**6. References**

156 Electrochemical Cells – New Advances in Fundamental Researches and Applications

After the second layer deposition, the film covered most of these irregularities, achieving the aimed goal of the intermediate deposition protocol. However, the second and first layer overlapping, led to the formation of an even more irregular layer, both before (Figure 13a)

The same behavior was observed after the last deposition. This layer apparently had some leveling effect on the film, slightly reducing the surface irregularities (Figure 14a). There were no significant morphological changes after the final heat treatment (Figure 14b). For the protocol of multi-layer depositions, with intermediate heat treatment, a crack-free film

Fig. 14. SEM images of the film obtained from intermittent deposition at substrate temperature of 350 °C: (a) after the final deposition; (b) after the final heat treatment at

Results showed that YSZ films can be obtained directly on porous LSM substrate by spray pyrolysis technique. A dense and homogeneous film can be obtained by multi-layers

**(a) (b)**

The heat treatment at 700 °C allowed the stabilization of the zirconia cubic phase, which is the phase of interest for application as electrolyte in solid oxide fuel cells, as indicated by xray diffraction analysis and confirmed by the Fourier transform infrared spectroscopy

The type of solvent used influences in the morphology of the films obtained. Solvents that have very low boiling point lead to the uncontrolled evaporation of the solvent, forming a quite brittle film. The increase in the solvent boiling temperature helps to a proper evaporation, resulting in films with more satisfactory morphological characteristics. In all cases of one-layer deposition, heat treatment caused an increase of surface discontinuities,

and after heat treatment (Figure 13b).

700 °C for 2 hours.

**4. Conclusions** 

analysis.

deposition with intermediate heat treatment.

demonstrating its influence on the films morphology.

was obtained, but the surface presented a roughness increase.


Fuel Cell: A Review and a New Approach

*Meeting*, Vol. 1, pp. 568.

*Ionics.* Vol. 179, pp. 1268.

*Power Sources*. Vol. 101, pp. 259.

*Energy Reviews*. Vol 6, pp. 433.

*Power Sources.* Vol. 195, pp. 4570.

Wand, G. (2006). *Fuel Cell History*, Part 1.

104, pp. 4727.

254, pp. 7159.

1437.

Tin Oxide. *Thin Solid Films*. Vol. 165, pp. 265.

177, pp. 1981.

Switzerland.

About YSZ Solid Oxide Electrolyte Deposition Direct on LSM Porous Substrate by Spray Pyrolysis 159

Neagu, R., Perednis, D., Princivalle, A. & Djurado, E. (2006). Influence of the process

O'Sullivan, J. B. (1999). Fuel cells in distributed generation. *Power Engineering Society Summer* 

Perednis, D. & Gauckler, L. J. (2004). Solid oxide fuel cells with electrolytes prepared via

Perednis, D. (2003). Thin Film Deposition by Spray Pyrolysis and the Application in Solide

Ralph, J. M., Schoeler, A.C. & Krumpelt, M. (2001). Materials for lower temperature solid

Sasaki, K., Muranaka, M., Suzuki, A. & Terai, T. (2008). Synthesis and characterization of

Sauvet, A.-L. & Fouletier, J. (2001). Catalytic properties of new anode materials for solid

Sears, W.M. & Gee, M.A. (1988). Mechanics of Film Formation During the Spray Pyrolysis of

Srivastava, P.K., Quach, T., Duan, Y.Y., Donelson, R., Jiang, S.P., Ciacchi, F.T. & Badwal,

Stambouli, A.B. & Traversa E. (2002a). Fuel cells, an alternative to standard sources of

Stambouli, A.B. & Traversa, E. (2002b). Solid oxide fuel cells (SOFCs): a review of an

Tao, S. & Irvine, J.T.S. (2002). Optimization of Mixed Conducting Properties of Y2O3–ZrO2–

Tucker, M.C. (2010). Progress in metal supported solid oxide fuel cells: a review. *Journal of* 

Wang, C.Y. (2004). Fundamental Models for Fuel Cell Engineering*. Chemical Reviews*. Vol.

Wattnasiriwech, D. Wattnasiriwech, S. & Stevens R. (2006). A sol-powder coating technique

Xiaodong, H., Bin, M., Yue, S., Bochao, L. & Mingwei, L. (2008). Electron beam physical

by DC magnetron sputtering. *Solid State Ionics.* Vol. 99, pp. 311.

energy. *Renewable and Sustainable Energy Reviews.* Vol 6, pp. 297.

Suntola, T. (1992). Atomic layer epitaxy. *Thin Solid Films*. Vol. 216, pp. 84.

Materials. *Journal of Solid State Chemistry.* Vol. 165, pp. 12.

spray pyrolysis. *Solid State Ionics*. Vol. 166, pp. 229.

oxide fuel cells. *Journal of Material Science*. Vol. 36, pp. 1161.

parameters on the ESD synthesis of thin film YSZ electrolytes. *Solid State Ionics*. Vol.

Oxide Fuel Fuel Cells. *Docotorate Thesis - Suiss Federal Institute of Technology*, Zurich,

LSGM thin films electrolyte by RF magnetron spputering for LT-SOFCS. *Solid State* 

oxide fuel cells operated under methane at intermediary temperature. *Journal of* 

S.P.S. (1997). Electrode supported solid oxide fuel cells: Electrolyte films prepared

environmentally clean and efficient source of energy. *Renewable and Sustainable* 

TiO2 and Sc2O3–Y2O3–ZrO2–TiO2 Solid Solutions as Potential SOFC Anode

for fabrication of yttria stabilized zirconia. *Materials Research Bulletin*. Vol. 41, pp.

vapor deposition of YSZ electrolyte coatings for SOFCs. *Applied Surface Science*. Vol.


Farooque, M. & Maru, H. C. (2001). Fuel cells-the clean and efficient power generators. *IEEE* 

Fridleifsson, I.B. (2001) Geothermal energy for the benefit of the people. *Renewable and* 

Garcia, B. L., Sethuraman, V.A., Weidner, J. W., White, R.E. & Dougal, R. (2004).

Gaudon, M., Laberty-Robert, Ch., Ansart, F. & Stevens, P. (2006). Thick YSZ films prepared

Gong, M., Bierschenk, D., Haag, J., Poeppelmeier, K.R., Barnett, S. A., Xu, C., Zondlo, J.W. &

He, Z., Yuan, H., Glasscock, J.A., Chatzichristodoulou, C., Phair, J.W., Kaiser, A. &

Hui, S. & Petric, Q. A. (2001). Electrical Properties of Yttrium-Doped Strontium Titanate

Huijsmans, J.P.P. (2001). Ceramics in solid oxide fuel cells. *Cur. Opinion in Solid State and* 

Khollam, Y.B., Deshpande, A. S., Patil, A. J., Potdar, H. S., Deshpande, S. B. & Date, S. K.

Kueir-Weei, C., Jong, C. & Ren, X. (1997). Metal-organic vapor deposition of YSZ electrolyte

Louie, H. & Strunz, K. (2007) Superconducting Magnetic Energy Storage (SMES) for Energy

Mendez, V.H., Rivier, J., de la Fuente, J.I., Gómez, T., Arceluz, J., Marín, J. & Madurga, A.

*International Journal of Electrical Power and Energy Systems*. Vol 28, pp. 244. Minh, N. Q. (1993). Ceramic Fuel Cells. *Journal of American Ceramic Society*. Vol. 76 pp.

*Transactions on Applied Superconductivity*. Vol. 17, pp. 2361.

hydrothermal route. *Materials Chemistry and Physics*. Vol. 71, pp. 235. Kirubakaran, V., Sivaramakrishnan, V., Nalini, R., Sekar, T., Premalatha, M. & Subramanian,

Ce0.9Gd0.1O1.95-δ in reducing atmosphere. *Acta Mater.* Vol 58, pp. 3860. Horita, T., Kishimoto, H., Yamaji, K., Xiong, Y., Sakai, N., Brito, M.E. & Yokokawa, H.

reducing atmosphere. *Journal of Power Sources.* Vol. 176, pp. 54.

phosphine-containing fuels. *Journal of Power Sources*. Vol. 195, pp. 4013. Haiqian, W., Weijie, J., Lei, Z., Yunhui, G., Bin, X., Yousong, J. & Yizhou, S. (2010).

Mathematical Model of a Direct Methanol Fuel Cell. *Journal of Fuel Cell Science and* 

via modifited sol-gel route: Thickness control (8-80 µm). *Journal of European Ceramic* 

Liu, X. (2010). Degradation of LaSr2Fe2CrO9−δ solid oxide fuel cell anodes in

Preparation of YSZ films by magnetron sputtering for anode-supported SOFC.

Ramousse, S. (2010). Densification and grain growth during early-stage sintering of

(2008)Evaluation of Laves-phase forming Fe–Cr alloy for SOFC interconnects in

under Reducing Conditions. *Journal of Electrochemical Society*. Vol. 149,

(2001). Synthesis of yttria stabilized cubic zirconia (YSZ) powders by microwave-

P. (2009). A review on gasification of biomass. *Renewable and Sustainable Energy* 

layers for solid oxide fuel cell applications. *Thin Solid Films*. Vol. 304, pp.

Cache Control in Modular Distributed Hydrogen-Electric Energy Systems. *IEEE* 

(2006). Impact of distributed generation on distribution investment deferral.

 *Proceedings.* Vol. 89, pp. 1819.

*Technology*. Vol. 1, pp. 43.

*Society.* Vol. 26, pp. 3153.

pp. 1.

106.

563.

*Solid State Ionics*. Article in press.

*Materials Science*. Vol. 5, pp. 317.

*Reviews*. Vol. 13, pp. 179.

*Sustainable Energy Reviews*. Vol 5, pp. 299.


**7** 

*USA* 

**Investigations of Intermediate-Temperature** 

**Alkaline Methanol Fuel Cell Electrocatalysis** 

*1Illinois Sustainable Technology Center, University of Illinois at Urbana-Champaign,* 

Direct methanol fuel cells (DMFCs) possess obvious advantages over traditional hydrogen fuel cells in terms of hydrogen storage, transportation, and the utilization of existing infrastructure. However, the commercialization of this fuel cell technology based on the use of proton-conductive polymer membranes has been largely hindered by its low power density owing to the sluggish kinetics of both anode and cathode reactions in acidic media and high cost owing to the use of noble metal catalysts. These could be potentially addressed by the development of alkaline methanol fuel cells (AMFCs). In alkaline media, the polarization characteristics of the methanol electrooxidation and oxygen electroreduction are far superior to those in acidic media (Yu et al., 2003; Prabhuram & Manoharan, 1998). Another obvious advantage of using alkaline media is less-limitations of electrode materials. The replacement of Pt catalysts with non-Pt catalysts will significantly decrease the cost of catalysts. Recently, the AMFCs have received increased attention (Dillon et al., 2004). However, these fuel cells are normally operated at temperature lower than 80 °C. In this low temperature range, both methanol electrooxidation and oxygen electroreduction reactions are not sufficiently facile for the development of high performance AMFCs. Considerable undergoing efforts are now focused on the development

Alternatively, increasing temperature has been proven as an effective way to accelerate electrode reactions. The changes of the reaction rates with increasing temperature are strongly determined by the values of activation energy, as described by the Arrhenius equation. More obvious changes are expected for the methanol electrooxidation in alkaline media than in acidic media since reported values of the activation energy are higher in alkaline media (Cohen et al, 2007). Additionally, increasing temperature may decrease concentration polarization, Ohmic polarization, and CO poisoning of the catalysts. All these

Further finding of increasing temperature for the methanol oxidation is that methanol can be efficiently converted with water in the aqueous phase over appropriate heterogeneous catalysts at temperatures near 200 °C to produce primarily H2 and CO2 (Huber et al., 2003;

of highly active catalysts for accelerated electrode reactions.

advantages can contribute to the performance improvement of the AMFCs.

**1. Introduction** 

**Using a Pressurized Electrochemical Cell** 

*2Energy and Environmental Research Center, University of North Dakota,* 

Junhua Jiang1 and Ted Aulich2

