New Journal of Glass and Ceramics, 2011, 1, 58-62

doi:10.4236/njgc.2011.12007 Published Online July 2011 (http://www.SciRP.org/journal/njgc)

Synthesis and Characterization of La0.75Sr0.25Cr0.5Mn0.5O3- Nanoparticles Using a Combustion Method for Solid Oxide Fuel Cells
V. S. Reddy Channu , Rudolf Holze , Edwin H. Walker Jr. , Rajamohan R. Kalluru
1

Institut fr Chemie, AG Elektrochemie, Technische Universitt Chemnitz, Chemnitz, Germany; 2Department of Chemistry, Southern University and A&M College, Baton Rouge, USA; 3KITE College of Professional Engineering Sciences, Jawaharlal Nehru Technological University of Hyderabad, Shabad, India. Email: subbu5reddy@yahoo.co.in Received April 11th, 2011; revised May 9th, 2011; accepted May 16th, 2011.

ABSTRACT
La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite nanoparticles for use as anode material in intermediate temperature solid oxide fuel cells (IT-SOFCs) were synthesized using 3,3,3-nitrilotripropionic acid (NTP), citric acid and oxalic acid as carriers via a combustion method. The influence of the carrier on phase and morphology of the obtained pristine products was characterized using X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM). XRD results showed, that the LSCM had rhombohedral symmetry with R-3c space group; a single phase LSCM perovskite formed after calcination of fired gel at 1200C for 7 h. Scanning electron microscopy analysis of the pristine powders showed spherical shape and particle sizes in the range of 50 - 500 nm.. Keywords: Nanoparticles, Combustion method, Morphology, Carriers

1. Introduction
A fuel cell is an electrochemical device that converts chemical energy of fuels (hydrogen, methane, butane or even gasoline and diesel) into electrical energy by exploiting the natural tendency of oxygen and hydrogen to react. Fuel cells are simple devices containing no moving parts and only four functional components namely cathode, electrolyte, anode and interconnect. Solid oxide fuel cells (SOFCs) are considered to be among the most versatile power production facilities. Their unique characteristics include extreme efficiency, significant energy conversion rate with a wide range of fuels and pollution-free operation. On the other hand high operating temperature (about 1000C) of the SOFC results in problems including difficult sealing between cells with flat plate configurations and thermal expansion mismatches between components. In addition, the high operating temperature places rigorous constraints on materials selection and results in difficult fabrication processes [1]. Recently, perovskite based conducting oxides, such as

substituted lanthanum chromites or lanthanum manganates and strontium titanates, received great attention as alternative anode materials for solid oxide fuel cells [2]. Particularly, (La0.75Sr0.25)1-xCr0.5Mn0.5O3 perovskite phase (LSCM) has been considered as a capable anode material for SOFCs due to its electrocatalytic/catalytic activity for oxidation of methane fuel in the absence of steam, reduced carbon deposition, and high durability against sulfur poisoning and good electrical properties [3,4]. Predominantly, this composition of LSCM has shown good stability in fuels and in air, and has good resistance towards carbon deposition and low polarization resistance when used with hydrocarbon fuels [5]. LSCM can also be used as a cathode, thus facilitating fuel cells with a symmetrical structure (LSCM/electrolyte/LSCM) [6,7]. Up till now, various chemical methods were reported in the literature for the synthesis of LSCM powders, for example, glycine nitrate method [3], EDTA (ethylenedia minetetraacetic acid) chelating method [8,9], combustion synthesis [7,10], solid-state reaction [4,6,11-15], gel-casting [16,17] and co-precipitation method [18]. The solid-state

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method has some disadvantages such as high temperature (above 1300C) and long duration of synthesis of LSCM and non-homogeneity in particle size and low purity [19]. However, to synthesize homogeneous fine particles of pure phase LSCM powders requires low temperature and short duration of synthesis. The solution combustion method is suitable to synthesize nanosize LSCM particles with good homogeneity [20]. The present work reports on the synthesis of nanostructured La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) perovskite by a combustion method using 3,3,3-nitrilotripropionic acid, oxalic acid and citric acid as carriers.

2. Experimental
Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) perovskite anode material was synthesized by a combustion technique. Three batches of LSCM solutions are prepared with stoichiometric amounts of lanthanum nitrate (La(NO3)36H2O), strontium nitrate (Sr(NO3)2), chromium nitrate (Cr(NO3)39H2O) and manganese nitrate (Mn(NO3)2) in distilled water under constant stirring. First, a stoichiometric amount of citric acid (C6H8O7 H2O) and 15 ml ethylene glycol, second, oxalic acid and 15 ml ethylene glycol, and 3,3,3-nitrilotripropionic acid and 15 ml ethylene glycol which are chelating agents and fuel, were also dissolved in LSCM solution. The stoichiometric ratio of carriers to nitrates was 2 [21]. A gel was formed with continuous stirring and mild heating at 120C. The gel was dried at room temperature for overnight and then heated at 350C for 30 min. The resulting powders were ground in an agate mortar and heated in air at 1000C for 7 h. Finally, the ground product was heated at 1200C for 7 h in air. Crystallographic information of the samples was obtained using an X-ray powder diffractometer (D8 Advanced Brucker) with graphite monochromatized Cu K radiation ( = 1.54187 ). Diffraction data were collected over the 2 range of 15 to 80. The morphol ogies of the resulting products were characterized using a scanning electron microscope (SEM, JEOL JSM 6390). For the TGA measurements a TA 600, operating in dynamic mode (heating rate = 10C/min), was employed.

rhombohedral symmetry with a = 5.4736 , b = 5.4736 , c = 13.2898 and R-3c space group (JCPDS # 01-070-8673). No impurity phases were observed presumably because in the solid-state reaction the pure phase of La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite was formed at 1200C [21]. The crystallite size of the LSCM nanoparticles was calculated using Debye-Scherrer formula at (110) plane. The size of the LSCM-particles prepared NTP-assisted is 57.65 nm, with citric acid and oxalic acid the value is 68.63 nm. In the synthesis of La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite nanoparticles the carriers (NTP, oxalic acid and citric acid) help in obtaining a homogeneous mixture of the cations in a solution through forming metal complexes, they also help in the reduction of nitrates in a combustion process, releasing a large amount of heat. This is shown by an exothermic peak at 377C on a DSC curve (Figure 2). During the solid-state reduction process, metal cations and oxygen anions stay in the react and mixture during the formation of perovskite phase in this combustion process. The large heat released during combustion might be of the help to overcome the lattice energy, which is required for the formation of the perovskite phase, and also the completion of the nucleation by the rearrangement of atoms by short distance diffusion. The fast combustion process might not be of help for the diffusion of atoms far from each other and hence the particle size of LSCM powder remained in the nanometer range [22]. Thermogravimetric analysis and differential scanning calorimetry (TGA-DSC) curves with NTP-assisted LSCM dried as a gel at 120C are shown in Figure 2. The weight losses happen in three steps. The total weight loss
(024) (110) (104)(202) (113) (006)
(JCPDS # 01-070-8673)

(012)

(214)

Intensity/s-1

La0.75Sr0.25Cr0.5Mn0.5O3-(CA+EG at 1200OC)

68.63 nm
La0.75Sr0.25Cr0.5Mn0.5O3-(OA+EG at 1200OC)

68.63 nm

3. Results and Discussion

Phase purity and crystallographic information of the synthesized La0.75Sr0.25Cr0.5Mn0.5O3-perovskite nanoparticles were characterized using powder X-ray diffraction. The XRD patterns of LSCM perovskite nanoparticles are shown in Figure 1. All diffraction patterns of La0.75Sr0.25Cr0.5Mn0.5O3- perovskite nanoparticles show characteristic peaks of the perovskite phase. The XRD patterns are in good agreement with the standard data for
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57.65 nm
La0.75Sr0.25Cr0.5Mn0.5O3-(NTP +EG at 1200OC)

20

30

40

50

60

70

80

2/

Figure 1. XRD patterns of La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite phase nanoparticles.

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Synthesis and Characterization of La0.75Sr0.25Cr0.5Mn0.5O3- Nanoparticles Using a Combustion Method for Solid Oxide Fuel Cells
6 0.33mg TGA DSC 5
Weight loss/mg

200
6.0 0.32mg 0.9mg

100
5.5

0 1.25 mg -100

Weight loss/mg

0.2mg 0.25mg

Heat flow (mW)

5.0 4.5 4.0 3.5

0.42mg LaSrCrMnO3+NTP LaSrCrMnO3+Citiric Acid LaSrCrMnO3+Oxalic Acid 0 200 400 600 800 1000 1200 1400

0.5mg

-200 LaSrCrMnO3+NTP -300

3 0 200 400 600 800 1000 1200 1400 Temperature/OC

Temperature/OC

Figure 2. TGA-DSC curves of La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite gel precursor dried at 120C.

Figure 3. TGA curves of La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite gel precursor dried at 120C and then fired at 350C for 1h.

was 2.1 mg from room temperature to 1300C. The first weight loss is 0.33 mg in the temperature range 22C 236C; this can be attributed to evaporation of water from the layers of LSCM. The second weight loss is 1.25 mg in the temperature range 236C - 383C and the third weight loss is 0.5 mg in the temperature range 383C 837C. The second and third weight losses are attributed to decomposition of the carrier (NTP) and evaporation of structurally bounded water. The peaks located at about 295C and 377C are exothermic on the DSC curve due to decomposition of nitrates and organic matter and correspond to the second weight loss of 1.25 mg from about 236C to 400C as observed in the TGA curve. To observe thermal effects above 350C, different carrier-assisted LSCM samples were fired at 350 C for 1 h. Figure 3 shows TGA-DTA curves of the different carriers assisted LSCM samples. The total weight loss was 0.97 mg in NTP assisted LSCM, 0.39 mg in oxalic acid assisted LSCM, and 0.77 mg in citric acid assisted LSCM from room temperature to 1300C. The first weight loss is 0.32 mg in NTP assisted LSCM in the temperature range 30C - 490C, whereas the first weight loss is 0.2 mg in the oxalic acid used LSCM in range 30C - 338C and the first weight loss is 0.25 mg in citric acid used LSCM in range 30C - 334C. The second weight loss is 0.9 mg in NTP used LSCM in the temperature range 490C - 822C, whereas the second weight loss is 0.42 mg in citric acid used LSCM in range 334C 688C. The second weight loss was attributed to the reaction between the residual nitrate and carriers after the decomposition of the precursor and subsequent combustion of organic components. The morphologies of La 0.75Sr0.25Cr0.5Mn0.5O3- perovskite nan-oparticles synthesized using different carCopyright 2011 SciRes.

1m

(a)

1m

(b)

1m

(c) Figure 4. SEM images of La0.75Sr0.25Cr0.5Mn0.5O3- perovskite phase nanoparticles (a) NTP-assisted, (b) oxalic acid assisted and (c) citric acid assisted.

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riers by combustion method as examined with scanning electron microscopy are shown in Figure 4. NTP-assisted LSCM shows many nanosized particles of sphericalshape in the range 100 - 500 nm (Figure 4(a)). The LSCM powders synthesized using oxalic acid and citric acid as carriers consist of uniform nanoparticles shwoing less agglomeration. The average particle size of the La0.75Sr0.25Cr0.5Mn0.5O3- perovskite powders calcinated at 1200C is about 50 - 500 nm (Figures 4(a) and (b)). The small size La0.75Sr0.25Cr0.5Mn0.5O3- perovskite nanoparticles are very active, small size is also beneficial for decreasing the fabrication temperature of the anode film and enhancing the catalytic properties.

Vol. 2, No. 5, 2003, pp. 320-323. doi:10.1038/nmat871 [6] J. C. Ruiz-Morales, J. Canales-Vazquez, J. Pena-Martinez, D. M. Lopez and P. Nunez, On the Simultaneous Use of La0.75Sr0.25Cr0.5Mn0.5O3 as Both Anode and Cathode Material with Improved Microstructure in Solid Oxide Fuel Cells, Electrochim. Acta, Vol. 52, No. 1, 2006, pp. 278-284. doi:10.1016/j.electacta.2006.05.006 D. M. Bastidas, S. Tao and J. T. S. Irvine, A Symmetrical Solid Oxide Fuel Cell Demonstrating Redox Stable Perovskite Electrodes, Journal of Materials Chemistry, Vol. 16, No. 17, 2006, pp. 1603-1605. doi:10.1039/b600532b J. Wan, J. H. Zhu and J. B. Goodenough, La0.75Sr0.25 Cr0.5Mn0.5O3 + Cu composite anode running on H2 and CH4 fuels, Solid State Ionics, Vol. 177, No. 13-14, 2006, pp. 1211-1217. doi:10.1039/b600532b X. C. Lu and J. H. Zhu, Cu(Pd)-Impregnated La0.75Sr0.25 Cr0.5Mn0.5O3 Anodes for Direct Utilization of Methane in SOFC, Solid State Ionics, Vol. 178, No. 25-26, 2007, pp. 1467-1475. doi:10.1016/j.ssi.2007.09.001

[7]

[8]

4. Conclusions
La0.75Sr0.25Cr0.5Mn0.5O3- (LSCM) perovskite phase nanoparticles were successfully synthesized by solution combustion method using different carriers (NTP, oxalic acid, and citric acid) after calcination of fired gel at 1200C for 7 h. Scanning electron microscopy of the as-synthesized powders showed spherical particle shapes and sizes in the range of 50 - 500 nm. An exothermic reaction between carriers and nitrates initiates the combustion process. TGA and DSC analysis confirmed the decomposition process of nitrates and the organic matter. The combustion reactions took place in the temperature range 200C to 400C.
[9]

[10] B. Huang, S. R. Wang, R. Z. Liu, X. F. Ye, H. W. Nie, X. F. Sun and T. L. Wen, Performance of La0.75Sr0.25Cr0.5 Mn0.5O3 Perovskite-Structure Anode material at Lanthanum Gallate Electrolyte for IT-SOFC Running on Ethanol Fuel, Journal of Power Sources, Vol. 167, No. 1, 2007, pp. 39-46. doi:10.1016/j.jpowsour.2007.02.022 [11] S. P. Jiang, X. J. Chen, S. H. Chan and J. T. Kwok, GDC-Impregnated (La0.75Sr0.25)(Cr0.5Mn0.5)O3 Anodes for Direct Utilization of Methane in Solid Oxide Fuel Cells, Journal of Electrochemical Society, Vol. 153, No. 5, 2006, pp. A850-A856. doi:10.1149/1.2179347 [12] J. Pena-Martinez, D. Marrero-Lopez, J. C. Ruiz-Morales, B. E. Buergler, P. Nunez and L. J. Gauckler, Fuel Cell Studies of Perovskite-Type Materials for IT-SOFC, Journal of Power Sources, Vol. 159, No. 2, 2006, pp. 914-921. doi:10.1016/j.jpowsour.2005.11.036 [13] S. P. Jiang, X. J. Chen, S. H. Chan, J. T. Kwok, K. A. Composite Khor, (La0.75Sr0.25)(Cr0.5Mn0.5)O3/YSZ Anodes for Methane Oxidation Reaction in Solid Oxide Fuel Cells, Solid State Ionics, Vol. 177, No. 1-2, 2006, pp. 149-157. doi:10.1016/j.ssi.2005.09.010 [14] J. Pena-Martinez, D. Marrero-Lopez, J. C. Ruiz-Morales, C. Savaniu, P. Nunez and J. T. S.Irvine, Anodic Performance and Intermediate Temperature Fuel Cell Testing of La0.75Sr0.25Cr0.5Mn0.5O3- at Lanthanum Gallate Electrolytes, Chemistry of Materials, Vol. 18, 2006, pp. 1001-1006. [15] J. C. Ruiz-Morales, J. Canales-Vazquez, B. Ballesteros-Perez, J. Pena-Martinez, D. Marrero-Lopez, J. T. S. Irvine and P. Nunez, LSCM(YSZCGO) Composites as Improved Symmetrical Electrodes for Solid Oxide Fuel Cells, Journal of the European Ceramic Society, Vol. 27, No. 13-15, 2007, pp. 4223-4227. doi:10.1016/j.jeurceramsoc.2007.02.117 [16] S. P. Jiang, L. Zhang and Y. Zhang, Lanthanum Stron-

5. Acknowledgements
One of the authors (V S Reddy Channu) thanks the Alexander von Humboldt Foundation for a fellowship.

REFERENCES
[1] Ch. Sun and U. Stimming, Recent Anode Advances in Solid Oxide Fuel Cells, Journal of Power Sources, Vol. 171, No. 2, 2007, pp. 247-260. doi:10.1016/j.jpowsour.2007.06.086 E. Lay, G. Gauthier, S. Rosini, C. Savaniu and J. T. S. Irvine, Ce-Substituted LSCM as New Anode Material for SOFC Operatingin Dry Methane, Solid State Ionics, Vol. 179, No. 2, 2008, pp.1562-1566. doi:10.1016/j.ssi.2007.12.072 S. Zha, P. Tsang, Z. Cheng and M. Liu, Electrical Properties and Sulfur Tolerance of La0.75Sr0.25Cr1xMnxO3 under Anodic Conditions, Journal of Solid State Chemistry, Vol. 178, No. 6, 2005, pp. 1844-1850. doi:10.1016/j.jssc.2005.03.027 S. Tao and J. T. S. Irvine, Synthesis and Characterization of (La0.75Sr0.25)Cr0.5Mn0.5O3A Redox-Stable, Efficient Perovskite Anode for SOFCs, Journal of the Electrochemical Society, Vol. 151, No. 2, 2004, pp. A252-A259. doi:10.1149/1.1639161 S. TaO and J. T. S. Irvine, A Redox-Stable, Efficient Anode for Solid-Oxide Fuel Cells, Nature Materials,

[2]

[3]

[4]

[5]

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Synthesis and Characterization of La0.75Sr0.25Cr0.5Mn0.5O3- Nanoparticles Using a Combustion Method for Solid Oxide Fuel Cells tium Manganese Chromite Perovskite Oxides Synthesized by Gelcasting for Solid Oxide Fuel Cells, Journal of Material Chemistry, Vol. 17, No. 25, 2007, pp. 26272635. doi:10.1039/b701339f Oxidation, Materials Letters, Vol. 59, No. 11, 2005, pp. 1373-1377. doi:10.1016/j.matlet.2004.12.047 [20] K. C. Patila, S. T. Arunab and T. Mimania, Combustion Synthesis: An Update, Current Opinion in Solid State and Materials Science, Vol. 6, No. 6, 2002, pp. 507-512. doi:10.1016/S1359-0286(02)00123-7 [21] M. A. Raza, I. Z. Rahman and S. Beloshapkin, Synthesis of Nanoparticles of La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) Perovskite by Solution Combustion Method for Solid Oxide Fuel Cell Application, Journal of Alloys and Compounds, Vol. 485, No. 1-2, 2009, pp.593-597. doi:10.1016/j.jallcom.2009.06.059 [22] B. Liu and Y. Zhang, Ba0.5Sr0.5Co0.8Fe0.2O3 Nanopowders Prepared by Glycine-Nitrate Process for Solid Oxide Fuel Cell Cathode, Journal of Alloys and Compounds, Vol. 453, No. 1-2, 2008, pp. 418-422. doi:10.1016/j.jallcom.2006.11.142

[17] L. Zhang, S. P. Jiang, C. S. Cheng and Y. Zhang, Synthesis and Performance of (La0.75Sr0.25)1x(Cr0.5Mn0.5)O3 Cathode Powders of Solid Oxide Fuel Cells by GelCasting Technique, Journal of Electrochemical Society, Vol. 154, No. 6, 2007, pp. B577-B582. doi:10.1149/1.2724759 [18] S. B. Ha, P-S. Cho, Y. H. Cho, D. Lee and J.-H. Lee, Preparation of La0.75Sr0.25Cr0.5Mn0.5O3 Fine Powders by Carbonate Coprecipitation for Solid Oxide Fuel Cells, Journal of Power Sources, Vol. 195, No. 1, 2010, pp. 124-129. doi:10.1016/j.jpowsour.2009.06.078 [19] Z. Hu, Y. Yang, X. Shang and H. Pang, Preparation and Characterization of Nanometer Perovskite-Type Complex Oxides LaMnO3.15 and Their Application in Catalytic

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