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Highly efficient and robust 3D nanoarchitecture electrocatalysts for energy conversion applications = 고활성 및 고내구성을 갖는 삼차원 나노아키텍처 전기화학촉매의 에너지 전환 분야 응용
서명 / 저자 Highly efficient and robust 3D nanoarchitecture electrocatalysts for energy conversion applications = 고활성 및 고내구성을 갖는 삼차원 나노아키텍처 전기화학촉매의 에너지 전환 분야 응용 / Jong Min Kim.
발행사항 [대전 : 한국과학기술원, 2018].
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Recently, clean energy sources derived from renewable energy have attracted much attention as an alternative to global climate change and petroleum-based energy source depletion. Therefore, it is essential to secure environmentally friendly clean energy sources for the survival, health and life of human beings in the future. To achieve this, one of the key technologies is the energy conversion, production, and storage using electrocatalysts. Thus, in this dissertation, the development of highly efficient and robust electrocatalysts and its application will be described. First, in Chapter 2, we will describe multiscale Pt nanoarchitecture as electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs) that converts hydrogen energy into electrical energy. In contrast with conventional commercial catalysts such as Pt/C, multiscale Pt nanoarchitecture catalyst have no carbon corrosion phenomenon and dramatically reduce the thickness of the electrodes resulting in superior durability and mass transfer enhancement. In addition, it is possible to control the crystal plane of the catalyst surface to achieve excellent specific activity via oblique angled deposition process. Secondly, in Chapter 3, we will describe the development of high-performance 3D Au nanoarchitectural electrocatalysts for $CO_2$ reduction systems which convert $CO_2$ to electro-fuels. Herein, we controlled the microstructure of Au nanowires to form high index plane and high density of grain boundaries. Simultaneously, by fabricating 3D Au nanoarchitectures to induce local pH gradient effect, high faradaic efficiency at low overpotential could be obtained. Lastly, the aforementioned 3D nanoarchitecture electrocatalysts were fabricated by nanotransfer printing process. Because this process is very simple and can be mass-produced, thus, it can be applied to real industry. Furthermore, if we extend these processes to a variety of materials, it will be able to provide a new pathway for the development of highly efficient and robust electrocatalysts to various energy application fields.

최근 들어 재생 가능한 에너지로부터 얻어지는 청정 에너지원은 전 세계의 기후 변화나 에너지원의 고갈 문제를 해결할 수 있는 대안으로 많은 각광받고 있다. 따라서 미래에 인류의 생존과 건강, 풍요로운 생활을 위해서는 이러한 청정에너지 자원의 확보가 필수적인데, 이를 달성하기 위한 핵심기술 중에 하나는 전기화학촉매를 이용한 에너지 변환, 생산, 저장이라고 할 수 있다. 이에 본 학위 논문에서는 우수한 촉매 활성을 가지며 내구성이 우수한 전기화학촉매를 개발하고 에너지 전환 분야에 응용 하고자 한다. 먼저 2장에서는 수소 에너지를 전기에너지로 전환하는 연료전지에 적용되는 삼차원 백금 아키텍처 촉매연구에 관한 내용으로, 촉매 표면의 결정면을 제어하고 촉매층 내의 물질의 이동거리를 감소시켜 우수한 활성 및 물질전달특성을 구현하였다. 더불어 탄소지지체가 없기에 기존 상용 촉매의 탄소부식에 의한 촉매 열화 문제를 해결하였다. 3장에서는 이산화탄소 환원촉매로 활용될 수 있는 삼차원 금 아키텍처 촉매연구에 관한 연구로, 표면의 미세조직을 제어하고, 동시에 삼차원 아키텍처 구조를 통해 국부적 pH 농도변화를 통해 유도함으로써 높은 일산화탄소 패러데이 효율을 달성하였다. 이러한 삼차원 아키텍처 기반의 촉매들의 경우 진공 증착 기반의 나노전사 프린팅 공정을 통해 구현되는데, 간단하고 저렴하며 대량생산이 가능한 공정적인 장점으로 인해 향후 에너지분야의 필요한 전기화학촉매 연구에 새로운 방향을 제시할 수 있으리라 예상된다.

서지기타정보

서지기타정보
청구기호 {DMS 18004
형태사항 vi, 101 p. : 삽화 ; 30 cm
언어 영어
일반주기 저자명의 한글표기 : 김종민
지도교수의 영문표기 : Yeon Sik Jung
지도교수의 한글표기 : 정연식
수록잡지명 : " Eliminating the Trade-Off between the Throughput and Pattern Quality of Sub-15 nm Directed Self-Assembly via Warm Solvent Annealing ". Advanced Functional Materials, vol 25, Issue 2, 306-315(2014)
학위논문 학위논문(박사) - 한국과학기술원 : 신소재공학과,
서지주기 Including references.
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World climate summit and greenhouse gas emissions warning. (a) Paris

Schematic ofPEMFCsoperation. Singlemembrane electrode assemblycomposing

Typical PEMFCs polarization curve exhibiting the various region ofoverpotential

Electrocatalytic oxygen reduction reaction. (a) The oxygen reduction reaction

Simplified representation of suggested degradation mechanisms for platinum

The major issues of nanostructured thin film electrode (NSTF) by 3M company. (a) Water management problem in stacks due to small surface area and amountofpore and (b) water management strategies for NSTF MEA by controlling systematic variables.「47

An overall schematic ofelectro-fuel enabled energy storage to mitigate the mismatch between renewable energy generation and demand.[13]

Mechanism for electrochemical CO2 reduction reaction on various metal surface in water.[12]

Standard redox potentials for CO2 reduction reaction.[13]

Various strategies forhigh faradaic efficiency for CO conversion. (left) Microstructure engineered electrocatalysts by controlling grain boundary densityand surface facet.[14, 16] (right) 3D nanostructure engineered electrocatalysts for maximizing local pH gradient effect.[15,17]

Schematic images of(a) conventional nanotransfer printing[18] and(b) solven assisted nanotransfer printing.[23]

Schematic illustration thatthe possible texture evolution mechanism for (a) normal incidence deposition and (b) oblique angle deposition.[24]

Roll-to-roll based nanotransfer printing process for high-throughput

Schematic illustration of (a) commercial Pt/C electrode and (b) multiscale P nanoarchitecture electrode. Multiscale Ptnanoarchitecture electrode exhibits enhanced oxyger reduction reaction as well as mass transport. Furthermore, the stability of multiscale P nanoarchitecture is much higher than that ofcommercial Pt/C dueto the carbon-free condition

Fabrication process of3D Pt nanoarchitectures via solvent-assisted nanotransfer printing (s-nTP).

Transfer process offabricated the PtNA onto glassy carbon electrode or nafion membrane. In this process, PMMA polymer was used as a transfer medium and Cu foil was used sacrificial substrate.

Schematic illustration and corresponding SEM images of(b) narrow, (c) sparse, and (d) multiscale Pt nanoarchitecture. Multiscale Pt nanoarchitecture is fabricated by alternatinglayers ofnarrow and sparse Pt nanowire arrays.

X-ray photoelectron spectra (XPS) for the commercial Pt/C and Pt nanowires.

The ratio ofPt and Pt oxidation properties of commercial Pt/C and the narrow PtNA.

Surface crystal orientation analysis forcommercial Pt/C andPtnanowire. ASTAR orientation map for(a-b) conventional Pt/C and (c-d)3DPtPtNArespectively. (e)Color-coded inverse polefiguremap ofplatinum.

ASTAR orientation map of(a) pristine the narrow PtNW and (b) thermal treated PtNW respectively. After thermal treatment at 500'C in reducing atmosphere using rapid thermal annealing process, Pt(110)-oriented crystal plane still was observed.

TEM images, SAED patterns (inset) andX-ray diffraction (XRD) patterns collected for the Pt nanowires. The Grain size was calculated using scherrer equations.

a) Oxygen reduction reaction (ORR) curves ofthe commercial Pt/C and PtNWs in O2-saturated 0.1 MHCIO4 solution atroom temperature. (Sweep rate 10 mVs-).b)cyclic voltammetry curves obtained from the commercial Pt/C and PtNWsin N2-saturated 0.1M HCIO4 solutions at 50mVs-l

Comparison ofelectorochemical durability ofthe commercial Pt/C and PtNWs. The durability test was carried out atroom temperature in N2-saturated 0.1MHCI04 solutions with a sweep rate of100 mVS-1. (Scan range 0.6V-1.0V)

ECSAs for the commcercial Pt/C and PtNWs. Mass activity and specific activity for commercial Pt/C and PtNWs at0.9V versus reversible hydrogen electrode (RHE).

Comparison ofelectorochemical durability ofthe commercial Pt/C and PtNWs. The durability test were carried out at room temperature in N2-saturated 0.1MHCI04 solutions with a sweep rate of100 mVS-1. (scan range 0.6V- 1.1V)

Comparison ofelectorochemical durability ofthe commercial Pt/C and PtNWs. The durability test were carried out atroom temperature in N2-saturated 0.1MHCI04 solutions with a sweep rate of100 mVS-1. (scan range 0.6V-1.1V)

Normalized ECSAs for commercial Pt/C and PtNWs.

Photograph of preparation for practical PEMFC single cell.

Polarization curves ofPtNA electrode-based MEA depending on the number of layers and humidity test. Test at80 'C H2/Airin MEA with ambient pressure.

Schematic illustration of 3D multiscale Pt nanoarchitectures. By combining narrow PtNA (50 nm width and 200 nm pitch) and sparse PtNA (200nm width and 1.2 um pitch), multiscale Pt nanoarchitecture were designed and fabricated.

Polarization curves ofPtNA electrode-based MEA. Testat80 SC/Airin MEA; fully humidified with ambientpressure and total outlet pressure of150kPa. For the all MEAs, the cathode catalyst loading was ~ 0.08 mg cm-2.

a) The graph for the oxygen gain obtained by calculating potential difference when oxygen and air are supplied respectively. b) The difference of power density between conventional Pt/C and PtNAs-based electrode under the conditions ofH2/Air.

Cyclic voltammograms of electrodes (left) commercial Pt/C, (b) Narrow PtNA and Multiscale PtNA cathode in the potential range of0.05-1.20V,and the scan rate was 50 mV/s.

.Accelerated degradation test(ADT) withthe cyclicpotential sweeping betweer 1.0 and 1.5 V ata scan rate of50 mVs-1 in single cell. Cyclic voltammetry of(a) Pt/C and (b nultiscale PtNA based MEAs before and after ADT.

a) Schematic illustration ofmicrostructure engineering process for fabricated A nanowires based on oblique angled deposition. TEM images ofb) bare Au c) Au nanowire Theinsetsinb) and c) are the corresponding selected area electron diffraction (SAED) patter d)X-ray diffraction (XRD) patternsande) thecolor-coded inversepolefiguremaps byelectrc backscattering diffraction (EBSD) characterization for t

TEM images and XRD results ofAu NWs depending on deposition angles, a) 0 andb) 850respectively. The green colorindicate preferential crystal orientation and blue co

Electron backscattering diffraction (EBSD) results forAuNWs. a) color-mapping ofa) normally transferred Au NWs and b) inversely transferred Au NWs. For more accurate measurement, Au NWs were fabricated by obliqueangled deposition with 750 and used in this experiment.

Au 4f X-ray photoelectron spectrometer (XPS) spectra of bare Au and Au nanowires respectively.

(a)Schematicillustration ofarchitecture engineeringprocessbysequential printing. Top-view and cross-sectional SEM images of (b), (e) Au nanowires and multi-stacked Au nanowires with (c), (f)5layers and (d), (g) 10 layers.

a) Linear sweep voltammetry (LSV) curve of bare Au and Au NWs stacked electrodes in COz-saturated 0.2 M KHCO3. b)CO selectivity ofbare Au and Au NWs stacked electrodes as a function oftheapplied potential in CO2-saturated 0.2 MKHCO3.

a) CO evolvingpartial current density (jco), b) H2 evolving par (jH2) ofbare Au and stackedAu NWs electrodes. All current densities are nol current densitv with ECSA

The Tafel slopes ofbareAu,stacked Au NWs electrodes with 1,5 and 10 layers are 126,91,85 and 85 mV dec-1, respectively.

Catalytic stability graph MS-Auand bare Au electrodes forCO2reduction. CO2RR activity ofthe MS-Auand bare Au electrodes gradually decrease with reaction times. (-0.39V VS RHE, COz-saturated 0.2 M KHCO3 aqueous solution)

Electron backscattering diffraction (EBSD) results for Au NWs a) before and b) after CO2 reduction reaction. Transforming high index plane of Au NWs to low index plane and agglomerating largegrains to small grains were observed.

Geometric current density before ECSA normalization ofMS-Au and bare A electrodes versus applied potential in 0.2 M KHCO3 aqueous solution.

Cross sectional SEM images ofMS-Au electrodes (1,5 and 10 layers) after the 30 minutes reaction at-0.39 V VS RHE in 0.2 MKHCO3 aqueous solution. Multi-stacked Au NWs structures are maintained even after reaction without any significant structural changes compared to Figure 2.

Catalytic stability graph MS-Au and bare Au electrodes for CO2 reduction CO2RR activity ofthe MS-Au and bare Au electrodes gradually decrease with reaction times. (-0.89 V VS RHE, COz-saturated 0.2 M KHCO3 aqueous solution)

Electron backscattering diffraction (EBSD) results forAu NWs a) before and b) after CO2 reduction reaction. Transforming high index plane ofAu NWs to low index plane and agglomerating largegrains to small grains were observed.