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dc.contributor.advisor Shanmugam, Sangaraju -
dc.contributor.author Suh, Won Kyo -
dc.date.accessioned 2017-05-10T08:49:51Z -
dc.date.available 2016-05-18T00:00:00Z -
dc.date.issued 2013 -
dc.identifier.uri http://dgist.dcollection.net/jsp/common/DcLoOrgPer.jsp?sItemId=000002262497 en_US
dc.identifier.uri http://hdl.handle.net/20.500.11750/1326 -
dc.description.abstract Polymer electrolyte membrane fuel cell (PEMFC) has been studied widely due to its higher energy efficiency than a conventional internal combustion engine by generates electrical energy directly from chemical energy. However, the fuel cells faces lots of challenges to commercialization. Cost reduction and improvement of catalysts activities are two major problems impedes the commercialization. Since costly platinum has been used as a catalyst at both anode and cathode of fuel cells, it is required to decrease amounts of Pt. Alloying Pt with secondary transition metals such as Fe, Co, and Ni can reduce the amount of Pt and leading to the cost reduction. In terms of activities, not only Pt-M (M=Fe, Co, Ni, etc.) alloys but carbon support materials should be considered. Graphite materials such as Valcan carbon XC-72 (VXC) and carbon nanotubes (CNT) have been utilized as a carbon support materials for fuel cells. Moreover, since it discovered, graphene has been widely used as a support for electrocatalysts with different metal nanoparticles because of its specific features like high electro-conductivity, surface area and thermal stability.
In an attempt to develop low cost and highly active oxygen reduction reaction (ORR) catalysts, graphene supported Pt-Ni alloy catalyst was synthesized, and the electrochemical ORR performance was evaluated. Due to the ORR sluggish on cathode side plays an important role in fuel cells performance, it is necessary to improve the ORR activities of electrocatalysts. The ORR activity of Pt-Ni supported on graphene was compared with commercial Pt/C catalyst, and Pt-Ni alloy supported on other carbon support materials such as carbon black (VXC) and carbon nanotube (CNT). Among three different electrocatalysts, Pt-Ni alloy catalyst supported on graphene showed highest ORR activity. All Pt-Ni alloy catalysts were followed the direct 4 electron pathway. Among three catalysts, Pt-Ni/graphene catalyst was observed lowest hydrogen peroxide production. Moreover, Pt-Ni/graphene catalysts showed highest methanol resistance. Pt-Ni alloy catalysts were characterized using various physical-chemical techniques, such as scanning electron microscopy, transmission electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy. The electrocatalytic activity and stability of Pt-Ni alloy catalysts were studied using CV, LSV, RDE and RRDE techniques. Thus, developing Pt-Ni alloy supported on various carbon materials with desired properties of ORR activities will be discussed. ⓒ 2013 DGIST
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dc.description.tableofcontents Chapter 1: Introduction 1
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1.1. Forewords 1
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1.2. Objectives of the work 3
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1.3. Advantages & disadvantages of fuel cells 4
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1.4. Fundamental principles of the fuel cells systems 6
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1.5. Various types of fuel cells 9
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1.6. Studies of carbon allotropes for fuel cell carbon support materials 13
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1.7. Structure and characteristic of graphene 15
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1.8. Oxygen reduction reaction (ORR) studies 18
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1.8.1. Low temperature ORR mechanism 18
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1.8.2. Oxygen reduction reaction on Pt catalyst surface 19
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Chapter 2: Experimental 20
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2.1. Chemicals 20
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2.2. Synthesis of graphene 20
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2.2.1. Preparation of graphene oxide 20
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2.2.2. Chemical reduction of graphene oxide to graphene 21
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2.3. Surface modification of carbon nanotube (CNT) 21
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2.4. Preparation of Pt-Ni (1:1) (20 wt % metal loading) alloy catalysts supported on carbon black (Vulcan XC-72), CNT, and graphene 22
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2.5. Characterization 22
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2.5.1. Physical characterization 22
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2.5.2. Elemental characterization 23
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2.5.3. Electrode preparation and electrochemical measurement 23
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Chapter 3: Results and Discussion 25
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3.1. Morphologies and size distribution of Pt-Ni based electrocatalysts 25
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3.2. Crystalline structure analysis of Pt-Ni based electrocatalysts 31
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3.3. Chemical and electronic properties of Pt-Ni based electrocatalysts 34
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3.4. Electrochemical studies of Pt-Ni based electrocatalysts 39
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3.4.1. Electrochemical surface area 39
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3.4.2. Oxygen reduction reaction activities of Pt-Ni based electrocatalysts 41
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3.4.3. Methanol tolerance studies of Pt-Ni based electrocatalysts 46
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3.4.4. Stability of Pt-Ni based electrocatalysts 49
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Conclusions 51
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Reference 53
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국문 요약문 61
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Acknowledgement 63
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dc.format.extent 62 -
dc.language eng -
dc.publisher DGIST -
dc.subject Fuel cells -
dc.subject Graphene -
dc.subject Pt-Ni alloy catalysts -
dc.subject Oxygen reduction reaction (ORR) -
dc.subject 연료전지 -
dc.subject 그라핀 -
dc.subject 백금-니켈 합금 촉매 -
dc.subject 산소 환원 반응(ORR) 능력 -
dc.title Oxygen Reduction Reaction (ORR) Activities of Pt-Ni Alloy Nanoparticles Supported on Graphene -
dc.title.alternative 그라핀 지지체를 사용한 백금-니켈 나노입자 합금의 산소 환원 반응(ORR) 능력 -
dc.type Thesis -
dc.identifier.doi 10.22677/thesis.2262497 -
dc.description.alternativeAbstract 고분자 전해질 막 연료전지 (PEMFC)는 화학 에너지로부터 직접 전기 에너지를 발생시켜 기존 내연 기관보다 높은 효율을 가진다는 점에서 널리 연구되어 왔다. 하지만 연료전지는 상업화를 이루기 위해 많은 도전 과제를 품고 있다. 높은 가격 절감과 촉매 활성 촉진이 연료전지 상업화를 위한 주된 과제에 해당한다. 높은 가격의 백금이 연료전지 양극과 음극에 모두 사용되기 때문에, 가격 절감을 위해 백금의 양을 감소하는 것이 요구된다. 백금과 Fe, Co, 그리고 Ni과 같은 이차 전이 금속과의 합금은 백금 촉매의 양을 줄일 수 있고 연료전지 가격 절감을 기대할 수 있다. 촉매 활성 부분에서는 백금-M(M=Fe, Co, Ni, etc.) 합금뿐만 아닌 촉매의 탄소 지지체 역시 고려되어야 한다. 카본 블랙(Vulcan XC-72) 및 탄소나노튜브(CNT)와 같은 흑연 물질은 연료전지 촉매의 탄소 지지체로 널리 사용되어 왔다. 또한 그라핀은 이것이 가지는 높은 전기 전도도와 넓은 표면적, 열적 안정성 등의 이유로 발견 이래 금속 나노입자 지지체로써 폭넓게 사용되었다.
가격 절감과 높은 산소환원반응(ORR) 능력을 위해 백금-니켈 합금 촉매를 합성 하였고 촉매의ORR 능력을 평가하였다. 음극에서의 ORR은 양극에 비해 활성이 낮으며 이것은 연료전지 성능의 막대한 영향을 미치기 때문에 음극에서의 촉매 ORR 능력 향상은 필수적이다. 그라핀을 지지체로 사용한 백금-니켈 나노입자 합금 촉매는 상업용 Pt/C 촉매와 카본 블랙(Vulcan XC-72) 및 탄소나노튜브(CNT)를 지지체로 사용한 백금-니켈 나노입자 합금 촉매와도 비교 분석 하였다. 세가지 다른 전극촉매는 모두 연료전지 성능에 우세한 4전자 반응을 따랐으며 그 중 그라핀을 지지체로 사용한 백금-니켈 나노입자 합금 촉매가 ORR면에 있어 가장 높은 활성을 보였다. 또한 그라핀을 지지체로 사용한 백금-니켈 나노입자 합금 촉매는 메탄올의 내성면에 있어서도 가장 높은 내성을 가진 촉매로 평가되었다. 백금-니켈 나노입자 합금 촉매들은 주사전자현미경, 투과전자현미경, X선 회절법, 그리고 X선 광전자 분광법과 같은 물리적-화학적 기법들을 이용하여 분석 되었다. 백금-니켈 나노입자 합금 촉매의 전기화학적 특성은 CV, LSV, RDE, 그리고 RRDE와 같은 기법들을 이용하여 비교 분석 하였다. 본 연구에서는 다양한 탄소 지지체와 함께 백금-니켈 나노입자 합금 촉매의 구체적인 특성과 ORR 활성에 대하여 논의될 것이다. ⓒ 2013 DGIST
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dc.description.degree Master -
dc.contributor.department Energy Systems Engineering -
dc.contributor.coadvisor Han, Oc Hee -
dc.date.awarded 2013. 2 -
dc.publisher.location Daegu -
dc.description.database dCollection -
dc.date.accepted 2016-05-18 -
dc.contributor.alternativeDepartment 대학원 에너지시스템공학전공 -
dc.contributor.affiliatedAuthor Suh, Won Kyo -
dc.contributor.affiliatedAuthor Shanmugam, Sangaraju -
dc.contributor.alternativeName 서원교 -
dc.contributor.alternativeName 상가라쥬샨무감 -
dc.contributor.alternativeName 한옥희 -
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