KR102198369B1 - Photoelectrochemical Hydrogen production system with wavelength selective type - Google Patents
Photoelectrochemical Hydrogen production system with wavelength selective type Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 4
- 230000003247 decreasing effect Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 description 14
- 230000007423 decrease Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002061 nanopillar Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- C25B9/60—Constructional parts of cells
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
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- H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
- H01L31/03048—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP comprising a nitride compounds, e.g. InGaN
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
개시되는 파장 선택형 광전기화학적 수소 생산 시스템는, 서로다른 파장이 혼합된 혼합광이 유입되는 광전극;으로서, In(x)Ga(1-x)N (0≤x<1)으로 마련되되, 상기 혼합광이 유입되는 방향으로 순차로 밴드갭 에너지가 작아지는 복수개의 광흡수층이 적층되어 구비되는 광전극; 상기 광전극과 전기적으로 연결되는 상대전극; 및 상기 광전극과 상기 상대전극이 침지되는 전해액;을 포함한다.The disclosed wavelength-selective photoelectrochemical hydrogen production system is a photoelectrode into which mixed light mixed with different wavelengths is introduced; provided with In(x)Ga(1-x)N (0≦x<1), the mixing A photoelectrode provided by stacking a plurality of light absorbing layers whose band gap energy is sequentially decreased in a direction in which light is introduced; A counter electrode electrically connected to the photoelectrode; And an electrolyte solution in which the photoelectrode and the counter electrode are immersed.
Description
본 발명(Disclosure)은, 파장 선택형 광전기화학적 수소 생산 시스템에 관한 것으로서, 구체적으로 다양한 파장의 빛이 혼합된 혼합광으로부터 얻어지는 전류밀도를 높일 수 있는 파장 선택형 광전기화학적 수소 생산 시스템에 관한 것이다.The present invention (Disclosure) relates to a wavelength-selective photoelectrochemical hydrogen production system, and more particularly, to a wavelength-selective photoelectrochemical hydrogen production system capable of increasing the current density obtained from mixed light in which light of various wavelengths is mixed.
여기서는, 본 발명에 관한 배경기술이 제공되며, 이들이 반드시 공지기술을 의미하는 것은 아니다(This section provides background information related to the present disclosure which is not necessarily prior art).Here, background technology related to the present invention is provided, and these do not necessarily mean known technology (This section provides background information related to the present disclosure which is not necessarily prior art).
기존 화석연료에 기반한 에너지 시스템은 지구온난화, 환경오염, 자원고갈 등의 문제를 일으키므로, 그 대안으로 이른바 ‘수소 경제(hydrogen economy)’가 제안되었다. Existing fossil fuel-based energy systems cause problems such as global warming, environmental pollution, and resource depletion, so a so-called “hydrogen economy” has been proposed as an alternative.
수소 경제란 기존 화석연료 대신에 수소연료를 에너지 수송자(energy carrier)로 사용하는 것으로, 이를 실현하기 위한 가장 원천적이고 핵심적인 문제 중 하나는 수소 연료를 온실가스나 오염 물질을 배출하지 않으면서 경제적으로 생산하는 것이다.Hydrogen economy is the use of hydrogen fuel as an energy carrier instead of conventional fossil fuels. One of the most fundamental and core problems for realizing this is that hydrogen fuel is economical without emitting greenhouse gases or pollutants. Is to produce.
1) 최근 전세계적인 관심과 연구 대상이 되고 있는 광전기화학적 수소 생산법(photoelectrochemical hydrogen production)은 반도체와 전해액 사이 계면에 태양광을 비춰 주어 계면에서 물분해를 수행하는데, 반도체/전해액 계면이 광자를 흡수하여 그 에너지를 화학적 에너지, 즉 수소 연료로 변환시키는 핵심적인 역할을 한다.1) Photoelectrochemical hydrogen production, which has recently been a subject of worldwide interest and research, performs water decomposition at the interface by shining sunlight at the interface between a semiconductor and an electrolyte, and the semiconductor/electrolyte interface absorbs photons. Thus, it plays a key role in converting the energy into chemical energy, that is, hydrogen fuel.
2) 광전극으로도 불리는 반도체 물질은 Si, GaAs 등 단결정 물질부터 TiO2 등 금속 산화물까지 다양한 물질들이 연구되고 있다. 2) Semiconductor materials, also called photoelectrodes, are being studied for a variety of materials from single crystal materials such as Si and GaAs to metal oxides such as TiO 2 .
1972년에 Fujishima와 Honda가 TiO2 전극에 빛을 쪼여 줄 때 수소 발생이 가능하다는 것을 보인 이후 수 많은 연구들이 진행되었으나, 실용적인 소자를 구현하기 위해서는 크게 두 가지 문제점을 해결해야 한다.A number of studies have been conducted since Fujishima and Honda showed that hydrogen can be generated when light is applied to TiO 2 electrodes in 1972, but two problems must be largely solved in order to implement a practical device.
첫째로, 광전극의 에너지 변환 효율을 높여야 한다.First, it is necessary to increase the energy conversion efficiency of the photoelectrode.
태양광을 이용한 광전기화학적 수소 생산에서 에너지 변환 효율은 반도체 물질의 에너지 띠간격 (energy band gap)과 직결된다. 현재 대부분의 산화 금속 물질(TiO2, ZnO 등)은 에너지 띠간격이 너무 커서 태양광 스펙트럼 중 자외선 영역 광자만 흡수하고 다른 영역의 빛은 흡수하지 못하므로 이런 광전극들은 상당히 작은 에너지 변환 효율을 나타낸다. In photoelectrochemical hydrogen production using sunlight, energy conversion efficiency is directly related to the energy band gap of semiconductor materials. Currently, most metal oxide materials (TiO 2 , ZnO, etc.) have too large an energy band gap to absorb photons in the ultraviolet region of the solar spectrum and cannot absorb light in other regions. .
반면, Si, GaAs 등 저에너지에서 중에너지 사이 띠간격 (low to mid bandgap)을 갖는 반도체 물질들은 띠간격이 1.0 ~ 1.5 eV 사이이어서 적외선부터 자외선까지 대부분의 빛을 흡수할 수 있다. On the other hand, semiconductor materials having a low to mid bandgap, such as Si and GaAs, can absorb most of the light from infrared to ultraviolet since the band gap is between 1.0 and 1.5 eV.
그러나, 외부로부터 전압 공급 없이 물분해를 일으키기 위해서는 1.5 V 이상의 광전압(photovoltage)가 필요한데 일반적으로 이러한 광전극들이 나타내는 광전압은 이에 비해 상당히 작다. 즉, 광전극의 에너지 띠간격 선택에 있어서 딜레마가 발생한다.However, in order to cause water decomposition without supplying voltage from the outside, a photovoltage of 1.5 V or more is required. In general, the photovoltage exhibited by these photoelectrodes is considerably smaller than this. That is, a dilemma arises in selecting the energy band interval of the photoelectrode.
두번째로, 광전극의 신뢰성(reliability)도 중요한 이슈이다. Second, the reliability of the photoelectrode is also an important issue.
일반적인 발전소 규모(utility scale) 태양전지에 요구되는 수명이 15~20년임을 감안하면, 궁극적으로 태양광 수소 생산기의 작동 수명도 이에 견줄 만한 수준이 되어야 한다. 그러나 일반적으로 반도체 전극은 부식되기 쉬운 물질이고, 강산이나 강염기성의 전해액 속에서 지속적으로 태양광을 조사받기 때문에, 요구되는 수명을 달성하기 매우 도전적인 상황이다.Considering that the lifespan required for a typical utility scale solar cell is 15-20 years, ultimately the operating life of the solar hydrogen generator must be comparable. However, since semiconductor electrodes are generally corrosive materials and are continuously irradiated with sunlight in a strong acid or strong basic electrolyte, it is a very challenging situation to achieve the required lifespan.
본 발명(Disclosure)은, 서로다른 밴드갭 에너지를 가지는 물질을 적층하여 광전기화학적 물질을 전극으로 활용함으로써, 다양한 파장이 혼합된 혼합광으로부터 전기발생효율을 향상시킬 수 있는 파장 선택형 광전기화학적 수소 생산 시스템의 제공을 일 목적으로 한다.The present invention (Disclosure) is a wavelength-selective photoelectrochemical hydrogen production system capable of improving electricity generation efficiency from mixed light mixed with various wavelengths by stacking materials having different bandgap energies and using a photoelectrochemical material as an electrode. It is for the purpose of providing.
본 발명(Disclosure)은, 광전기화학적 물질을 단일물질로 구비하고, 그 조성비의 조절을 통해 다양한 밴드갭 에너지를 가지도록 함으로서, 전극의 내구성을 향상시킬 수 있는 파장 선택형 광전기화학적 수소 생산 시스템의 제공을 일 목적으로 한다.The present invention (Disclosure) provides a wavelength-selective photoelectrochemical hydrogen production system capable of improving the durability of an electrode by providing a photoelectrochemical material as a single material and having various bandgap energies by adjusting the composition ratio. It is for work purposes.
여기서는, 본 발명의 전체적인 요약(Summary)이 제공되며, 이것이 본 발명의 외연을 제한하는 것으로 이해되어서는 아니 된다(This section provides a general summary of the disclosure and is not a comprehensive disclosure of its full scope or all of its features).Here, a summary of the present invention is provided, and this section provides a general summary of the disclosure and is not a comprehensive disclosure of its full scope or all of its features).
상기한 과제의 해결을 위해, 본 발명을 기술하는 여러 관점들 중 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템은, 서로다른 파장이 혼합된 혼합광이 유입되는 광전극;으로서, In(x)Ga(1-x)N (0≤x<1)으로 마련되되, 상기 혼합광이 유입되는 방향으로 순차로 밴드갭 에너지가 작아지는 복수개의 광흡수층이 적층되어 구비되는 광전극; 상기 광전극과 전기적으로 연결되는 상대전극; 및 상기 광전극과 상기 상대전극이 침지되는 전해액;을 포함한다.In order to solve the above problems, a wavelength-selective photoelectrochemical hydrogen production system according to any one of the various aspects describing the present invention includes a photoelectrode into which mixed light mixed with different wavelengths is introduced; as, A photoelectrode in which In(x)Ga(1-x)N (0≦x<1) is provided by stacking a plurality of light absorbing layers whose band gap energy is sequentially decreased in a direction in which the mixed light is introduced; A counter electrode electrically connected to the photoelectrode; And an electrolyte solution in which the photoelectrode and the counter electrode are immersed.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 복수개의 광흡수층은, 상기 혼합광이 유입되는 방향으로 x가 0으로부터 커지는 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the plurality of light absorbing layers are characterized in that x increases from 0 in a direction in which the mixed light is introduced.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 복수개의 광흡수층은, In 조성비의 변화에 의해 상기 혼합광을 구성하는 다양한 파장의 빛이 가지는 에너지와 실질적으로 동일한 밴드갭 에너지를 가지도록 구비되는 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the plurality of light absorbing layers are substantially equal to the energy of light of various wavelengths constituting the mixed light by a change in the In composition ratio. It is characterized in that it is provided to have a band gap energy.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 광전극은, 상기 혼합광이 유입되는 면에 Al(y)Ga(1-y)N으로 구비되는 광흡수층이 더 적층 구비되며, y는 상기 혼합광이 유입되는 방향으로 점차 작아져 0으로 수렴하는 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the photoelectrode has a light absorbing layer formed of Al(y)Ga(1-y)N on a surface through which the mixed light is introduced. It is further stacked, and y gradually decreases in a direction in which the mixed light is introduced and converges to zero.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 전해액은, NaOH 수용액으로 구비되는 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the electrolyte is characterized in that it is provided as an aqueous NaOH solution.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 광전극은, 표면이 NiO로 촉매처리되는 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the photoelectrode is characterized in that the surface is catalytically treated with NiO.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 광전극은, 상기 혼합광이 조사되는 면의 면방향이 c면인 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the photoelectrode is characterized in that a surface direction of a surface to which the mixed light is irradiated is a c-plane.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 광전극은 전도성물질로 구비되는 와이어와 In에 의해 오믹컨텍 되는 것을 특징으로 한다.In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the photoelectrode is characterized in that the photoelectrode is ohmic contacted by In and a wire provided with a conductive material.
본 발명의 어느 일 관점(aspect)에 따른 파장 선택형 광전기화학적 수소 생산 시스템에서, 상기 광전극은, Si으로 도핑되어 n형 반도체로 구비되는 것을 특징으로 한다. In the wavelength-selective photoelectrochemical hydrogen production system according to an aspect of the present invention, the photoelectrode is doped with Si and provided as an n-type semiconductor.
본 발명에 따르면, 서로다른 밴드갭 에너지를 가지는 광흡수층을 적층하여 광전극을 형성하되, 혼합광이 유입되는 방향으로 밴드갭 에너지가 작아지도록 구비함으로써, 파장에 따른 에너지와 밴드갭 에너지의 차이로 발생되는 에너지 손실(Stokes shift)을 방지할 수 있게 된다. 따라서 수소생성효율이 향상된다.According to the present invention, a photoelectrode is formed by stacking light absorbing layers having different band gap energies, but by providing the band gap energy to decrease in the direction in which the mixed light is introduced, the difference between energy according to wavelength and band gap energy Energy loss (Stokes shift) can be prevented. Therefore, the hydrogen generation efficiency is improved.
본 발명에 따르면, 광전극 물질로 GaN 또는 InGaN을 채용함으로서, 광전극 물질의 내구성이 향상된다.According to the present invention, by employing GaN or InGaN as the photoelectrode material, the durability of the photoelectrode material is improved.
본 발명에 따르면, 광전극 물질인 GaN 또는 InGaN의 면방향을 C면으로 구비함으로써, 장시간 사용에도 수소생성효율이 유지되는 신뢰성을 가지게 된다.According to the present invention, since the surface direction of GaN or InGaN, which is a photoelectrode material, is provided as a C-plane, it is possible to have reliability in maintaining hydrogen generation efficiency even when used for a long time.
도 1은 본 발명에 따른 파장 선택형 광전기화학적 수소 생산 시스템의 일 실시형태를 보인 도면.
도 2는 도 1에서 광전극을 자세히 보인 도면.
도 3은 도 1에서 조촉매에 따른 생성 전류밀도-시간의 선도.
도 4는 도 1에서 광전극의 면방향에 따른 생성 전류밀도-시간의 선도.1 is a view showing an embodiment of a wavelength-selective photoelectrochemical hydrogen production system according to the present invention.
FIG. 2 is a detailed view of the photoelectrode in FIG. 1.
3 is a graph of the current density-time generated according to the cocatalyst in FIG. 1.
4 is a graph of the generated current density-time according to the surface direction of the photoelectrode in FIG. 1.
이하, 본 발명에 따른 파장 선택형 광전기화학적 수소 생산 시스템을 구현한 실시형태를 도면을 참조하여 자세히 설명한다.Hereinafter, an embodiment implementing the wavelength-selective photoelectrochemical hydrogen production system according to the present invention will be described in detail with reference to the drawings.
다만, 본 발명의 본질적인(intrinsic) 기술적 사상은 이하에서 설명되는 실시형태에 의해 그 실시 가능 형태가 제한된다고 할 수는 없고, 본 발명의 본질적인(intrinsic) 기술적 사상에 기초하여 통상의 기술자에 의해 이하에서 설명되는 실시형태를 치환 또는 변경의 방법으로 용이하게 제안될 수 있는 범위를 포섭함을 밝힌다. However, the intrinsic technical idea of the present invention cannot be said to be limited by the embodiments to be described below, and the intrinsic technical idea of the present invention is given below by a person skilled in the art. It turns out to cover the range that can be easily proposed by a method of substitution or change of the embodiment described in FIG.
또한, 이하에서 사용되는 용어는 설명의 편의를 위하여 선택한 것이므로, 본 발명의 본질적인(intrinsic) 기술적 사상을 파악하는 데 있어서, 사전적 의미에 제한되지 않고 본 발명의 기술적 사상에 부합되는 의미로 적절히 해석되어야 할 것이다. In addition, since the terms used below are selected for convenience of description, in grasping the intrinsic technical idea of the present invention, it is not limited to the dictionary meaning and is appropriately interpreted as a meaning consistent with the technical idea of the present invention. Should be.
도 1은 본 발명에 따른 파장 선택형 광전기화학적 수소 생산 시스템의 일 실시형태를 보인 도면, 도 2는 도 1에서 광전극을 자세히 보인 도면, 도 3은 도 1에서 조촉매에 따른 생성 전류밀도-시간의 선도, 도 4는 도 1에서 광전극의 면방향에 따른 생성 전류밀도-시간의 선도이다.1 is a view showing an embodiment of a wavelength-selective photoelectrochemical hydrogen production system according to the present invention, FIG. 2 is a view showing the photoelectrode in detail in FIG. 1, and FIG. 3 is a current density generated according to the cocatalyst in FIG. And FIG. 4 is a graph of generated current density-time according to the surface direction of the photoelectrode in FIG. 1.
도 1 내지 도 4를 참조하면, 본 실시형태에 따른 파장 선택형 광전기화학적 수소 생산 시스템(100)은, 광전극(120), 상대전극(130) 및 전해액(140)으로 구비된다.1 to 4, the wavelength-selective photoelectrochemical
광전극(120)은, 서로다른 파장이 혼합된 혼합광(110)이 유입되어 전류를 생성하는 구성이다.The
본 실시형태에서, 광전극(120)은 In(x)Ga(1-x)N (0≤x<1)으로 마련되며, 혼합광(110)이 유입되는 방향으로 순차로 밴드갭 에너지가 작아지는 복수개의 광흡수층(121)이 적층되어 구비된다.In this embodiment, the
복수개의 광흡수층(121)은, 혼합광(110)이 유입되어 이동하는 방향으로 x가 0으로부터 커지는 순서로 배치된다.The plurality of
구체적으로, 복수개의 광흡수층(121)은, In 조성비의 변화에 의해 혼합광(110)을 구성하는 다양한 파장의 빛이 가지는 에너지와 실질적으로 동일한 밴드갭 에너지를 가지도록 구비된다.Specifically, the plurality of
이에 의해, 혼합광(110)이 유입되어 이동하는 방향으로, 자외선, 가시광선, 적외선 순으로 흡수되어 전류를 생성하게 된다.Accordingly, in the direction in which the
여기서, 복수개의 광흡수층(121)은, 적층되어 구비되는데, 상대적으로 저온 성장이 가능한 MBE 방법에 의해 적층되는 것이 바람직하다. Here, the plurality of
이와 달리, 복수개 광흡수층(121)이 독립적으로 구비되고, 이를 접합하여 구성할 수도 있다. 이때 각각의 광흡수층(121)의 양면은 산란에 의한 손실을 방지하기 위해 폴리싱되어 구비되는 것이 바람직하다. Alternatively, a plurality of
한편, 본 실시형태에서, 광전극(120)은, 혼합광(110)이 유입되는 면에 Al(y)Ga(1-y)N으로 구비되는 광흡수층(121)이 더 적층 구비될 수 있다.Meanwhile, in the present embodiment, the
여기서, y는 혼합광(110)이 유입되는 방향으로 점차 작아져 0으로 수렴하도록 구비된다.Here, y is provided to gradually decrease in the direction in which the
또한, 본 실시형태에서, 광전극(120)은, Si로 도핑된 n형 반도체로 구비되는 것이 바람직하다.In addition, in this embodiment, the
상대전극(130)은, 광전극(120)과 전기적으로 연결되어 구비되어, 전기분해에 의한 수소발생을 가능하게 하는 구성이다.The
상대전극(130)의 재질로는, Pt, p형 전도성을 가지는 GaN을 예로 들 수 있다. 내구성에 있어서, p형 전도성을 가지는 GaN이 우수하다.The
전해액(140)은, 전기분해에 의한 수소생성을 위한 구성으로서, 광전극(120)과 상대전극(130)이 침지되어 구비되며, 전극의 내구성 향상을 위해 NaOH 수용액으로 구비되는 것이 바람직하다.The
도 1에서 101은 수조이다.In Fig. 1, 101 is a water tank.
한편, 본 실시형태에서, Ag/AgCl/NaCl로 구비되는 기준전극(미도시)이 더 구비될 수 있다. Meanwhile, in the present embodiment, a reference electrode (not shown) made of Ag/AgCl/NaCl may be further provided.
또한, 본 실시형태에서, 광전극(120)은, 혼합광(110)이 조사되는 면을 향하여 형성되는 나노필라(Nano pillar) 형상으로 구비되는 것이 바람직하다.In addition, in this embodiment, the
이는 에칭에 의해 형성될 수 있다It can be formed by etching
이는 혼합광(110)이 조사되는 면적을 향상시킴으로서, 전기 발생 효율을 향상시킬 수 있게 된다.This improves the area to which the
다만, 광전극 표면의 나노필라(Nano pillar)는 규칙적으로 배열되는 것이 요구된다. 불규칙한 형상으로 배열되는 경우 반사 또는 산란에 의한 효율감소가 커지는 문제가 있다.However, it is required that the nano pillars on the surface of the photoelectrode be arranged regularly. When arranged in an irregular shape, there is a problem that the efficiency decrease due to reflection or scattering increases.
한편, 본 실시형태에서, 광전극(120)은, 표면이 NiO로 촉매처리되는 것이 바람직하다.On the other hand, in this embodiment, it is preferable that the surface of the
촉매처리는, Colloidal 방법 또는 E-beam 증착을 예로 들 수 있다.The catalytic treatment is, for example, a colloidal method or E-beam deposition.
도 3을 참조하면, Colloidal 방법(A)와 E-beam 증착(B)에서 공통적으로 촉매처리가 되지 않은 reference에 비해 전류밀도가 높은 것을 확인할 수 있다.Referring to FIG. 3, it can be seen that in the colloidal method (A) and E-beam deposition (B), the current density is higher than that of a reference that is not commonly subjected to catalyst treatment.
특히, 시간이 지남에 따라 reference는 전류밀도가 감소하는데 반해, 촉매처리된 전극의 경우 일정한 전류밀도를 유지하고 있음을 확인할 수 있다.In particular, it can be seen that the reference current density decreases over time, whereas the catalytic electrode maintains a constant current density.
이는 전극의 내구성이 향상됨을 의미한다.This means that the durability of the electrode is improved.
한편, 본 실시형태에서, 광전극(120)은, 혼합광(110)이 조사되는 면의 면방향이 c면인 것이 바람직하다. 즉 극성면인 것이 바람직하다. On the other hand, in this embodiment, it is preferable that the surface direction of the surface to which the
도 4를 참조하면, 혼합광(110)이 조사되는 면이 극성면인 경우가 반극성면인 경우에 비해 생성되는 전류밀도가 크고, 350시간 이후에서도 내구성이 유지되고 있음을 확인할 수 있다.Referring to FIG. 4, it can be seen that when the surface to which the
한편, 본 실시형태에서, 광전극(120)은 전도성물질로 구비되는 와이어와 오믹컨택을 위해, In에 의해 접합되는 것이 바람직하다.Meanwhile, in the present embodiment, the
Claims (9)
상기 광전극과 전기적으로 연결되는 상대전극; 및
상기 광전극과 상기 상대전극이 침지되는 전해액;을 포함하고,
상기 복수개의 광흡수층은, 상기 혼합광이 유입되는 방향으로 x가 0으로부터 커지는 것을 특징으로 하고,
상기 복수개의 광흡수층은, In 조성비의 변화에 의해 상기 혼합광을 구성하는 다양한 파장의 빛이 가지는 에너지와 동일한 밴드갭 에너지를 가지도록 구비되는 것을 특징으로 하며,
상기 광전극은, 상기 혼합광이 유입되는 면에 Al(y)Ga(1-y)N으로 구비되는 광흡수층이 더 적층 구비되며, y는 상기 혼합광이 유입되는 방향으로 점차 작아져 0으로 수렴하는 것을 특징으로 하고,
상기 전해액은, NaOH 수용액으로 구비되는 것을 특징으로 하며,
상기 광전극은, 표면이 NiO로 촉매처리되는 것을 특징으로 하고,
상기 광전극은, 상기 혼합광이 조사되는 면의 면방향이 극성인 c면인 것을 특징으로 하며,
상기 광전극은 전도성물질로 구비되는 와이어와 In에 의해 오믹컨텍 되는 것을 특징으로 하고,
상기 광전극은, Si으로 도핑되어 n형 반도체로 구비되는 것을 특징으로 하는 파장 선택형 광전기화학적 수소 생산 시스템.
A photoelectrode into which mixed light of different wavelengths is introduced; as In(x)Ga(1-x)N (0≦x<1), a band gap sequentially in a direction in which the mixed light is introduced A photoelectrode provided by stacking a plurality of light absorbing layers for reducing energy;
A counter electrode electrically connected to the photoelectrode; And
Including; an electrolyte in which the photoelectrode and the counter electrode are immersed,
The plurality of light absorbing layers are characterized in that x increases from 0 in a direction in which the mixed light is introduced,
The plurality of light absorbing layers are provided to have the same band gap energy as the energy of light of various wavelengths constituting the mixed light by a change in the In composition ratio,
In the photoelectrode, a light absorbing layer formed of Al(y)Ga(1-y)N is further stacked on a surface through which the mixed light is introduced, and y is gradually decreased in a direction in which the mixed light is introduced to zero. Characterized by convergence,
The electrolyte solution is characterized in that it is provided as an aqueous NaOH solution,
The photoelectrode is characterized in that the surface is catalytically treated with NiO,
The photoelectrode is characterized in that the surface direction of the surface to which the mixed light is irradiated is a polarity c surface,
The photoelectrode is characterized in that ohmic contact is made by a wire provided with a conductive material and In,
The photoelectrode is a wavelength-selective photoelectrochemical hydrogen production system, characterized in that provided with an n-type semiconductor doped with Si.
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