YSZ La0.85Sr015MnO3--YSZ LSMYSZ (impregnation) Composition Thermal treatment (LSM:YSZ) 50:50 473221 80:20 50:50 50:50 8:2 1:1 1100 C, 1 min (200 C min 1) 1100 C, 4 h 1200 C, 2 h 1175 C, 1 h 1150 C, 4 h 1000 C, 3 h 650750 C, 1 h Thickness Mean particle Electrolyte (m) size 12 2530 10 2024 20 1 35 1020 80120 nm 3050 nm 12 m 200 nm 0.30.4 m 0.24 m YSZ 0.5 m impregnated LSM 50 nm 0.20.3 m 8YSZ, 0.7 mm 8YSZ, 0.5 mm 8YSZ, 0.6 mm 8YSZ , a 8YSZ, 1.2 mm 8YSZ, 0.5 mm 8YSZ, 10 m ASR (800 C) ASR (750 C) ASR (700 C) References ( cm2) ( cm2) ( cm2) 0.25 0.445 0.25 0.50
b

0.39
b

0.52 3.0
b b

0.52
b

0.58
b

1.31 1.63 0.74

2.49
b b

Present work Song et al. [4] Piao et al. [8] Wilson et al. [9] Murray et al. [10] Song et al. [11] Liang et al. [12]

(La0.85Sr015)0.9MnO3-- 6:4 Zr0.85Y015MnO1.92

a b

1150 C, 2 h

10

8YSZ, 0.2 mm

0.9

Kim et al. [13]

Not reported. Not reported or could not get precise values.

N. Zhang et al. / Electrochemistry Communications 13 (2011) 570573

573

nano-tube structure feature of LSM/YSZ is retained even after a 1100 C thermal treatment. The cathode with nano-tube structure shows ASR values of 0.17, 0.25, 0.39 and 0.52 cm2 at 850, 800, 750 and 700 C, respectively, much lower than those reported values of materials exhibiting conventional microstructures. The high specic surface area and multi-scale porosity of the nano-tube structure composite cathode are the main reasons for the promising performance. Acknowledgment This work is funded by National Natural Science Foundation of China (No. 20906015) and Natural Scientic Research Innovation Foundation of Harbin Institute of Technology (No. HIT.NSRIF.2008.23). References
[1] S.J. Lee, P. Muralidharan, S.H. Jo, D.K. Kim, Electrochem. Commun. 12 (2010) 808. [2] V.B. Vert, J.M. Serra, J.L. Jord, Electrochem. Commun. 12 (2010) 278.

[3] D.K. Niakolas, J.P. Ouweltjes, G. Rietveld, V. Dracopoulos, S.G. Neophytides, Int. J. Hydrogen Energ. 35 (2010) 7898. [4] H.S. Song, S. Lee, S.H. Hyun, J. Kim, J. Moon, J. Power Sources 187 (2009) 25. [5] M.G. Bellino, J.G. Sacanell, D.G. Lamas, A.G. Leyva, N.E. Walse de Reca, J. Am. Chem. Soc. 129 (2007) 3066. [6] M. Prestat, A. Morandi, A. Heel, L. Holzer, P. Holtappels, T.J. Graule, Electrochem. Commun. 12 (2010) 292. [7] J. Sacanell, A.G. Leyva, M.G. Bellino, D.G. Lamas, J. Power Sources 195 (2010) 1786. [8] J. Piao, K. Sun, N. Zhang, S. Xu, J. Power Sources 175 (2008) 288. [9] J.R. Wilson, J.S. Cronin, A.T. Duong, S. Rukes, H.Y. Chen, K. Thornton, D.R. Mumm, S. Barnett, J. Power Sources 195 (2010) 1829. [10] E.P. Murray, S.A. Barnett, Solid State Ionics 143 (2001) 265. [11] H.S. Song, S.H. Hyun, J. Moon, R.H. Song, J. Power Sources 145 (2005) 272. [12] F. Liang, J. Chen, S.P. Jiang, B. Chi, J. Pu, J. Li, Electrochem. Commun. 11 (2009) 1048. [13] J.H. Kim, R.H. Song, J.H. Kim, T.H. Lim, Y.K. Sun, D.R. Shin, J. Solid State Electrochem. 11 (2007) 1385. [14] X. Zhou, K. Sun, J. Gao, S. Le, N. Zhang, P. Wang, J. Power Sources 191 (2009) 528. [15] Y. Zhang, S. Zha, M. Liu, Adv. Mater. 17 (2005) 23. [16] T.Z. Sholklapper, V. Radmilovic, C.P. Jacobson, S.J. Visco, L.C. De Jonghe, Electrochem. Solid State Lett. 10 (2007) B74.