以十二烷基胺修飾之碳材及海膽型碳材為質子交換膜燃料電池觸媒載體之研究

陸瑞東

doi:10.6844/NCKU.2012.01517

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以十二烷基胺修飾之碳材及海膽型碳材為質子交換膜燃料電池觸媒載體之研究

Study on the performance of proton exchange membrane fuel cell with dodecylamine-modified carbon and urchin-like carbon as the catalyst supports

陸瑞東 , Ph.D　　Advisor：楊明長　　

繁體中文 DOI： 10.6844/NCKU.2012.01517

質子交換膜燃料電池；奈米碳管；十二烷基胺；海膽型碳材； Proton exchange membrane fuel cell ； nanotube ； dodecylamine ； urchin-like carbon

Abstract │ Reference (142) │ Times Cited (6) │ Altmetrics

Abstract 〈TOP〉

在質子交換膜燃料電池研究上，為了增加觸媒的電化學活性面積，高表面積的碳材可作為觸媒的載體。許多研究也顯示碳材載體的特性會影響觸媒的電化學特性，因此擁有特殊官能基和高導電度的碳材載體，不但可以增加白金觸媒的分散性，也可以幫助電子的傳遞，提升電池的放電效率。本研究成功地製備出以十二烷基胺修飾的碳材和以海膽型碳材作為陰極觸媒的載體，並將其應用在質子交換膜燃料電池上。利用XRD (X-ray diffraction)分析所得之觸媒的晶粒大小、利用TEM (transmission electron microscopy)觀察其粒徑大小、利用EDS (energy dispersive spectroscopy)分析觸媒的組成、利用TGA (Thermogravimetric analysis)分析Pt-Ru觸媒在碳材上的負載量。利用三極式膜電極組所測得的陰極極化曲線進行分析，獲得氧氣還原之塔弗斜率及陰極之阻抗；利用交流阻抗分析，獲得電荷轉移電阻、歐姆阻抗。本研究發現極化曲線達到完全濃度極化(complete concentration polarization)之前，極化曲線會受到質傳所造成的濃度過電壓的影響，因此我們定義陰極極化曲線獲得的陰極阻抗與交流阻抗分析歐姆阻抗的差值，為質傳阻抗。本研究將探討不同碳材載體對陰極電極的影響。
第一個部份先利用有機合成的方式將疏水性十二烷基胺修飾在碳材上，再利用甲醇還原的方式將Pt-Ru觸媒製備在此十二烷基胺修飾的碳材上，使具有很好的觸媒分散性。將此十二烷基胺修飾的觸媒混合未修飾的觸媒，在觸媒層中會形成反應物氣體輸送的孔道，以利氣體擴散至活性點。以此複合觸媒作為陰極觸媒，最佳的混合比例為20~40%。在此混合比例下電池其最大功率密度高出商用觸媒E-TEK (125 mW cm−2)約29%。相較於一般碳材載體，40%複合式觸媒具有較低的質傳阻抗，因此獲得高的電池放電效能。
第二部份首先在中孔洞碳材上，利用含浸硝酸鐵並於高溫下還原Fe觸媒；XC-72碳材上利用熱裂解法還原製備Co觸媒。接著利用氣相沉積的方式，在沉積有Fe觸媒的中孔洞碳材和沉積有Co觸媒的XC-72碳材上成長奈米碳管，製備成海膽型碳材。Pt-Ru觸媒再分別以甲醇還原和微乳化法製備於XC-72與中孔洞海膽型碳材上。海膽型結構的碳材作為觸媒載體，上面的奈米碳管直接連接於碳材上，可以增加觸媒層中電子的導電度，而對於XC-72與中孔洞海膽型觸媒來說，碳管成長時間分別為40和60分鐘時，觸媒可獲得最高的最大放電功率，XC-72與中孔洞海膽型觸媒的最大放電功率分別高出E-TEK觸媒約43%和59%。海膽型觸媒皆具有較高的電子導電度，此外中孔洞海膽型觸媒具有較低的質傳阻抗，因此獲得較高的電池放電效能。

Parallel Abstract 〈TOP〉

In order to increase the catalyst electrochemical surface area, carbon with a high surface area has been a catalyst support in proton exchange membrane fuel cells (PEMFCs). Many studies have revealed that the properties of the carbon support can greatly affect the electrochemical properties of the catalyst. It has been reported that a carbon support with special function group and good conductivity can not only provide a high dispersion of Pt nanoparticles, but also facilitate electron transfer, resulting in better performance. In this study dodecylamine modified carbon and urchin-like carbon were successfully prepared and used as cathode catalysts in PEMFC.
The grain size, particle size, atomic composition and metal loading were analyzed by XRD (X-ray diffraction), TEM (transmission electron microscopy), EDS (energy dispersive spectroscopy) and TGA (Thermogravimetric analysis), respectively. By using three-electrode membrane electrode assembly, the curve fitting of polarization curve was used to study the Tafel slopes and cathode resistance, at medium range of current densitiy, on cathode; and AC-impedance spectra was also used to study the charge transfer and ohmic resistance on cathode. Before complete concentration polarization, the polarization curves contained the concentration overpotential at medium current density region. Therefore, the difference between the cathode resistance and the ohmic resistance was defined as mass transfer resistance in this study.
In the first part, hydrophobic dodecylamine modified carbon supports were prepared by organic synthesis. Well-dispersed Pt-Ru nanoparticles, with a narrow size distribution, were then deposited on the dodecylamine modified carbon supports by methanol reduction. These dodecylamine modified catalysts were separately mixed with either a commercial catalyst or unmodified catalyst to provide hydrophobic channels to convey the reaction gas to the active sites in the catalyst layer. The best cathode composite catalyst, containing 20–40 wt% of modified-catalyst, gave approximate 29% increase in the maximum power density, comparing to E-TEK catalyst (125 mW cm−2). The composite catalyst, containing 40 wt% of modified-catalyst, showed lower mass transfer resistance in cell performance.
In the second part, the Fe catalyst was first prepared on the mesoporous carbon by immersion process followed by a high temperature reduction; the Co catalyst was prepared on XC-72 carbon by thermal decomposition reduction. Urchin-like structured carbons were prepared by growing carbon nanotubes grown on either Fe catalyst-seeded mesoporous carbon or Co catalyst-seeded XC-72 carbon by chemical vapor deposition. The Pt-Ru nanoparticles were then deposited on the urchin-like XC-72 carbon and urchin-like mesoporous carbon by methanol reduction and microemusion method, respectively. It was believed that the Urchin-like structure, comprising intimately connected carbon and carbon nanotubes, offered conductivity advantages as a catalytic support for PEMFCs. Forty and sixty of CNT growth time for urchin-like XC-72 catalyst and urchin-like mesoporous catalyst, respectively, gave the highest maximum power density. In comparison with the commercial E-TEK catalyst, the urchin-like XC-72 catalyst and urchin-like mesoporous catalyst showed higher maximum power densities by 43% and 59%, respectively. The urchin like catalysts revealed good electron conductivity in cell performance. Moreover, the urchin-like catalyst (MC) showed lower mass transfer resistance in cell performance.

Reference ( 142 ) 〈TOP〉

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Times Cited (6) 〈TOP〉

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