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Effect of titanium nitride thin films on the use of catalyst support for direct methanol fuel cells
|關鍵字:||氮化鈦;直接甲醇燃料電池;載體;TiN;DSSC;support||引用:|| L. E. Toth , Transition Metal Carbides and Nitrides, New York: Academic Press. (1971).  汪建民，陶瓷技術手冊，中華民國冶金協會，1972年。  H. E. Hintermann, “Thin solid films to combat friction, wear, and corro-sion,” J. Vac Sci. Technol. B, 2 (1984) 816.  M. Birkholz, K. E. Ehwald, D. Wolansky, I. Costina, C. B. Kaynak, M. Fröhlich, H. Beyer, A. Kapp, and F. Lisdat, “Corrosion-resistant metal lay-ers from a CMOS process for bioelectronic applications,” Surf. Coat. Technol. (2010) 204.  K. H. Xue, T. L. Ren, D. Xie, Z. Jia, M. M. Zhang, and L. T. Liu, “Nitro-gen-rich titanium nitride serving as Pt-Aldiffusion barrier for FeRAM ap-plication,” Taylor & Francis Group Integrated Ferroelectrics, 96 (2008) 19–26.  O.T. Muhammed Musthafa, and S. Sampath, “High performance plati-nized titanium nitride catalyst for methanol oxidation,” Chem.Commun. (2008) 67–69.  M. H. Yeh, U. Y. Lin, C. P. Lee, H. Y. Wei, C. Y. Chen, C. G. Wu, R. Vit-tala, and K. C. 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Consider the shortage of energy, the development of alternative energies is an important issue. Direct methanol fuel cell (DMFC) has attracted much attention on this issue. However, the often used support material of anode is carbon which is sus-ceptible to erosion and poison during the development of DMFC. Thus, the develop-ment of non-carbon material support is one of the most important targets for many re-search teams.
Titanium nitride (TiN) is a suitable electrode because of its good conductivity and chemical stability. In this study, TiN films were deposited by DC magnetron sputter-ing using nitrogen as a reactive gas. TiN films were prepared with nitrogen flow rate of 3 ~ 6 sccm and deposition time of 10 - 60 min. Moreover, TiN films were analyzed in exploring the influences of TiN on the anode of DMFC.
TiN films were divided into three experiment of groups. The first one was the films prepared by changing nitrogen flow rate to study the relationship between maximum current density (catalytic effect) and properties of TiN films. The result is that the maximum current density decreased with increasing resistivity, and dropped after the first rise with increasing the film thickness. Surface particle size had the same effect on the catalytic effect like film thickness.
The second set was the films prepared by changing both deposition time and the nitrogen flow rate, which had different resistivities, with the same thickness and sur-face particle size. The result is that maximum current density increased with decreas-ing resistivity.
The third was the films prepared by changing the deposition time, which had different thickness and surface particle size, but with similar resistivities. Then the TiN films have similar resistivities when deposition time were 30 - 60 min. The maximum current density decreased with increasng the TiN film thickness. Moreover we found that surface particle size increased with the thickness. Thus, the surface particles size may also cause the maximum current density to decrease. From SEM results, platinum particles were found to increase with increasing the surface particle size. When plati-num particles size increased, the reaction area decreased, which reduced the catalytic effect.
Overall analyze show the characteristics of titanium nitride films with lattice constant of 0.424 - 0.428 nm, resistivity of 44.6±0.2 - 129±1 μΩ-cm, and thickness of 250±1 - 1441±7 nm. The maximum current densities are between 49 - 125 mA/mgPt. The TiN film with the lowest resistivity 47.3±0.3 μΩ-cm has the highest maximum current density 125 mA/mgPt.
氮化鈦因其良好的導電性與化學穩定性，適合作為電極，本研究中，以直流磁控濺鍍法，通入氮氣作為反應性氣體製備氮化鈦薄膜，改變製備薄膜時氮氣流量3 - 6 sccm與鍍著時間10 - 60 min，並對薄膜性質進行分析，探討氮化鈦性質對於直接甲醇燃料電池陽極電極的影響。
第三組改變鍍著時間，製備相近電阻率但不同厚度之薄膜，發現於鍍著時間30 - 60 min有相近之電阻率，但最大電流密度隨鍍著薄膜厚度增加而下降，此外發現薄膜表面形貌大小隨膜厚增加而上升，因此推測是否由於表面形貌改變造成最大電流密度下降，藉由實驗驗證，經SEM觀察附著白金後的表面，發現白金顆粒隨表面形貌大小增加而變大，反應面積減少使催化效果下降。
根據各項分析確定本研究所鍍著為氮化鈦薄膜，其晶格常數介0.424 - 0.428 nm之間，電阻率範圍44.6±0.2 - 129±1 μΩ-cm，薄膜厚度250±1 – 1441±7 nm，氧化最大電流密度介於49 - 125 mA/mgPt之間，氮化鈦薄膜有最低電阻率為47.3±0.3 μΩ-cm時，有最大電流密度125 mA/mgPt。
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