中文摘要

以氫氣為陽極進料之質子交換膜型燃料電池，若氫氣中存在少量之CO，將導致電池放電效能嚴重衰退。本研究以含浸法製備不同白金與釕組成比之Pt-Ru/C觸媒，分別使用甘油與水為電極漿料溶劑製備膜電極組，在不同CO濃度下，進行電池放電測試，以三極式系統，利用放電極化曲線與交流阻抗分析，對電池放電效能進行探討。
以含浸法製備觸媒，以H2PtCl6及RuCl3為原料，V XC-72碳粉為載體，使用甲醇為還原劑，在70℃回流溫度下，可成功製備得不同白金-釕組成比之Pt-Ru/C觸媒。隨著釕的組成比由0增加到3.33，觸媒中之金屬粒徑由5～12nm降至2～6nm，且分散性越佳。釕-白金原子比(Ru/Pt)為1.13之觸媒，空氣環境中熱處理溫度在350℃以下，觸媒可維持穩定之結構。
本研究成功建立三極式系統進行電池之放電效能測試，相較於一般二極式系統只能得到兩極阻抗值之總和，此三極式系統在全電池放電下，可針對陽極或陰極個別造成之阻抗行為進行探討。
本研究亦提出一等效電路模組，用於模擬PEM燃料電池陰極與陽極之交流阻抗分析結果。模擬計算出之陰極電荷轉移電阻，與陰極極化曲線計算所得之電荷轉移電阻相比較，兩電阻值相當近似。於氫氣中存在CO的操作條件下，由交流阻抗分析之結果發現CO毒化於陽極產生之過電位，是由陽極電荷轉移電阻與電極層中電解質電阻共同增加所造成。
於氫氣中存在25與100 ppm CO的操作條件下，在放電過程中，與純氫氣進料相比，電池放電電位受CO毒化現象而明顯下降，此電位降主要反映在陽極過電位之增加。以陽極極化曲線計算所得之陽極電荷轉移電阻，隨放電電流增加而增加，在達一最大值後下降。CO濃度越高，此電阻最大值越高。同時隨著陽極中釕負載量的增加，此電阻最大值隨之降低。在含100 ppm CO之氫氣中，添加2% O2的操作條件下，因CO毒化造成之電池電位降幾乎可完全消除，同時隨著陽極組成中釕負載量的增加，所需添加之O2量隨之減少。

Abstract

In a proton exchange membrane fuel cell (PEMFC), when hydrogen is the anodic feed, the presence of CO in hydrogen causes a serious decay in cell performance. In this study, Pt-Ru/C catalysts were obtained with various ratios of platinum to ruthenium with impregnation method. Discharging test of the cell with CO presence in hydrogen were carried out in a three-electrode mode system. The performance of the full cell was demonstrated by the discharging polarization curves and AC impedance analysis.
The catalyst was prepared by using impregnation method whereat H2PtCl6, RuCl3, V XC-72 carbon powder, methanol were employed as the source of platinum, ruthenium, support and reducing agent, respectively. After refluxed in 70 ℃, different catalysts with various Pt-Ru/C ratios were obtained successfully. While the content of ruthenium in the catalyst increased from 0 to 3.33, the particle size of metal in the catalyst was reduced from 5~12 to 2~6 nm, and the dispersion of the metal in the catalyst was improved. The structure of catalyst with Ru/Pt ratio 1.13 were stable after calcination below 350 ℃.
The discharging performance of the cell was carried out in a three-electrode mode system successfully. In general, the resistances obtained from a two-electrode mode system are the sum of two electrodes. But in a three-electrode mode system, the anodic and cathodic impedances could be studied individually during the cell discharging.
In this study, an equivalent circuit model was proposed to explain the results of AC impedance analysis for the anode and cathode of the PEMFC. The cathodic charge transfer resistance obtained from AC impedance analysis was very similar to that obtained from the polarization curves. With the CO presence, the experimental results of AC impedance analysis suggested that the overpotential due to CO poisoned at anode was contributed by the resistances of both charge transfer and electrolyte in the catalyst layer.
Comparing the discharging process operated in the atmosphere of 25 and 100 ppm CO in hydrogen with that operated in pure hydrogen, the discharging potentials obviously dropped off due to the effect of CO poisoning. The anodic charge transfer resistance calculated from the anodic polarization curve increased with the discharging current and declined after a maximum value, whereat the potential drop caused the increasing of anodic overpotential. The maximum value of this charge transfer resistance increased with the CO concentration. On the other hand, higher ruthenium loading gave smaller value of this maximum resistance. The potential drop, caused by CO poisoned catalyst, can be overcome by adding 2% O2 into hydrogen gas containing 100 ppm CO. As the ruthenium loading in the catalyst increased, the required amount of O2 decreased.

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