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Fabrication of Pt-Ru/C Composite Catalyst Electrodes by Electrophoresis Deposition Method for DMFC Fuel Cell and their Characteristics (전기영동법에 의한 직접메탄올 연료전지용 Pt-Ru/C 복합촉매 전극제조 및 특성평가)

  • Kim, Jeonghyun;Song, Minkyeong;Kim, Jinwoo;Yu, Yeontae
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.11a
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    • pp.86.2-86.2
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    • 2011
  • 저온형 연료전지인 직접 메탄올 연료전지(Direct Methanol Fuel Cells, DMFC)는 친환경적인 발전 시스템, 높은 에너지 효율의 장점 때문에 주목을 받고 있으나 연료극의 촉매로 사용되는 금속은 고가의 귀금속인 Pt와 Ru가 요구되어 제조비용이 비싸기 때문에 촉매의 양을 줄이고, 반응 도중 생성되는 CO에 의한 촉매의 피독 문제 등 해결하여야 할 점이 산적해 있어 연료전지 중 촉매의 활성을 높이는 연구들이 활발히 이루어지고 있다. 종래의 MEA의 촉매층 제조공정은 우선 환원석출법에 의해 Pt-Ru/C를 합성하고 Nafion 용액에 혼합하여 Pt-Ru/C 슬러리를 제조한다. 이 방법에서는 carbon sheet에 spray 방법으로 Pt-Ru/C 촉매층이 만들어지기 때문에, Pt-Ru 촉매가 Nafion에 의해 부분적으로 매몰되어 촉매의 전기화학적 활성이 떨어지는 문제점이 있다. 이를 해결하는 방안으로 펄스전류를 이용하여 Pt-Ru 합금입자를 carbon sheet에 전기화학적으로 담지 시켜 Nafion에 매몰되는 것을 방지하는 펄스전해법 연구가 진행되고 있다. 그러나 촉매의 입자크기가 일반적으로 50~70 nm 이상으 크기 때문에 촉매의 낮은 활성이 문제점으로 야기되고 있다. 본 연구에서는 Pt-Ru/C 촉매층 제조 문제점을 해결하고, 촉매의 전기화학적 활성을 증가시키기 위해서 2~4 nm Pt-Ru 콜로이드를 전해액으로 사용하고, 전기영동법을 이용하여 Pt-Ru 나노 입자를 carbon sheet($1{\times}1cm^2$) 에 담지 시켰다. 전기영동법에서 균일한 Pt-Ru 촉매층의 제조를 위해 전류인가 방법으로는 펄스전류를 사용하였고, 실험변수로는 전해액 pH, duty cycle, 담지시간을 선정하였다. 합성된 Pt-Ru 콜로이드를 TEM분석으로 나노입자의 크기와 분산성 분석하였고, 콜로이드 나노입자의 표면전하 상태를 분석하기 위해 zeta-potential을 분석하였다. Pt-Ru/C의 촉매의 전기화학적 활성을 분석하기 위하여 0.5 M H_2SO_4$ 와 1 M $CH_3OH$ 혼합용액에 CV(Cyclic Voltammetry)실시하였고, carbon sheet 전극 상 Pt-Ru의 분산성 확인을 위하여 FE-SEM분석을 수행하였다.

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Characteristics of $RuO_2$/n-GaN Schottky Diode ($RuO_2$/n-GaN 구조의 Schottky Diode 특성)

  • Kim, Dong-Sik
    • 전자공학회논문지 IE
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    • v.46 no.3
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    • pp.1-5
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    • 2009
  • In this paper, we study the electrical characteristics of $RuO_2$/n-GaN Schottky diodes fabricated by using electrochemical metallization. The solution for GaN Schottky electrodes of $RuO_2$ is perchloric acid($HClO_4$). Thickness of $RuO_2$ layer depend on supplied voltage and dipping time. We verified the possibility of the rectifying and non-rectifying devices' electrode which was depend on the thickness of $RuO_2$ layer.

Characterization of $RuO_2$ Thin Films by Hot-wall Metal Organic Chemical Vapor Deposition (Hot-wall MOCVD에 의한 $RuO_2$ 박막의 특성)

  • 신웅철;윤순길
    • Journal of the Korean Ceramic Society
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    • v.33 no.9
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    • pp.969-976
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    • 1996
  • RuO2 thin films were deposited on SiO2(1000 $\AA$)/Si by hot-wall Metal Organic Chemical Vapor Depositon. The crystallinity of RuO2 thin films increased with increasing deposition temperature and the preferred orienta-tion of RuO2 films converted (200) plane to (101) plane with increasing film thicknesses. Such a change in preferred orientation was influenced on the crystallographic structure and the residual stress of RuO2 thin films. The resistivity of the 2700$\AA$-thick RuO2 thin films deposted at 30$0^{\circ}C$ was 52.7$\mu$$\Omega$-cm and they could be applicable to bottom electrodes of high dielectric materials. However the resistivity of RuO2 thin films increased with decreasing film thicknesses. The grain size and the resistivity of RuO2 thin films were densified with increasing the annealing temperature and showed the decrease of resistivity.

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Characteristic of Ru Thin Film Deposited by ALD

  • Park, Jingyu;Jeon, Heeyoung;Kim, Hyunjung;Kim, Jinho;Jeon, Hyeongtag
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.08a
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    • pp.78-78
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    • 2013
  • Recently, many platinoid metals like platinum and ruthenium have been used as an electrode of microelectronic devices because of their low resistivity and high work-function. However the material cost of Ru is very expensive and it usually takes long initial nucleation time on SiO2 during chemical deposition. Therefore many researchers have focused on how to enhance the initial growth rate on SiO2 surface. There are two methods to deposit Ru film with atomic layer deposition (ALD); the one is thermal ALD using dilute oxygen gas as a reactant, and the other is plasma enhanced ALD (PEALD) using NH3 plasma as a reactant. Generally, the film roughness of Ru film deposited by PEALD is smoother than that deposited by thermal ALD. However, the plasma is not favorable in the application of high aspect ratio structure. In this study, we used a bis(ethylcyclopentadienyl)ruthenium [Ru(EtCp)2] as a metal organic precursor for both thermal and plasma enhanced ALDs. In order to reduce initial nucleation time, we use several methods such as Ar plasma pre-treatment for PEALD and usage of sacrificial RuO2 under layer for thermal ALD. In case of PEALD, some of surface hydroxyls were removed from SiO2 substrate during the Ar plasma treatment. And relatively high surface nitrogen concentration after first NH3 plasma exposure step in ALD process was observed with in-situ Auger electron spectroscopy (AES). This means that surface amine filled the hydroxyl removed sites by the NH3 plasma. Surface amine played a role as a reduction site but not a nucleation site. Therefore, the precursor reduction was enhanced but the adhesion property was degraded. In case of thermal ALD, a Ru film was deposited from Ru precursors on the surface of RuO2 and the RuO2 film was reduced from RuO2/SiO2 interface to Ru during the deposition. The reduction process was controlled by oxygen partial pressure in ambient. Under high oxygen partial pressure, RuO2 was deposited on RuO2/SiO2, and under medium oxygen partial pressure, RuO2 was partially reduced and oxygen concentration in RuO2 film was decreased. Under low oxygen partial pressure, finally RuO2 was disappeared and about 3% of oxygen was remained. Usually rough surface was observed with longer initial nucleation time. However, the Ru deposited with reduction of RuO2 exhibits smooth surface and was deposited quickly because the sacrificial RuO2 has no initial nucleation time on SiO2 and played a role as a buffer layer between Ru and SiO2.

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Bulk Heterojunction Solar Cell using Ru Dye Attached PCBM

  • Il-Su Park;Jae-Keun Hwang;Yongseok Jun;Donghwan Kim
    • Journal of Electrochemical Science and Technology
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    • v.15 no.3
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    • pp.421-426
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    • 2024
  • Ru dye (Z-907) is a crucial photosensitizing material in dye-sensitized solar cells (DSSCs). To enhance the utilization of Ru dye's photosensitizing properties in bulk heterojunction solar cells, a method was developed to synthesize phenyl-C61-butyric acid methyl ester (PCBM) nanoparticles that are chemically linked to Ru dye. PCBM contains a methoxy (-OCH3) group, whereas Ru dye incorporates a carboxyl group (-COOH) within its molecular structure. By exploiting these complementary functional groups, a successful bond between Ru dye and PCBM was established through an anhydride functional group. The coupling of PCBM with Ru dye results in a modification of the energy levels, yielding lower LUMO (3.8 eV) and HOMO (6.1 eV) levels, compared with the LUMO (3.0 eV) and HOMO (5.2 eV) levels of Ru dye alone. This configuration potentially facilitates efficient electron transfer from Ru dye to PCBM, alongside promoting hole transfer from Ru dye to the conducting polymer. Consequently, the bulk heterojunction solar cells incorporating this Ru dye-PCBM configuration demonstrate superior performance, with an open circuit voltage (Voc) of 0.62 V, short circuit current (Jsc) of 0.63 mA cm-2, fill factor (FF) of 65.6%, and a photovoltaic conversion efficiency (η) of 0.25%.

3, 4성분계 DSA 전극의 제조와 성능 평가

  • Park, Yeong-Sik;Kim, Dong-Seok
    • Proceedings of the Korean Environmental Sciences Society Conference
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    • 2008.11a
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    • pp.482-487
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    • 2008
  • 성능이 우수한 다성분계 전극을 개발하기 위하여 Ru를 주 전극성분으로 Pt, Sn, Sb 및 Gd를 보조 전극성분으로 하여 3, 4성분계 전극의 성능과 산화제 생성량 및 전극 표면 분석을 행하여 다음의 결과를 얻었다. 1. 2분 동안 단위 W당 제거된 RhB 농토는 Ru:Sn:Sb=9:1:1 > Ru:Pt:Gd=5:5:1 > Ru:Sn=9:1 > Ru:Sn:Gd=9:1:1 > Ru:Sb:Gd=9:1:1로 나타났다. Ru:Sn:Sb=9:1.1 전극에서 발생하는 free Cl, ClO$_2$ 및 H$_2$O$_2$농도가 다른 전극보다 높은 것으로 나타나 산화제 생성경향과 RhB 분해율과는 상관관계가 있는 것으로 사료되었다. 4성분계 전극 중에서 Ru:Sn:Sb:Gd 전극의 성능이 가장 우수한 것으로 나타났으나 3성분계 전극인 Ru:Sn:Sb=9:1.1 전극보다 성능이 떨어지는 것으로 나타났다. Ru:Sn:Sb=9:1:1 전극에서 생성되는 산화제 농도가 다른 두 종류의 산화제 농도보다 높은 것으로 나타났고 4성분 전극의 경우 Ru:Sn:Sb:Gd 전극의 산화제 농도가 Ru:Sn:Sb:Gd 전극이 높거나 유사한 경우로 나타나 산화제 생성 경향과 RhB분해 능과는 상관관계가 있는 것으로 나타났다. 초기 RhB 분해 속도가 높은 전극의 COD 제거율도 높은 것으로 나타났다. OH 라디칼은 발생하지 않지만 염소계 산화제 농도가 높고 RhB제거율이 높아 Ru를 주 성분으로 한 전극의 RhB분해는 주로 간접 산화작용에 의한 것이며, 개발된 3, 4성분계 산화물 전극은 간접 산화용 전극임을 알 수 있었다. 에칭을 하기 전의 Ti판은 표면이 매끄러운 것으로 나타났으며, 35% 염산으로 에칭한 후의 Ti메쉬는 매우 거친 표면조직을 가지는 것을 관찰할 수 있었다. Ru:Sn:Sb=9:1:1 전극과 Ru:Sn:Sb:Gd 전극의 SEM 사진을 관찰한 결과 두 전극 모두 전극 물질이 균일하게 도포되어 있었으며, 두 전극 모두 열소성을 통해 전극 성분을 코팅할 때 발생하는 "mud crack"이 발생한 것이 관찰되었다 EDX 분석에서 Cl이 관찰되었는데, 전극 성분의 불완전 산화로 인한 비양론적 산화물 때문이며 이는 RhB 분해성능과 관련 있는 것으로 사료되었다.

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Studies on the Anodic Oxidation Behavior of Methanol and L-Ascorbic Acid by Using Glassy Carbon Electrodes Modified with Inorganic-Metal Polymeric Films (무기 금속 고분자 막을 도포시킨 유리질 탄소전극을 이용한 메탄올과 L-ascorbic acid의 양극 산화 거동에 관한 연구)

  • Yoo, Kwang-Sik;Woo, Sang-Beom
    • Analytical Science and Technology
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    • v.11 no.5
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    • pp.347-352
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    • 1998
  • A study was carried out on the elelctrochemical characteristics of chemically modified electrodes (CMEs) by cyclic voltammetry. Fabrication of CMEs was made by coating with mixed valence (mv) inorganic-metal polymeric films on the glassy carbon electrode surface by potential cycling. Anodic oxidation behavior of methanol and L-ascorbic acid was studied by using CMEs working electrode. Deposition of films such as mv ruthenium oxo/ruthenium cyanide film (mv Ru-O/CN-Ru), mv ruthenium oxo/ferrocyanide film (mv Ru-O/$Fe(CN)_6$), and mv ruthenium oxo/ruthenium cyanide/Rhodium film (mv Ru-O/CN-Ru/Rh) was obtained to coat by scan rate of 50 mV/sec within the specified potential range (-0.5V ~ +1.2V). Film thickness was controlled by the repeat of the potential cycling. Anodic oxidation behavior of methanol was as follow. Calibration graph by using mv Ru-O/CN-Ru film showed linearly from 10 mM to 80 mM MeOH with slope factor of $-7.552{\mu}A/cm^2$. Although slope factor by using mv Ru-O/$Fe(CN)_6$ film was $-5.13{\mu}A/cm^2$, yet linear range of calibration graph could be extended from 10 mM to 100 mM MeOH. Anodic oxidation behavior of L-ascorbic acid was studied by mv Ru-O/CN-Ru film on the glassy carbon electrode and the glassy carbon electrode with Rh film, Glassy carbon electrode modified with Ru polymeric film was showed better sensitivity than the Rh-glassy carbon modified electrode (mv Ru-O/CN-Ru/Rh). Calibration graph was linear from 0.1 mM to 5 mM L-ascorbic acid by using glassy carbon electrode modified with Ru polymeric film. Solpe factor and relative coefficient are $-84.78{\mu}A/mM$ and 0.998, respectively.

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