KR101480978B1 - Graphene Counter Electrodes for Dye-sensitized Solar Cell, method for preparing the same and Dye-sensitized Solar Cell comprising the Same - Google Patents
Graphene Counter Electrodes for Dye-sensitized Solar Cell, method for preparing the same and Dye-sensitized Solar Cell comprising the Same Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
본 발명은 a) 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조하는 단계; 및 b) 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명 전극에 표면처리하는 단계를 포함하는 염료감응 태양전지용 그래핀 상대전극, 이의 제조방법 및 이를 포함하는 염료감응 태양전지에 관한 것이다.The present invention relates to a method for producing a graphene compound, comprising the steps of: a) preparing a graphene compound doped with a nitrogen element by doping nitrogen in a graphite; And b) subjecting the graphene compound prepared in step a) to an FTO transparent electrode using electrostatic spray deposition, a graphene counter electrode for a dye-sensitized solar cell, a method for producing the same, And a dye-sensitized solar cell comprising the same.
Description
본 발명은 염료감응 태양전지용 그래핀 상대전극, 이의 제조방법 및 이를 포함하는 염료감응 태양전지에 관한 것이다.The present invention relates to a graphene counter electrode for a dye-sensitized solar cell, a method for producing the same, and a dye-sensitized solar cell comprising the same.
염료감응 태양전지의 원리는, 표면에 염료분자가 화학적으로 흡착된 n-형 나노입자 반도체 산화물 전극에 태양빛(가시광선)이 흡수되면 염료 분자가 전자-홀 쌍을 생성하고, 상기전자는 반도체 산화물의 전도띠로 주입되어 나노입자간 계면을 통하여 투명전도성 막으로 전달되어 전류를 발생시키며, 상기 홀은 산화-환원 전해질에 의해 전자를 받아 다시 환원되며 산화된 전해질이 상대전극으로 이동된 전자를 받아 다시 환원되는 것이다.The principle of a dye-sensitized solar cell is as follows. When sunlight (visible light) is absorbed on an n-type nanoparticle semiconductor oxide electrode on which dye molecules are chemically adsorbed on the surface, dye molecules generate electron-hole pairs, The electrons are injected into the conduction band of the oxide and transferred to the transparent conductive film through the interface between the nanoparticles to generate electric current. The holes are received by the oxidation-reduction electrolyte and reduced again. The oxidized electrolyte receives electrons transferred to the counter electrode It will be reduced again.
현재까지 염료감응 태양전지에 사용되는 상대전극 물질로는 예를 들어, WO98/050393에서와 같이 주로 Pt(platinum)를 사용하였지만, 상기 Pt를 사용하는 경우에는 산화-환원 전해질에 의한 반응으로 인한 부식성으로 인한 안정성이 약하며, 특히 Pt의 가격이 높기 때문에 경제성이 떨어진다는 문제점이 있었다. 따라서, 이러한 문제점을 극복할 수 있는 새로운 상대전극 물질에 대한 개발의 필요성이 요구되고 있다.As the counter electrode material used in the dye-sensitized solar cell up to now, for example, Pt (platinum) is mainly used as in WO98 / 050393, but in the case of using Pt, corrosiveness due to the reaction by the oxidation- And the economical efficiency is low due to the high price of Pt. Therefore, there is a demand for development of a new counter electrode material capable of overcoming such a problem.
본 발명은 기존에 사용해오던 Pt(platinum) 상대전극보다 장기안정성, 촉매 특성이 매우 우수한 염료감응 태양전지용 그래핀 상대전극 및 이의 제조방법을 제공함에 그 목적이 있다.An object of the present invention is to provide a graphene counter electrode for a dye-sensitized solar cell which is superior in long-term stability and catalytic properties to a Pt (platinum) counter electrode that has been used in the past, and a method for manufacturing the same.
상술한 목적을 달성하기 위하여, In order to achieve the above object,
본 발명은 a) 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조하는 단계; 및 b) 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명 전극에 표면 처리하는 단계를 포함하는 염료감응 태양전지용 그래핀 상대전극의 제조방법을 제공한다.The present invention relates to a method for producing a graphene compound, comprising the steps of: a) preparing a graphene compound doped with a nitrogen element by doping nitrogen in a graphite; And b) subjecting the graphene compound prepared in the step a) to surface treatment with an FTO transparent electrode using an electrostatic spray deposition method. do.
또한, 본 발명은 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제공한다.The present invention also provides a graphene counter electrode for a dye-sensitized solar cell comprising a graphene compound doped with a nitrogen element.
또한, 본 발명은 상기 그래핀 상대전극을 포함하는 염료감응 태양전지를 제공한다.The present invention also provides a dye-sensitized solar cell comprising the graphene counter electrode.
상기 과제의 해결 수단에 따른 본 발명의 그래핀 상대전극을 포함하는 염료감응 태양전지는 장기안정성, 촉매 특성이 기존의 Pt 상대전극을 이용한 태양전지에 비하여 매우 우수하다.The dye-sensitized solar cell including the graphene counter electrode of the present invention according to the solution means of the present invention is superior to the solar cell using the conventional Pt counter electrode.
도 1(a)은 본 발명의 합성예 1의 그래핀 화합물 제조단계를 모식화하여 나타낸 도면이다.
도 1(b)은 본 발명의 합성예 2의 그래핀 화합물 제조단계를 모식화하여 나타낸 도면이다.
도 2는 본 발명의 상대전극을 제조하는 단계를 모식화하여 나타낸 도면이다.
도 3(a)는 FTO 표면 상태를 나타낸 사진이다.
도 3(b)는 본 발명의 합성예 1에서 제조한 그래핀을 FTO 투명전극에 정전 방사 전착법으로 표면처리한 후의 상태를 나타낸 사진이다.
도 3(c)는 FTO 표면 상태를 확대하여 나타낸 사진이다.
도 3(d)는 본 발명의 합성예 2에서 제조한 그래핀을 FTO 투명전극에 정전 방사 전착법으로 표면처리한 후의 상태를 나타낸 사진이다.
도 4(a)는 본 발명의 실시예 1 내지 실시예 6에서 제조한 상대 전극을 나타낸 사진이다.
도 4(b)는 본 발명의 실시예 7 내지 실시예 13에서 제조한 상대 전극의 표면을 나타낸 사진이다.
도 5(a)는 본 발명의 실시예 1 내지 실시예 6에서 제조한 상대전극의 투과도를 나타낸 그래프이다.
도 5(b)는 본 발명의 실시예 7 내지 실시예 13에서 제조한 상대전극의 투과도를 나타낸 그래프이다.
도 6(a)은 본 발명의 실시예 1 내지 실시예 6 및 비교예 1에서 제조한 상대전극의 촉매특성을 측정한 그래프이다.
도 6(b)은 본 발명의 실시예 7 내지 실시예 13 및 비교예 1에서 제조한 상대전극의 촉매특성을 측정한 그래프이다.
도 7(a)은 본 발명의 실시예 1 내지 실시예 6 및 비교예 1에서 제조한 상대전극의 안정성을 측정한 그래프이다.
도 7(b)은 본 발명의 실시예 7 내지 실시예 13 및 비교예 1에서 제조한 상대전극의 안정성을 측정한 그래프이다.
도 8(a)은 본 발명의 실시예 14 내지 실시예 19 및 비교예 2에서 제조한 상대전극의 전류-전압 곡선을 측정한 그래프이다.
도 8(b)은 본 발명의 실시예 20 내지 실시예 26 및 비교예 2에서 제조한 상대전극의 전류-전압 곡선을 측정한 그래프이다.
도 9는 본 발명의 실시예 13에서 제조한 상대전극의 그래핀 화합물의 enRP를 측정한 사진이다.
도 10은 본 발명의 합성예 1에서 제조한 그래핀 화합물을 XPS 성분분석한 결과를 나타낸 사진이다.
도 11은 본 발명의 합성예 2에서 제조한 그래핀 화합물을 XPS 성분분석한 결과를 나타낸 사진이다.Fig. 1 (a) is a diagram schematically illustrating the step of preparing the graphene compound of Synthesis Example 1 of the present invention.
Fig. 1 (b) is a diagram schematically illustrating the step of preparing the graphene compound of Synthesis Example 2 of the present invention.
Fig. 2 is a schematic view showing the step of producing the counter electrode of the present invention.
3 (a) is a photograph showing the surface state of the FTO.
Fig. 3 (b) is a photograph showing the state after graphene produced in Synthesis Example 1 of the present invention is surface-treated with an FTO transparent electrode by electrospinning electrodeposition.
3 (c) is a photograph showing an enlarged view of the surface state of the FTO.
FIG. 3 (d) is a photograph showing the state after graphene produced in Synthesis Example 2 of the present invention is surface-treated with an FTO transparent electrode by electrodeposition electrodeposition.
4 (a) is a photograph showing the counter electrode prepared in Examples 1 to 6 of the present invention.
4 (b) is a photograph showing the surface of the counter electrode prepared in Examples 7 to 13 of the present invention.
5 (a) is a graph showing the transmittance of the counter electrode prepared in Examples 1 to 6 of the present invention.
5 (b) is a graph showing the transmittance of the counter electrode prepared in Examples 7 to 13 of the present invention.
6 (a) is a graph showing the catalyst characteristics of the counter electrode prepared in Examples 1 to 6 and Comparative Example 1 of the present invention.
6 (b) is a graph showing the catalytic characteristics of the counter electrode prepared in Examples 7 to 13 and Comparative Example 1 of the present invention.
7 (a) is a graph showing the stability of the counter electrode prepared in Examples 1 to 6 and Comparative Example 1 of the present invention.
7 (b) is a graph showing the stability of the counter electrode prepared in Examples 7 to 13 and Comparative Example 1 of the present invention.
8 (a) is a graph showing current-voltage curves of the counter electrode prepared in Examples 14 to 19 and Comparative Example 2 of the present invention.
8 (b) is a graph showing current-voltage curves of the counter electrode prepared in Examples 20 to 26 and Comparative Example 2 of the present invention.
9 is a photograph of the enRP of the graphene compound of the counter electrode prepared in Example 13 of the present invention.
10 is a photograph showing the XPS component analysis of the graphene compound prepared in Synthesis Example 1 of the present invention.
11 is a photograph showing the XPS component analysis of the graphene compound prepared in Synthesis Example 2 of the present invention.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 염료감응 태양전지용 그래핀 상대전극의 제조방법은 a) 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조하는 단계; 및 b) 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명 전극에 표면처리하는 단계를 포함한다.
A method for preparing a graphene counter electrode for a dye-sensitized solar cell according to the present invention comprises the steps of: a) preparing a graphene compound doped with nitrogen element by doping nitrogen in graphite; And b) surface-treating the graphene compound prepared in step a) on the FTO transparent electrode using an electrostatic spray deposition method.
본 발명의 염료감응 태양전지용 그래핀 상대전극을 제조하기 위해서, 먼저 그래파이트(Graphite)에 질소를 도핑(doping)하여 질소 원소가 도핑된 그래핀화합물을 제조한다. 본 발명에 있어서, 상기 그래파이트에 질소를 도핑하는 방법으로는 특별한 제한은 없으나, 바람직하게는 PPA(polyphosphoric acid)와 P2O5를 이용하여 그래파이트의 표면을 개질함으로써 분산력을 높인 후, 분산된 그래파이트에 질소 분위기 하에서 열처리하여 질소 원소를 도핑시켜 그래핀 화합물을 제조할 수 있다. 또한 그래파이트에서 질소를 도핑하는 다른 방법으로 ball milling방식으로 질소 분위기하에서 그래파이트의 표면을 ball mill사용하여 개질함과 동시에 질소가 도핑시켜 그래핀 화합물을 제조 할 수 있다. 구체적으로, 상기 질소 원소를 도핑시켜 그래핀 화합물의 제조는 도 1(a)에서와 같다. 먼저 순수한 그래파이트의 가장자리 부분에서 선택적인 작용이 수행된다. 이 후, 4-아미노벤조산(4-aminobenzoic acid)의 존재하에서 폴리(인산)/오산화인(P2O5)와 반응하여 가장자리부분에 아미노벤조일기가 형성된 그래파이트(EFG)가 형성한다. 상기 EFG는 다른 변수를 최소화 하기 위하여, 속슬레 추출(Soxhlet extractions)에 의하여 추출한다. 상기 EFG 파우더는 질소 분위기하에서 900℃에서 2시간동안 열처리한다. 열처리하는 동안, EFG의 가장자리에 공유결합된 4-아미노벤조일 부분(4-H2N-Ph-CO-)은 C-용접 및 N-도핑 동안 그래핀 화합물을 만들기 위하여 초기 상태로 있을 수 있다.In order to prepare a graphene counter electrode for a dye-sensitized solar cell of the present invention, graphite is first doped with nitrogen to prepare a graphene compound doped with a nitrogen element. In the present invention, the method of doping the graphite with nitrogen is not particularly limited. Preferably, the surface of the graphite is modified by using PPA (polyphosphoric acid) and P 2 O 5 to increase the dispersing power, Is subjected to heat treatment in a nitrogen atmosphere to thereby form a graphene compound by doping a nitrogen element. Another method of doping nitrogen in graphite is to modify the surface of the graphite using a ball mill in a ball milling manner under nitrogen atmosphere, and at the same time, the graphene compound can be prepared by doping with nitrogen. Specifically, the preparation of the graphene compound by doping the nitrogen element is the same as in FIG. 1 (a). First, a selective action is performed at the edges of the pure graphite. Thereafter, a graphite (EFG) having an aminobenzo group formed at the edge portion is formed by reacting with poly (phosphoric acid) / phosphorus pentoxide (P 2 O 5 ) in the presence of 4-aminobenzoic acid. The EFG is extracted by Soxhlet extractions to minimize other variables. The EFG powder is heat-treated at 900 DEG C for 2 hours in a nitrogen atmosphere. During the heat treatment, covalently linked 4-amino-benzoyl portions (4-H 2 N-Ph -CO-) in the edge of the EFG may be in its initial state to produce a graphene compound during welding and C- N- doping.
또한 그래파이트에서 질소를 도핑하는 다른 방법으로는 도 1(b)에서와 같다.Another method of doping nitrogen in graphite is the same as in Fig. 1 (b).
스텐레스 캡슐안을 질소 분위기하에서 순수한 그래파이트와 5mm지름의 ball mill을 500 RPM속도로 교반시켜 줌으로써 순수한 그래파이트가 깨지면서 활성 라디칼이 생성되어 질소가 쉽게 도핑되는 원리를 이용하였다. In the stainless capsule, pure graphite and a ball mill having a diameter of 5 mm were stirred at a speed of 500 RPM under a nitrogen atmosphere, whereby pure graphite was broken, and an active radical was generated and nitrogen was easily doped.
상기와 같이 제조되는 본 발명의 질소 원소가 도핑된 그래핀화합물은 질소 원소를 1~15 중량% 포함하는 것이 바람직하다. 질소 원소가 1 중량% 미만으로 포함되는 경우 촉매특성 및 안정성에 문제가 있으며, 질소 원소가 15 중량% 초과로 포함되었을 경우에는 질소량 증가에 따른 효과의 증가가 별로 없다. The graphene compound doped with the nitrogen element of the present invention produced as described above preferably contains 1 to 15% by weight of nitrogen element. When the nitrogen element is contained in an amount of less than 1% by weight, there is a problem in the catalyst characteristics and stability. When the nitrogen element is contained in an amount exceeding 15% by weight,
상기 제조된 각각의 그래핀 화합물은 일반적으로 사용되는 유기 용제에 분산될 수 있으며, 이를 이용하여 FTO/유리기판에 증착시킬 수 있다. 종래의 스핀코팅을 이용하는 경우에는 두께, 형태 및 균일성을 제어하기 어렵다는 문제가 있었으나 본 발명에서는 이러한 문제점을 해결하기 위하여, 다음과 같이 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하였다.
Each of the prepared graphene compounds can be dispersed in a commonly used organic solvent and can be deposited on an FTO / glass substrate. In the conventional spin coating method, it is difficult to control thickness, shape, and uniformity. However, in order to solve such a problem, electrostatic sputter deposition is used as follows.
본 발명의 염료감응 태양전지용 그래핀 상대전극을 제조하기 위해서, 이 후, 정전 방사 전착법(Electrostatic Spray Deposition)을 이용하여 상기 제조된 그래핀 화합물을 FTO 투명 전극에 표면 처리하여 상대전극을 제조한다. 상기 정전 방사 전착법은 특별한 제한은 없으나, 바람직하게는 도 2와 같은 장치를 이용할 수 있다. 본 발명의 그래핀 상대전극의 제조방법을 도 2와 함께 살펴보면, 상기 단계에서 제조된 그래핀 화합물은 2-프로판올에 분산된 후, 약 10 kV의 높은 전압하에서 약 200μL/min의 일정한 속도로 분사 모세 혈관에 주입된다. 전기장은 상기 그래핀 화합물을 포함하는 전하를 띤 수많은 미세 방울들을 최소화한 결과로 각 방울의 표면 장력을 극복하게 된다. 이를 통하여, 질소 원소가 도핑된 그래핀화합물이 균일한 FTO/유리 기판 상에 증착되어 FTO 투명 전극의 표면처리를 하게 된다. 상기 FTO 투명 전극에 표면처리하는 단계는 4분 내지 9분의 시간으로 표면처리를 하는 것이 바람직하다. 본 발명의 도 3(a), 도 3(b), 도 3(c), 도 3(d)를 비교해 보면, 정전 방사 전착법으로 표면처리를 한 도 3(b)와 도 3(d)의 FTO 투명 전극은 표면처리를 하지 않은 도 3(a), 도 3(c) 의 FTO 투명 전극에 비하여 강한 촉매특성을 지닌 상대전극이 된다.
In order to prepare the graphene counter electrode for the dye-sensitized solar cell of the present invention, the prepared graphene compound is then surface-treated with an FTO transparent electrode using Electrostatic Spray Deposition to prepare a counter electrode . The electrostatic radiation electrodeposition method is not particularly limited, but an apparatus as shown in Fig. 2 can be preferably used. 2, the graphene compound prepared in the above step is dispersed in 2-propanol and then sprayed at a constant rate of about 200 μL / min under a high voltage of about 10 kV. It is injected into the capillary. The electric field overcomes the surface tension of each droplet as a result of minimizing the number of fine droplets charged with the graphene compound. Through this, a graphene compound doped with a nitrogen element is deposited on a uniform FTO / glass substrate to perform surface treatment of the FTO transparent electrode. It is preferable that the step of performing the surface treatment on the FTO transparent electrode is performed for 4 minutes to 9 minutes. 3 (a), 3 (b), 3 (c) and 3 (d) of the present invention are compared with FIGS. 3 (b) and 3 (d) The FTO transparent electrode of Comparative Example 1 becomes a counter electrode having strong catalytic characteristics as compared with the FTO transparent electrode of Figs. 3 (a) and 3 (c) without surface treatment.
또한, 본 발명은 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제공한다.The present invention also provides a graphene counter electrode for a dye-sensitized solar cell comprising a graphene compound doped with a nitrogen element.
구체적으로 본 발명의 염료감응 태양전지용 그래핀 상대전극은 전도성 투명 기판을 포함하는 제1전극; 및 상기 제1전극 표면에 질소가 도핑된 그래핀 화합물을 포함하는 표면처리 층을 포함한다.More specifically, the graphene counter electrode for a dye-sensitized solar cell of the present invention includes a first electrode including a conductive transparent substrate; And a surface treatment layer comprising a graphene compound doped with nitrogen on the surface of the first electrode.
상기 염료감응 태양전지용 그래핀 상대전극을 구성하는 소재들을 예를 들어 설명하면 다음과 같다. Materials constituting the graphene counter electrode for the dye-sensitized solar cell will be described as follows.
먼저 전도성 투명 기판을 포함하는 제1전극은 질소가 도핑된 그래핀 화합물을 방사 전착법에 의하여 표면처리 할 수 있도록, 투광성 전극을 포함하는 유리 기판 또는 플라스틱 기판일 수 있다. First, the first electrode including the conductive transparent substrate may be a glass substrate or a plastic substrate including a transparent electrode so that the graphene compound doped with nitrogen can be surface-treated by spin-coating.
상기 질소가 도핑된 그래핀 표면층은 산화-환원 특성을 갖는 전해질을 환원 시켜주는 작용을 하는데, 상기 전해질로써는 I-/I3 -, 코발트 착화합물, 페로센 등이 있다.
The graphene surface layer doped with nitrogen serves to reduce an electrolyte having oxidation-reduction properties. Examples of the electrolyte include I - / I 3 - , cobalt complex, ferrocene, and the like.
또한, 본 발명은 상기 그래핀 상대전극을 포함하는 염료감응 태양전지를 제공한다.
The present invention also provides a dye-sensitized solar cell comprising the graphene counter electrode.
이하, 실시예를 통해 본 발명을 구체적으로 설명한다. 그러나, 이러한 실시예는 본 발명을 좀 더 명확하게 설명하기 위하여 제시되는 것일 뿐, 본 발명의 범위를 제한하는 목적으로 제시되는 것은 아니다. 본 발명의 범위는 후술하는 특허청구범위의 기술적 사상에 의해 정해질 것이다.
Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are provided to explain the present invention more clearly and not to limit the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.
그래핀Grapina 화합물의 제조 Preparation of compounds
[합성예 1][Synthesis Example 1]
순수한 그래파이트(Aldrich Chemicals 사 제품) 0.5g와 4-아미노벤조산(4-aminobenzoic acid) 0.5g을 섞은 후, 여기에 PPA(83% P2O5 assay: 20.0 g)/오산화인(P2O5) 5.0g을 넣은 후, 이를 130℃에서 72시간 교반하였다. 이 후, 생성된 화합물을 속슬레 추출(Soxhlet extractions)에 의하여 추출한 후, 생성된 화합물을 질소 분위기하에서 900℃에서 2시간 동안 열처리하여, 질소 원소가 도핑된 그래핀 화합물을 제조하였다. 상기 그래핀 화합물 내의 질소함량을 XPS 분석법을 이용하여 측정하여 도 9에 나타내었으며, 그래핀 화합물의 구성비는 탄소(C) 95.16%, 질소(N) 1.73%, 산소(O) 1.78% 이었다.0.5 g of pure graphite (manufactured by Aldrich Chemicals) and 0.5 g of 4-aminobenzoic acid were mixed, and PPA (83% P 2 O 5 assay: 20.0 g) / phosphorus pentoxide (P 2 O 5 ), And the mixture was stirred at 130 占 폚 for 72 hours. Thereafter, the resulting compound was extracted by Soxhlet extractions, and the resultant compound was heat-treated at 900 ° C for 2 hours under a nitrogen atmosphere to prepare a graphene compound doped with a nitrogen element. The content of the graphene compound was 95.16% of carbon (C), 1.73% of nitrogen (N), and 1.78% of oxygen (O), as measured by XPS analysis.
[합성예 2][Synthesis Example 2]
스텐레스로 이루어진 캡슐에 지름 5mm 스텐레스 ball을 넣고 순수한 그래파이트(Aldrich Chemicals 사 제품) 5g과 8 bar압력에 해당되는 질소가스를 주입하여 밀봉하고 5200 RPM속도로 48시간동한 교반하였다. 이 후, 생성된 화합물을 1M HCl을 이용하여 세척하여주고 세척된 화합물을 0.05 mmHg 압력으로 -120℃ 로 48시간 동한 냉건조 시켜주어 질소 원소가 도핑된 그래핀 화합물을 제조하였다. 상기 그래핀 화합물 내의 질소함량을 XPS 분석법을 이용하여 측정하여 도 9에 나타내었으며, 그래핀 화합물의 구성비는 탄소(C) 70.67%, 질소(N) 14.84%, 산소(O) 7.43%, 수소(H) 0.79% 이었다.
5 g of stainless steel balls were placed in a stainless steel capsule, and 5 g of pure graphite (manufactured by Aldrich Chemicals) was injected with nitrogen gas at a pressure of 8 bar, and the mixture was sealed and stirred at 5200 rpm for 48 hours. Thereafter, the resulting compound was washed with 1M HCl, and the washed compound was cooled and dried at -120 DEG C under 0.05 mmHg pressure for 48 hours to prepare a graphene compound doped with a nitrogen element. The composition ratio of the graphene compound was 70.67% by weight of carbon (C), 14.84% by weight of nitrogen (N), 7.43% by weight of oxygen (O) H) of 0.79%.
상대전극의 제조Production of counter electrode
[실시예 1][Example 1]
상기 합성예 1을 사용하여 질소 원소가 도핑된 그래핀 화합물을 2-프로판올에 분산시킨 후, 10 kV의 전압하에서 200μL/min의 일정한 속도로 분사 모세 혈관에 주입시켰다. Using the above Synthesis Example 1, a graphene compound doped with a nitrogen element was dispersed in 2-propanol, and injected into a jet capillary at a constant rate of 200 μL / min under a voltage of 10 kV.
이 후, 전기장을 가한 후, 1분간 질소 원소가 도핑된 그래핀화합물이 균일한 FTO/유리 기판 상에 증착되도록 FTO 투명 전극의 표면처리를 하여, 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.08 μm 이었다.Thereafter, after the electric field was applied, the FTO transparent electrode was subjected to a surface treatment so that the graphene compound doped with the nitrogen element for one minute was deposited on the uniform FTO / glass substrate to obtain a dye containing a graphene compound doped with nitrogen element A graphene counter electrode for a solar cell was prepared. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.08 μm.
[실시예 2][Example 2]
상기 FTO 투명 전극의 표면처리를 2분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.17 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 1, except that the surface treatment of the FTO transparent electrode was performed for 2 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for a dye-sensitized solar cell was 0.17 μm.
[실시예 3][Example 3]
상기 FTO 투명 전극의 표면처리를 3분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.26 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 1, except that the surface treatment of the FTO transparent electrode was performed for 3 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for a dye-sensitized solar cell was 0.26 탆.
[실시예 4][Example 4]
상기 FTO 투명 전극의 표면처리를 4분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.35 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 1, except that the surface treatment of the FTO transparent electrode was performed for 4 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for a dye-sensitized solar cell was 0.35 μm.
[실시예 5][Example 5]
상기 FTO 투명 전극의 표면처리를 5분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.44 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 1, except that the surface treatment of the FTO transparent electrode was performed for 5 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.44 μm.
[실시예 6][Example 6]
상기 FTO 투명 전극의 표면처리를 6분간 하는 것을 제외하고는 실시예 1과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.51 μm 이었다.
A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 1, except that the surface treatment of the FTO transparent electrode was performed for 6 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.51 μm.
[실시예 7][Example 7]
상기 합성예 2를 사용하여 질소 원소가 도핑된 그래핀 화합물을 2-프로판올에 분산시킨 후, 10 kV의 전압하에서 200μL/min의 일정한 속도로 분사 모세 혈관에 주입시켰다. Using the above Synthesis Example 2, a graphene compound doped with a nitrogen element was dispersed in 2-propanol, and injected into a jet capillary at a constant rate of 200 μL / min under a voltage of 10 kV.
이 후, 전기장을 가한 후, 1분간 질소 원소가 도핑된 그래핀화합물이 균일한 FTO/유리 기판 상에 증착되도록 FTO 투명 전극의 표면처리를 하여, 질소 원소가 도핑된 그래핀화합물을 포함하는 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.08 μm 이었다.Thereafter, after the electric field was applied, the FTO transparent electrode was subjected to surface treatment so that the graphene compound doped with the nitrogen element for one minute was deposited on the uniform FTO / glass substrate, and the dye containing the graphene compound doped with the nitrogen element A graphene counter electrode for a solar cell was prepared. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.08 μm.
[실시예 8][Example 8]
상기 FTO 투명 전극의 표면처리를 2분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.17 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 2 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for a dye-sensitized solar cell was 0.17 μm.
[실시예 9][Example 9]
상기 FTO 투명 전극의 표면처리를 3분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.26 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 3 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for a dye-sensitized solar cell was 0.26 탆.
[실시예 10][Example 10]
상기 FTO 투명 전극의 표면처리를 4분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.35 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 4 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for a dye-sensitized solar cell was 0.35 μm.
[실시예 11][Example 11]
상기 FTO 투명 전극의 표면처리를 5분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.44 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 5 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.44 μm.
[실시예 12][Example 12]
상기 FTO 투명 전극의 표면처리를 6분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.51 μm 이었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 6 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.51 μm.
[실시예 13][Example 13]
상기 FTO 투명 전극의 표면처리를 7분간 하는 것을 제외하고는 실시예 7과 동일한 방법으로 염료감응 태양전지용 그래핀 상대전극을 제조하였다. 제조된 염료감응 태양전지용 그래핀 상대전극의 그래핀 화합물의 두께는 0.58 μm 이었다. 상기 그래핀 화합물의 두께 측정을 도 9에 나타내었다.A graphene counter electrode for a dye-sensitized solar cell was prepared in the same manner as in Example 7, except that the surface treatment of the FTO transparent electrode was performed for 7 minutes. The thickness of the graphene compound of the prepared graphene counter electrode for the dye-sensitized solar cell was 0.58 μm. The measurement of the thickness of the graphene compound is shown in Fig.
[비교예 1][Comparative Example 1]
종래의 염료감응 태양전지용 그래핀 상대전극으로 Pt(platinum) 상대전극을 사용하였다.A Pt (platinum) counter electrode was used as a graphene counter electrode for a conventional dye-sensitized solar cell.
상기 제조된 실시예 1 내지 13의 염료감응 태양전지용 그래핀 상대전극을 도 4(a), 도 4(b)에 나타내었다.
The graphene counter electrodes for the dye-sensitized solar cells of Examples 1 to 13 thus prepared are shown in Figs. 4 (a) and 4 (b).
염료 용액 제조 Dye solution preparation
에탄올 용매 (6mL)에 다음과 같은 염료 및 공흡착 정공수송물질 몰농도로 혼합하여 용액를 제조하였다.Ethanol solution (6 mL) was mixed with the following dyes and a molar concentration of the co-adsorbed hole transporting material to prepare a solution.
0.3m몰(M) 농도의 O-alkylated-JK-225-sensitizer 염료 용매O-alkylated-JK-225-sensitizer dye solvent at a concentration of 0.3mol (M)
30m몰(M) 농도의 DCA 용매
A 30mol (M) concentration of DCA solvent
전해질 제조Electrolyte manufacture
Co(bpy)3(BCN4)2을 0.22 몰(M), Co(bpy)3(BCN4)3을 0.05 몰(M), LiClO4를 0.1 몰(M) 및 4-tert-butylpyridine을 0.8 몰(M) 첨가하여 아세토나이트릴 전해질(2 mL)을 제조하였다.
0.05 mol (M) of Co (bpy) 3 (BCN 4 ) 2 , 0.2 mol of Co (bpy) 3 (BCN 4 ) 3 , 0.1 mol of LiClO 4 (M) and 0.8 of 4-tert-butylpyridine (M) was added thereto to prepare an acetonitrile electrolyte (2 mL).
염료감응 태양전지의 제조 Manufacture of dye-sensitized solar cell
[실시예 14][Example 14]
다음의 공정에 따라 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared according to the following process.
1. FTO 유리기판을 수산화나트륨 세정용액에 넣고 1시간 동안 초음파 세척한 후, 증류수와 에탄올을 이용하여 세척하고, 질소가소를 이용해 건조시켰다.1. The FTO glass substrate was immersed in a sodium hydroxide cleaning solution, ultrasonically cleaned for 1 hour, washed with distilled water and ethanol, and dried using nitrogen gas.
2. 세척된 FTO 유리기판을 40mM 농도의 TiCl4 수용액에 담근 후에 70℃ 오븐에서 30분간 가열하였다.2. The washed FTO glass substrate was immersed in an aqueous solution of TiCl 4 at a concentration of 40 mM and then heated in an oven at 70 ° C for 30 minutes.
3. TiCl4 처리된 FTO 유리기판을 증류수와 에탄올을 이용하여 세척한 후, 질소 가스를 이용하여 건조시키고, 80℃ 오븐에서 10분간 가열하였다.3. The FTO glass substrate treated with TiCl 4 was washed with distilled water and ethanol, dried using nitrogen gas, and heated in an oven at 80 ° C for 10 minutes.
4. 이어서, TiCl4 처리된 FTO 유리기판에 13nm 입자 크기의 Ti02 페이스트를 닥터 블레이드(doctor blade) 방법으로 코팅하고, 상온에서(20℃) 2시간 동안 건조시켰다.4. Next, a 13 nm particle size TiO 2 paste was coated on a TiCl 4 -treated FTO glass substrate by a doctor blade method and dried at room temperature (20 ° C) for 2 hours.
5. Ti02가 코팅된 FTO 유리기판을 80℃ 오븐에서 2시간 동안 건조시켰다.5. TiO 2 -coated FTO glass substrate was dried in an oven at 80 ° C for 2 hours.
6. 이어서, Ti02가 코팅된 FTO 유리기판을 가열로를 이용하여 서서히 온도를 올리면서 최대 500℃에서 30분간 소성시켰다.6. Then, the FTO glass substrate coated with TiO 2 was fired at 500 ° C for 30 minutes with the temperature being gradually raised by using a heating furnace.
7. 상기 소성된 FTO 유리기판을 입자크기 400nm인 Ti02 페이스트를 닥터 블레이드 방법으로 코팅하였다. 그리고 상온에서(20℃) 2시간 동안 건조시킨 후, 가열로를 이용하여 서서히 온도를 올리면서 최대 500℃에서 30분간 소성시켰다.7. The fired FTO glass substrate was coated with a TiO 2 paste having a particle size of 400 nm by a doctor blade method. After drying at room temperature (20 ° C) for 2 hours, the mixture was calcined at 500 ° C for 30 minutes while gradually raising the temperature using a heating furnace.
8. 이어서, 상기 소성된 FTO 유리기판을 40mM TiCl4 수용액에 30분 동안 담근 후, 증류수와 에탄올을 이용하여 세척하고 질소가스를 이용하여 건조시키고, 80℃ 오븐에서 10분 동안 건조하였다.8. Subsequently, the fired FTO glass substrate was immersed in an aqueous 40 mM TiCl 4 solution for 30 minutes, washed with distilled water and ethanol, dried using nitrogen gas, and dried in an oven at 80 ° C for 10 minutes.
9. 이어서, 상기 건조된 FTO 유리기판을 히팅건(heating gun)을 이용하여 30분 동안 소결한 후에 상기에서 제조된 0.3mM로 희석된 O-alkylated-JK-225-sensitizer의 용액에 딥핑(dipping)하여 12시간 동안 염료와 공흡착 전공수송물질을 흡착시켰다. 9. Then, the dried FTO glass substrate was sintered for 30 minutes using a heating gun, and then dipped in a solution of the O-alkylated-JK-225-sensitizer diluted to 0.3 mM prepared in the above ) For 12 hours to adsorb the dye and the vacancy-adsorbing carrier.
10. 상기 염료가 흡착된 FTO 유리기판을 에탄올로 세척한 후, 질소가스를 이용하여 건조시켰다.10. The FTO glass substrate on which the dye was adsorbed was washed with ethanol and then dried using nitrogen gas.
11. FTO 유리기판(상대전극용)에 전해질을 주입하기 위한 지름 0.6mm의 두개 구멍을 뚫었다.11. Two holes with a diameter of 0.6 mm were drilled to inject the electrolyte into the FTO glass substrate (for the counter electrode).
12. 이어서, FTO 유리기판을 H2O/아세톤/HCl(4:4:2, v/v/v%) 수용액에 1시간 동안 담가서 초음파 세척기로 세척하고, 70℃ 오븐에서 30분 동안 건조시켰다.12. Next, the FTO glass substrate was immersed in an aqueous solution of H 2 O / acetone / HCl (4: 4: 2, v / v / v%) for 1 hour and washed with an ultrasonic cleaner and dried in a 70 ° C. oven for 30 minutes .
13. 이어서, 실시예 1에서 제조된 FTO 상대전극을 준비한다.13. Next, the FTO counter electrode prepared in Example 1 is prepared.
14. 상기에서 제조된 산화전극과 환원전극을 고분자 실링 필름(sealing film)을 이용하여 80℃로 가열된 핫프레스(hot press)를 이용하여 합체하였다.14. The oxidation electrode and the reducing electrode prepared above were combined using a polymer sealing film using a hot press heated to 80 ° C.
15. 상기 두개 구멍을 통하여 상기에서 제조된 전해질을 주입하고 실링필름과 커버 글래스(cover glass)로 밀봉하였다.
15. The electrolyte prepared above was injected through the two holes and sealed with a sealing film and a cover glass.
[실시예 15][Example 15]
상기 FTO 상대전극을 실시예 2에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the counter electrode prepared in Example 2 was used as the FTO counter electrode.
[실시예 16][Example 16]
상기 FTO 상대전극을 실시예 3에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the counter electrode prepared in Example 3 was used as the FTO counter electrode.
[실시예 17][Example 17]
상기 FTO 상대전극을 실시예 4에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the FTO counter electrode was replaced with the counter electrode prepared in Example 4.
[실시예 18][Example 18]
상기 FTO 상대전극을 실시예 5에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the FTO counter electrode was replaced with the counter electrode prepared in Example 5.
[실시예 19][Example 19]
상기 FTO 상대전극을 실시예 6에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.
A dye-sensitized solar cell was prepared in the same manner as in Example 14 except that the FTO counter electrode was replaced with the counter electrode prepared in Example 6.
[실시예 20][Example 20]
상기 FTO 상대전극을 실시예 7에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the counter electrode prepared in Example 7 was used as the FTO counter electrode.
[실시예 21][Example 21]
상기 FTO 상대전극을 실시예 8에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the FTO counter electrode was replaced with the counter electrode prepared in Example 8.
[실시예 22][Example 22]
상기 FTO 상대전극을 실시예 9에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the FTO counter electrode was replaced with the counter electrode prepared in Example 9.
[실시예 23][Example 23]
상기 FTO 상대전극을 실시예 10에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the counter electrode prepared in Example 10 was used as the FTO counter electrode.
[실시예 24][Example 24]
상기 FTO 상대전극을 실시예 11에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14 except that the FTO counter electrode was replaced with the counter electrode prepared in Example 11.
[실시예 25][Example 25]
상기 FTO 상대전극을 실시예 12에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14 except that the FTO counter electrode was replaced with the counter electrode prepared in Example 12.
[실시예 26][Example 26]
상기 FTO 상대전극을 실시예 13에서 제조된 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the counter electrode prepared in Example 13 was used as the FTO counter electrode.
[비교예 2][Comparative Example 2]
상기 FTO 상대전극을 비교예 1에서 사용한 상대전극으로 하는 것을 제외하고는 실시예 14와 동일한 방법으로 염료감응 태양전지를 제조하였다.
A dye-sensitized solar cell was prepared in the same manner as in Example 14, except that the FTO counter electrode was used as a counter electrode used in Comparative Example 1.
실험예Experimental Example 1: 염료감응 태양전지 상대전극의 투과도 측정 1: Measurement of transmittance of dye-sensitized solar cell counter electrode
상기 제조된 실시예 1 내지 실시예 13의 투과도를 측정하여 도 5(a), 도 5(b)에 나타내었다. 합성예 1을 이용한 실시예 1의 투과도가 가장 높았으며 실시예 6의 투과도가 가장 낮았다. 합성예 2를 이용한 실시예 7의 투과도가 가장 높았고 실시예 13의 투과도가 가장 낮았다.
The transmittances of the prepared Examples 1 to 13 were measured and shown in Figs. 5 (a) and 5 (b). The transmittance of Example 1 using Synthesis Example 1 was the highest and the transmittance of Example 6 was the lowest. The transmittance of Example 7 using Synthesis Example 2 was the highest and the transmittance of Example 13 was the lowest.
실험예Experimental Example 2: 염료감응 태양전지 상대전극의 촉매특성 측정 2: Measurement of catalytic properties of dye-sensitized solar cell counter electrode
상기 합성예 1을 이용한 실시예 1 내지 실시예 6 및 비교예 1의 상대전극의 촉매 특성의 확인하기 위하여, dummy cell을 제작하여 전해질에 대한 산화-환원 전류값을 측정하였다. 측정된 결과를 도6(a)에 나타내었다. 상기 합성예 2를 이용한 실시예 7 내지 실시예 13 및 비교예 1의 상대전극의 촉매 특성을 같은 방법으로 측정하여 도 6(b)에 나타내었다. 이를 통하여 실시예 4 내지 실시예 6의 경우, 비교예 1(기존의 Pt 상대전극)보다 촉매적 특성이 우수하다는 것을 확인할 수 있었고, 실시예 7 내지 실시예 13의 경우, 비교예 1(기존의 Pt 상대전극)보다 촉매적 특성이 우수하다는 것을 확인하였다.
In order to confirm the catalytic properties of the counter electrodes of Examples 1 to 6 and Comparative Example 1 using Synthesis Example 1, a dummy cell was prepared and the oxidation-reduction current value of the electrolyte was measured. The measured results are shown in Fig. 6 (a). The catalyst characteristics of the counter electrodes of Examples 7 to 13 and Comparative Example 1 using the above Synthesis Example 2 were measured by the same method and shown in Fig. 6 (b). As a result, it was confirmed that the catalytic properties of Examples 4 to 6 were superior to those of Comparative Example 1 (conventional Pt counter electrode). In Examples 7 to 13, Comparative Example 1 Pt counter electrode) of the present invention.
실험예Experimental Example 3: 염료감응 태양전지 상대전극의 안정성 측정 3: Stability measurement of dye-sensitized solar cell counter electrode
실시예 6의 상대전극과 비교예 1의 상대전극의 안정성을 측정하기 위해서 dummy cell 을 제작하여, 다음과 같이 연속적으로 각각의 상대전극에 전압을 연속적으로 가하여 (0 V → 1 V → -1 V → 0 V) 안정성을 테스트하였다. 측정된 테스트 결과를 도 7에 나타내었다. 이를 통하여 실시예 6의 상대전극이 비교예 1(기존의 Pt 상대전극)보다 내부저항 크기가 작음을 확인하여 안정성이 우수함을 확인할 수 있었다. 또한 실시예 12의 상대전극과 비교예 1의 상대전극을 상기와 같은 방법으로 안정성을 테스트하여 실시예 12의 상대전극이 비교예 1보다 내부저항 크기가 작음을 확인하여 안정성이 우수함을 확인하였다.
To measure the stability of the counter electrode of Example 6 and the counter electrode of Comparative Example 1, a dummy cell was prepared, and a voltage was successively applied to each counter electrode continuously (0 V → 1 V → -1 V Gt; 0 V). ≪ / RTI > The measured test results are shown in Fig. As a result, it was confirmed that the counter electrode of Example 6 had a smaller internal resistance than that of Comparative Example 1 (a conventional Pt counter electrode), and thus the stability was excellent. The counter electrode of Example 12 and the counter electrode of Comparative Example 1 were tested for stability in the same manner as described above, and it was confirmed that the counter electrode of Example 12 had a smaller internal resistance than that of Comparative Example 1, and thus the stability was excellent.
실험예Experimental Example 4: 염료감응 태양전지의 성능 평가 4: Performance evaluation of dye-sensitized solar cell
실시예 14 내지 실시예 26 및 비교예 2에서 제조한 각각의 염료감응 태양전지를 사용하여 1 sun(100 mW/cm2) 일루미네이션(illumination) 조건에서 광전류-전압을 측정하여 그 결과를 도 8(a), 8(b) 및 하기 표 1에 나타내었다.
The photocurrent-voltage was measured under illumination conditions of 1 sun (100 mW / cm 2 ) using the respective dye-sensitized solar cells prepared in Examples 14 to 26 and Comparative Example 2. The results are shown in FIG. 8 a), 8 (b) and Table 1 below.
상기에서와 같이, 본 발명에 의한 상대전극을 사용한 실시예 17 내지 26의 태양전지의 VOC, JSC 및 Filter Factor가 종래의 상대전극을 사용한 비교예 2의 태양전지에 비하여 동등 또는 우위의 성능을 갖는 것을 알 수 있다.
As described above, the VOC, J SC and the filter factor of the solar cells of Examples 17 to 26 using the counter electrode according to the present invention are equivalent or superior to those of the solar cell of Comparative Example 2 using the conventional counter electrode .
Claims (7)
b) 정전 방사 전착법(Electronic Spray Deposition)을 이용하여 상기 a) 단계에서 제조된 그래핀 화합물을 FTO 투명전극에 표면처리하는 단계를 포함하고,
상기 FTO 투명 전극에 표면처리하는 단계는 4분 내지 9분간 표면처리를 하여,
FTO 투명 전극에 증착된 그래핀 화합물의 두께가 0.3 내지 0.6μm가 되도록 하는 것을 특징으로는 염료감응 태양전지용 그래핀 상대전극의 제조방법.a) modifying the surface of the graphite using PPA (polyphosphoric acid) and P 2 O 5 , and then heat treating the surface of the graphite under a nitrogen atmosphere to thereby form a graphene compound doped with a nitrogen element step; And
b) surface-treating the graphene compound prepared in step a) with an FTO transparent electrode using an electrodeposition method (Electronic Spray Deposition)
The step of subjecting the FTO transparent electrode to a surface treatment may be a surface treatment for 4 minutes to 9 minutes,
Wherein the thickness of the graphene compound deposited on the FTO transparent electrode is 0.3 to 0.6 占 퐉.
상기 염료감응 태양전지용 그래핀 상대전극은
전도성 투명 기판을 포함하는 제1전극; 및
상기 제1전극 표면에 질소가 도핑된 그래핀 화합물의 두께가 0.3 내지 0.6μm인 표면처리 층을 포함하는 것을 특징으로 하는 염료감응 태양전지용 그래핀 상대전극.A graphene counter electrode for a dye-sensitized solar cell comprising a graphene compound doped with a nitrogen element, which is produced by the method of claim 1,
The graphene counter electrode for the dye-sensitized solar cell
A first electrode comprising a conductive transparent substrate; And
Wherein the graphene counter electrode comprises a surface treatment layer having a thickness of 0.3 to 0.6 占 퐉 in which a nitrogen-doped graphene compound is formed on the surface of the first electrode.
상기 그래핀 화합물은 질소 원소를 1~15 중량% 포함하는 것을 특징으로 하는 염료감응 태양전지용 그래핀 상대전극.The method of claim 4,
Wherein the graphene compound comprises 1 to 15% by weight of a nitrogen element.
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