中文摘要
以甲醇為原料之直接甲醇燃料電池存在嚴重的甲醇滲透問題，不
但造成甲醇燃料的流失，亦會與氧氣形成混成電位(mixed potential)
降低陰極電位使電池效能變差。本研究以含浸法製備Pt/C 作為陰極
觸媒，Pt-Ru/C 作為陽極觸媒，在不同的進料濃度、溫度、流速及電
池溫度進行放電測試，以氫參考電極、陰極、陽極形成三極式系統作
放電極化曲線及交流阻抗分析，分別以陰陽兩極的角度探討操作條件
對甲醇滲透及電池效能的影響。
本研究氫參考電極設計在操作條件下不存在甲醇滲透對參考電
極的影響，可長時間維持穩定與可靠性。三極式有別於一般二極式系
統僅可得到兩極阻抗值的總和，對陰陽兩極分別探討更可了解阻抗的
研究發現，進料甲醇濃度對甲醇滲透的影響甚鉅，陰極電位隨著
甲醇濃度的上升而明顯下降。陽極電位明顯上升，推測和甲醇氧化的
中間物一氧化碳的吸附性質有關。
除了操作條件外，擴散層對電池效能也有影響。擴散層的疏水性
可以幫助陽極二氧化碳的排除及陰極水分的排除，但疏水性材質較不
導電，會增加電池的內電阻，因此在擴散層的選擇上必須取決於膜電
II
極組的特性、系統特性以及操作條件。對本系統而言，由於陰極的氧
氣無增濕，在大電流下亦不會產生泛溢現象，因此陰極採非疏水性材
質，陽極採疏水性材質時可得到最佳的效能。
甲醇進料溫度升高到60oC 對陽極效能的提升非常有幫助，推測甲
醇在此溫度以上活性大增，有助於氧化反應的進行。甲醇流速越高，
對一氧化碳排除的效果越好，電極表面不受二氧化碳覆蓋時甲醇的質
傳顯得容易，陽極效能隨之上升。

Abstract
One of the most serious problems of direct methanol fuel cell
(DMFC) is methanol crossover. The methanol permeability through the
membrane not only loses the fuel of methanol but also decreases the cell
potential due to mixed potential of cathode with oxygen. This research
used the impregnation method to prepare Pt/C as cathode catalyst,
Pt-Ru/C as anode catalyst. The discharging test of the cell was operated at
different concentrations, temperatures, flow rates of the fuel and the cell
temperature. Hydrogen reference electrode、cathode electrode、anode
electrode were applied in the three-electrode mode system to obtain the
discharging polarization curve and AC impedance analysis. The effects of
operating condition on the methanol permeation and cell performance
were investigated from the points of view of anode and cathode.
This research has fabricated a hydrogen reference electrode with
good stability and reliability. The inference from the methanol
permeation to the reference electrode can be neglected in 12-hour
operation. Three-electrode mode system is better than two-electrode
mode system was the sum of those on two electrodes and three-electrode
mode system can separate the anode impedance and cathode impedance.
In this study, the methanol permeation was strongly affected by the
methanol concentration. Cathode potential decrease if methanol
concentration increased. Anode potential increase with methanol
IV
concentration probably caused by different kinds of (CO)ads on the
electrode.
Beside the operating condition, the type of diffusion layer also
effected for the cell performance. The hydrophobic property of diffusion
layer can help expulsing carbon dioxide from the anode side and water
from the cathode side. But hydrophobic property degraded conductivity
and hence increased the inner resistance of fuel cell. In this system,
oxygen in cathode side was not humidified, no flooding on the electrode
happened even at high current density. Therefore, the best performance
was obtained when the diffusion layers were hydrophilic at cathode and
hydrophobic at anode.
Higher temperature of methanol than 60oC can be much helpful to
improve the anode performance. Increase in the temperature increase the
methanol activity significantly and helped the process of oxidation
reaction. The higher methanol flow rate, the better carbon dioxide
expulsing. When the coverage of carbon dioxide on the electrode
decrease, the mass transfer of methanol across the diffusion layer was
easier and the anode performance improved.

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