KR101117156B1 - Manufacturing methods of electrode comprising PEDOT-PSSA cathode and transparent conducting layer of the same to dye-sensitized solar cell electrode - Google Patents
Manufacturing methods of electrode comprising PEDOT-PSSA cathode and transparent conducting layer of the same to dye-sensitized solar cell electrode Download PDFInfo
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- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 12
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000012756 surface treatment agent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004065 semiconductor Substances 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
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- 229920000642 polymer Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 230000029553 photosynthesis Effects 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- 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
- 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
- Y02E10/549—Organic PV 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
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
Abstract
본 발명은 염료감응 태양전지 음극용 PEDOT-PSSA 복합층 및 이를 포함하는 염료감응 태양전지로, 보다 상세하게는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법 및 상기 제조방법에 따른 음극 전극을 구비하는 염료감응 태양전지에 관한 것으로, 상기 염료감응 태양전지는 PEDOT-PSSA 복합층을 구비함으로써 2 내지 100 ohm/sq의 면저항 및 5B의 접착력과 2H 이상의 경도에 따른 우수한 표면 물성을 가질 뿐 아니라 투명전극의 저항을 낮게 회복시킴으로써 크게 향상된 광전변환효율을 효과를 얻을 수 있는 장점이 있다.The present invention is a dye-sensitized solar cell negative electrode PEDOT-PSSA composite layer and a dye-sensitized solar cell comprising the same, and more particularly, the manufacturing method of the dye-sensitized solar cell negative electrode PEDOT-PSSA composite layer and the negative electrode according to the manufacturing method Dye-sensitized solar cell comprising a, the dye-sensitized solar cell has a surface resistance of 2 to 100 ohm / sq and the adhesion of 5B and excellent surface properties according to the hardness of more than 2H by having a PEDOT-PSSA composite layer By recovering the resistance of the transparent electrode low, there is an advantage that the effect can be greatly improved photoelectric conversion efficiency.
Description
본 발명은 염료감응 태양전지 음극용 PEDOT-PSSA 복합층 및 이를 포함하는 염료감응 태양전지에 관한 것으로, 보다 상세하게는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법 및 상기 제조방법에 따른 음극 전극을 구비하는 염료감응 태양전지에 관한 것이다.The present invention relates to a dye-sensitized solar cell negative electrode PEDOT-PSSA composite layer and a dye-sensitized solar cell comprising the same, and more particularly, to a method for producing a dye-sensitized solar cell negative electrode PEDOT-PSSA composite layer and It relates to a dye-sensitized solar cell having a cathode electrode.
기존의 실리콘 태양전지는 높은 가격과 원료고갈(실리콘)의 문제를 안고 있고, 순수 유기 태양전지는 화학적 불안전성과 낮은 에너지 변화효율로 인하여 아직은 순수 기초연구에 주력하고 있는 상황이다. 따라서 낮은 가격과 비교적 높은 변화효율을 가지고 있는 염료감응 태양전지의 개발이 부각되고 있다.Existing silicon solar cells have problems of high price and raw material depletion (silicon), and pure organic solar cells are still focusing on pure basic research due to chemical instability and low energy change efficiency. Therefore, the development of dye-sensitized solar cells with low price and relatively high change efficiency is emerging.
상기 염료감응 태양전지는 가시광선을 흡수하여 전자-홀 쌍(electron-hole pair)을 생성할 수 있는 감광성 염료분자와, 생성된 전자를 전달하는 전이금속 산화물을 주된 구성 재료로 하는 광전기화학적 태양전지이다.The dye-sensitized solar cell is a photoelectrochemical solar cell mainly composed of a photosensitive dye molecule capable of absorbing visible light to generate an electron-hole pair, and a transition metal oxide for transferring the generated electrons. to be.
상기 염료감응 태양전지의 음극은 유리기판상에 형성된 투명 도전막과 이산화티탄과 같은 산화물 반도체 나노 입자로 이루어진 산화물 반도체막으로 구성된다. 상기 산화물 반도체막상에는 염료 고분자가 흡착 등의 방법으로 제공된다. 상기 염료 감응 태양전지의 양극(상대전극)으로는 통상적으로 백금과 같은 물질이 사용되며 유리기판상에 제공된다. 음극과 상대전극이 합착된 사이에는 전해질이 제공된다. 이와 같은 구조로 이루어진 염료감응 태양전지는 식물의 광합성 원리를 응용하는 전지이다. 염료에 의한 광전현상에 관해서는 1887년 비엔나 대학의 모세르(Moser) 박사에 의해 보고된 이후 꾸준히 연구되어 왔으며, 현재는 1993년 에콜 폴리테크 페데랄(Ecole Polytechnique Federale)의 그라첼(Gratzel) 교수의 연구팀에 의해 보고된 Ru계 염료와 I-/I3-전해질을 사용한 10% 대의 최고 효율을 지닌 통칭 그라첼(Gratzel) 전지가 주로 연구되고 있다.The cathode of the dye-sensitized solar cell is composed of an oxide semiconductor film made of a transparent conductive film formed on a glass substrate and oxide semiconductor nanoparticles such as titanium dioxide. On the oxide semiconductor film, a dye polymer is provided by a method such as adsorption. As the anode (relative electrode) of the dye-sensitized solar cell, a material such as platinum is generally used and provided on a glass substrate. An electrolyte is provided between the negative electrode and the counter electrode. Dye-sensitized solar cells made of such a structure is a battery applying the photosynthesis principle of plants. Dye photoelectric phenomena have been steadily studied since it was reported by Dr. Moser of the University of Vienna in 1887 and is now Professor Gratzel of Ecole Polytechnique Federale in 1993. The most commonly known Grazelzel cells with Ru-based dyes and I- / I3-electrolytes reported by the team have been studied.
전술한 바와 같이, 염료감응 태양전지의 음극은 투명 도전막과 산화물 반도체막의 적층 구조로 이루어지는데, 반도체 산화막의 형성 과정에서 도입된 열처리에 의해 투명 도전막이 산화되는 것이 불가피하고, 따라서 투명 도전막의 전기적 특성이 열화되게 된다는 문제점을 가지고 있으며 공정이 복잡하거나 제조비용이 크다는 단점이 있다.As described above, the cathode of the dye-sensitized solar cell has a laminated structure of a transparent conductive film and an oxide semiconductor film, and it is inevitable that the transparent conductive film is oxidized by the heat treatment introduced in the process of forming the semiconductor oxide film. There is a problem in that the characteristics are deteriorated, there is a disadvantage that the process is complicated or expensive manufacturing.
이에 본 발명자들은 염료감응 태양전지의 적층 전극의 제조시 열처리에 의한 전기적 특성의 열화를 방지할 수 있으며, 광전변환효율이 보다 향상된 염료감응 태양전지를 발견하고 본 발명을 완성하였다.Accordingly, the present inventors can prevent the deterioration of the electrical properties by heat treatment during the manufacture of the laminated electrode of the dye-sensitized solar cell, and found a dye-sensitized solar cell with improved photoelectric conversion efficiency and completed the present invention.
본 발명의 목적은 다양한 기판위에 전기적 특성의 열화를 회복할 수 있는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법을 제공하고자 한다.An object of the present invention is to provide a method for producing a PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode capable of restoring the deterioration of electrical properties on a variety of substrates.
본 발명의 또 다른 목적은 상기 제조방법으로 제조된 PEDOT-PSSA 복합층을 구비하는 음극 전극에 따른 광전변환 효율이 보다 향상된 염료감응 태양전지를 제공하고자 한다.Still another object of the present invention is to provide a dye-sensitized solar cell having improved photoelectric conversion efficiency according to a cathode electrode having the PEDOT-PSSA composite layer manufactured by the above-described manufacturing method.
이하 첨부한 도면들을 참조하여 본 발명의 제조방법을 상세히 설명한다. 다음에 소개되는 도면들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이며 과장되어 도시될 수 있다. Hereinafter, a manufacturing method of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples and may be exaggerated in order to sufficiently convey the spirit of the present invention to those skilled in the art.
이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.
본 발명은 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법 및 상기 제조방법에 따른 음극 전극을 구비하는 염료감응 태양전지를 제공하고자 한다.The present invention is to provide a dye-sensitized solar cell having a method for producing a PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode and a cathode electrode according to the method.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 The present invention
a) EDOT(ethylene-2,3-dioxythiophene) 10 내지 30중량%, PSSA(Polystyrene sulfonic acid) 10 내지 20 중량% 및 물 60 내지 80중량%을 혼합하여 에멀젼을 제조하는 단계;a) preparing an emulsion by mixing 10-30 wt% of ethylene-2,3-dioxythiophene (EDOT), 10-20 wt% of polystyrene sulfonic acid (PSSA), and 60-80 wt% of water;
b) 상기 에멀젼에 암모늄퍼설페이트 5 내지 20 중량%를 첨가하여 PEDOT-PSSA 수분산 용액을 제조하는 단계;b) adding 5 to 20% by weight of ammonium persulfate to the emulsion to prepare a PEDOT-PSSA aqueous dispersion solution;
c) 상기 PEDOT-PSSA 수분산 용액에 PVP(polyvinylpyrrolidone) 1 내지 10 중량% 및 실리카 표면처리제 1 내지 5 중량%를 첨가하여 PEDOT-PSSA 코팅액을 제조하는 단계; 및c) preparing a PEDOT-PSSA coating solution by adding 1 to 10 wt% of polyvinylpyrrolidone (PVP) and 1 to 5 wt% of silica surface treatment agent to the PEDOT-PSSA aqueous dispersion solution; And
d) 상기 PEDOT-PSSA 코팅액을 이용하여 슬릿다이 코팅, 롤 코팅, 바 코팅 및 그라비아 코팅으로부터 선택되는 1종 이상의 방법으로 코팅하는 단계;d) coating using the PEDOT-PSSA coating solution by at least one method selected from slit die coating, roll coating, bar coating and gravure coating;
를 포함하는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법을 제공한다. 도 1을 참조한다.It provides a method for producing a PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode comprising a. Please refer to Fig.
본 발명에 있어서, PEDOT-PSSA 복합층의 제조방법은 PSSA(polystyrenesulfonic acid)를 고분자 안정화제 및 도판으로서 사용하여, PEDOT를 중합하여 제조하는 것으로, 암모늄퍼설페이트 산화제를 이용하는 것을 특징으로 한다.In the present invention, the PEDOT-PSSA composite layer is produced by polymerizing PEDOT using PSSA (polystyrenesulfonic acid) as a polymer stabilizer and a plate, characterized in that an ammonium persulfate oxidant is used.
본 발명에 있어서, 상기 PEDOT-PSSA 복합층은 200 내지 800 ㎚의 두께를 가지는 것을 특징으로 한다. In the present invention, the PEDOT-PSSA composite layer is characterized in that it has a thickness of 200 to 800 nm.
상기 PEDOT-PSSA 복합층은 PEDOT-PSSA 코팅액을 이용한 잉크의 고형분 함량에 따라 면저항을 다양하게 제어가능하나 바람직하게는 면저항이 2 내지 100 ohm/sq인 것으로, 상기 제조방법으로 제조된 PEDOT-PSSA 복합층을 구비하는 음극 전극은 5B의 접착력과 2H 이상의 경도의 표면 물성을 갖는 것을 특징으로 한다.The PEDOT-PSSA composite layer can control various sheet resistances according to the solid content of the ink using the PEDOT-PSSA coating liquid, but preferably, the sheet resistance is 2 to 100 ohm / sq. The cathode electrode having a layer is characterized by having an adhesion of 5B and surface properties of hardness of 2H or more.
상기 제조방법으로 제조된 PEDOT-PSSA 복합층은 광전변환 효율이 보다 향상된 염료감응 태양전지에 중요한 의미를 가지며, 이는 상기 PEDOT-PSSA 복합층이 가지는 우수한 물성이 투명전극의 저항을 낮게 회복시킴으로써 크게 향상된 광전변환효율을 효과를 얻을 수 있는 장점이 있다.The PEDOT-PSSA composite layer prepared by the above manufacturing method has an important meaning for dye-sensitized solar cells having improved photoelectric conversion efficiency, and the excellent physical properties of the PEDOT-PSSA composite layer are greatly improved by restoring the resistance of the transparent electrode. There is an advantage that the photoelectric conversion efficiency can be obtained.
본 발명은 전도성 제 1 기판, 상기 제 1 기판 상에 형성된 도전성 투명전극, 및 투명전극 상에 제 1항 내지 제 3항의 제조방법에 따른 PEDOT-PSSA 복합층을 구비하는 음극 전극; 및 The present invention includes a cathode electrode having a conductive first substrate, a conductive transparent electrode formed on the first substrate, and a PEDOT-PSSA composite layer according to the method of claim 1 on the transparent electrode; And
전도성 제 2 기판, 상기 제 2 기판 상에 형성된 상기 음극전극에 대응하는 양극부로서의 상대 전극;을 구비하는 염료감응 태양전지를 제공한다.It provides a dye-sensitized solar cell comprising a conductive second substrate, a counter electrode as an anode portion corresponding to the cathode electrode formed on the second substrate.
본 발명에 있어서, 상기 제 1 기판 및 제 2 기판은 각각 ITO(indium tin oxide), FTO (fluorine-doped tin oxide), 표면에 SnO2가 코팅되어 있는 유리 기판, 또는 전도성 고분자 기판으로 이루어질 수 있다.In the present invention, the first substrate and the second substrate may be made of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), a glass substrate coated with SnO 2 on the surface, or a conductive polymer substrate. .
상기 도전성 투명전극은 금, 은, 수은, 구리, 니켈, 철, 알루미늄으로부터 선택되는 1종 이상의 금속 분말을 포함하는 것을 특징으로 한다.The conductive transparent electrode is characterized in that it comprises at least one metal powder selected from gold, silver, mercury, copper, nickel, iron, aluminum.
본 발명에 있어서, 상기 PEDOT-PSSA 복합층은 EDOT(ethylene-2,3-dioxythiophene) 10 내지 30 중량%, PSSA(Polystyrene sulfonic acid) 10 내지 20 중량%, 암모늄퍼설페이트 5 내지 20 중량%, PVP(polyvinylpyrrolidone) 1 내지 10 중량%, 실리카 표면처리제 1 내지 5 중량% 및 나머지는 물로 이루어지는 것을 특징으로 한다.In the present invention, the PEDOT-PSSA composite layer is 10 to 30% by weight of EDOT (ethylene-2,3-dioxythiophene), 10 to 20% by weight of polystyrene sulfonic acid (PSSA), 5 to 20% by weight of ammonium persulfate, PVP (polyvinylpyrrolidone) 1 to 10% by weight, 1 to 5% by weight of the silica surface treatment agent and the rest is characterized in that consisting of water.
상기 조성으로 구성된 음극 전극의 PEDOT-PSSA 복합층은 면저항이 2 내지 100 ohm/sq를 가지며, 5B의 접착력과 2H 이상의 경도의 우수한 표면 물성을 가짐으로써 투명전극의 저항을 낮게 회복시켜 크게 향상된 광전변환효율을 효과를 얻을 수 있는 장점이 있다.The PEDOT-PSSA composite layer of the cathode electrode composed of the above composition has a sheet resistance of 2 to 100 ohm / sq, and has an adhesion of 5B and excellent surface properties of hardness of 2H or higher to restore low resistance of the transparent electrode, thereby greatly improving photoelectric conversion. There is an advantage that the efficiency can be obtained.
상기 음극 전극 및 상대 전극은 상기 음극 전극의 PEDOT-PSSA 복합층과 상기 상대 전극은 상호 대향하도록 배치된다. 상기 음극 전극과 상기 상대 극과의 사이에는 전해질이 채워져 있다. The cathode electrode and the counter electrode are disposed such that the PEDOT-PSSA composite layer of the cathode electrode and the counter electrode face each other. An electrolyte is filled between the cathode electrode and the counter electrode.
상기 전해질은 요오드계 산화-환원종과 고분자가 혼합된 고분자 전해질을 포함하나, 이에 한정되는 것은 아니다.The electrolyte includes a polymer electrolyte in which an iodine-based redox species and a polymer are mixed, but are not limited thereto.
보다 상세하게는 인쇄 가능한 염료가 흡착된 TiO2 잉크를 제조한 후, 스크린 프린팅의 인쇄 공정을 통하여 TiO2가 코팅된 ITO(indium tin oxide) 기판을 제조한 후, 상기 기판상에 은 배선이 인쇄된 기판상에 PEDOT-PSSA 복합층의 음극 전극을 접착한 후, 작은 구명을 뚫은 후 I-/I3-전해질 용액을 주입하고 실링하여 태양전지 셀을 제조하였다.More specifically, after preparing a TiO 2 ink in which a printable dye is adsorbed, the TiO 2 is coated through a printing process of screen printing. After preparing an indium tin oxide (ITO) substrate, the negative electrode of the PEDOT-PSSA composite layer was adhered onto the substrate on which the silver wiring was printed on the substrate, and then the I- / I3-electrolyte solution was prepared Injected and sealed to manufacture a solar cell.
본 발명에 따른 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법은 공정이 간단하고 경제적일 뿐 아니라 다양한 인쇄 및 코팅공정으로 염료감응 태양전지 뿐 아니라 인쇄전자 전 분야에 유용하게 응용될 수 있는 장점이 있다.The manufacturing method of PEDOT-PSSA composite layer for dye-sensitized solar cell anode according to the present invention is not only simple and economical but also can be usefully applied not only to dye-sensitized solar cell but also to all printed electronic fields by various printing and coating processes. There is an advantage.
또한, 본 발명에 따른 염료감응 태양전지는 PEDOT-PSSA 복합층을 구비함으로써 2 내지 100 ohm/sq의 면저항 및 5B의 접착력과 2H 이상의 경도에 따른 우수한 표면 물성을 가질 뿐 아니라 투명전극의 저항을 낮게 회복시킴으로써 크게 향상된 광전변환효율을 효과를 얻을 수 있는 장점이 있다.In addition, the dye-sensitized solar cell according to the present invention has a PEDOT-PSSA composite layer has a sheet resistance of 2 to 100 ohm / sq, an adhesion of 5B and excellent surface properties according to hardness of 2H or more, and lowers the resistance of the transparent electrode. There is an advantage that the effect can be obtained by greatly improved photoelectric conversion efficiency.
도 1은 본 발명에 따른 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조공정을 모식화한 것이고,
도 2는 본 발명의 은 배선이 20 ㎛ 선폭의 바둑판 형태로 인쇄된 기판의 이미지를 보여주는 것이며,
도 3은 본 발명에 따른 염료감응 태양전지 음극용 PEDOT-PSSA 복합층을 구비한 음극 전극의 이미지를 보여주는 것이고,
도 4는 본 발명의 PEDOT-PSSA 음극을 이용한 염료감응 태양전지의 광변환 효율을 확인한 도면이다.Figure 1 is a schematic of the manufacturing process of the PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode according to the present invention,
2 is a view showing an image of a substrate in which the silver wiring of the present invention is printed in the form of a checkerboard having a line width of 20 μm,
Figure 3 shows an image of a negative electrode having a PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode according to the present invention,
4 is a view confirming the light conversion efficiency of the dye-sensitized solar cell using the PEDOT-PSSA anode of the present invention.
본 발명은 하기 실시예 및 시험예에 의하여 더욱 구체적으로 설명한다. 그러나, 하기 실시예 및 시험예는 본 발명의 이해를 돕기 위한 것일 뿐, 어떤 의미로든 본 발명의 범위가 이러한 실시예 및 시험예에 의하여 한정되는 것은 아니다.The present invention will be described in more detail by the following examples and test examples. However, the following examples and test examples are only for the understanding of the present invention, and the scope of the present invention is not limited by these examples and test examples in any sense.
[제조예 1] PEDOT-PSSA 고팅액의 제조Preparation Example 1 Preparation of PEDOT-PSSA Gotting Liquid
PEDOT-PSSA 코팅액은 EDOT(ethylene-2,3-dioxythiophene) 15 중량%에 물 60 중량%, 및 PSSA(Polystyrene sulfonic acid, 평균 분자량 75,000g/mol) 10 중량%를 호모제나이저를 사용하여 에멀션을 제조 한 후, 암모니움퍼설페이트 5 중량%를 산화제로 사용하여 5℃ 온도에서 6시간 동안 교반하여 PEDOT PSSA 수분산 용액을 제조하였다.PEDOT-PSSA coating solution was prepared by using an homogenizer with 15% by weight of EDOT (ethylene-2,3-dioxythiophene), 60% by weight of water, and 10% by weight of polystyrene sulfonic acid (average molecular weight 75,000 g / mol). After the preparation, 5% by weight of ammonium persulfate was used as an oxidizing agent to stir at 5 ° C. for 6 hours to prepare a PEDOT PSSA aqueous dispersion solution.
상기 제조된 PEDOT PSSA 수분산 용액에 접착 강도 및 표면 강도를 높이기 위해 PVP(polyvinylpyrrolidone)를 7 중량% 첨가하며 동시에 실리카 표면 처리제 (LD-5701) 3중량%를 첨가하여 최종 PEDOT-PSSA 고팅액을 제조하였다.7% by weight of polyvinylpyrrolidone (PVP) was added to the prepared PEDOT PSSA aqueous dispersion solution and 3% by weight of silica surface treatment agent (LD-5701) was added to prepare a final PEDOT-PSSA coating solution. It was.
[제조예 2] 은 배선이 인쇄된 기판상에 PEDOT-PSSA 복합층의 음극 전극의 제조[Production Example 2] Preparation of Cathode Electrode of PEDOT-PSSA Composite Layer on Substrate Printed Wiring
그라비아를 이용한 은 배선이 인쇄된 기판은 상용화된 PET포일에 그라비아 인쇄용 점도 300 cP의 은 나노입자 기반의 잉크를 이용하여, 그라비아 인쇄기의 인쇄 속도 12 m/min, 롤압 8 mPa, 블레이딩 각도 63도로 셋팅하고, 그라비아 실린더는 선폭 15 ㎛ 에 선간 350 ㎛로 제판하여 도 2와 같은 은 배선이 인쇄된 기판을 제조하였다.The substrate printed with silver wire using gravure was printed on commercially available PET foil using silver nanoparticle-based ink with a viscosity of 300 cP for gravure printing, and the printing speed of gravure printing machine was 12 m / min, roll pressure 8 mPa, and blade angle was 63 degrees. After setting, the gravure cylinder was plated with a line width of 15 μm and a line width of 350 μm to prepare a substrate on which silver wirings as shown in FIG. 2 were printed.
상기 은 배선이 인쇄된 기판에 상기 제조예 1에서 제조한 PEDOT-PSSA 코팅액을 이용하여, 바코팅 방법을 이용하여 두께 600 nm의 PEDOT-PSSA 코팅액을 코팅한 후, 곧 바로 100℃ 공기 중에서 10분간 건조하여 PEDOT-PSSA 복합층의 음극 전극의 을 제조하였다.The PEDOT-PSSA coating solution prepared in Preparation Example 1 was coated on the printed substrate using the bar coating method and then coated with PEDOT-PSSA coating solution having a thickness of 600 nm. It was dried to prepare a cathode of the PEDOT-PSSA composite layer.
[실시예 1] PEDOT-PSSA 음극을 이용한 염료감응 태양전지Example 1 Dye-Sensitized Solar Cell Using PEDOT-PSSA Cathode
인쇄 가능한 염료가 흡착된 TiO2 잉크를 제조한 후, 스크린 프린팅의 인쇄 공정을 통하여 TiO2가 코팅된 ITO(indium tin oxide) 기판을 제조하였다.After preparing a TiO 2 ink adsorbed with a printable dye, the TiO 2 was coated through a printing process of screen printing. Indium tin oxide (ITO) substrates were prepared.
상기 기판상에 스페이스를 두고 상기 제조예 2에서 제조된 은 배선이 인쇄된 기판상에 PEDOT-PSSA 복합층의 음극 전극을 접착한 후, 작은 구명을 뚫은 후 I-/I3-전해질 용액을 주입하고 실링하여 태양전지 셀을 제조하였다.After attaching the cathode electrode of the PEDOT-PSSA composite layer on the silver printed printed circuit board prepared in Preparation Example 2 with a space on the substrate, the I- / I3-electrolyte solution was injected after a small hole was drilled. Sealing to produce a solar cell.
[[ 시험예Test Example ] ] PEDOTPEDOT -- PSSAPSSA 음극을 이용한 염료감응 태양전지의 광전변환효율 조사 Investigation of photoelectric conversion efficiency of dye-sensitized solar cell using cathode
상기 실시예 1의 PEDOT-PSSA 음극을 이용한 염료감응 태양전지에 대한 광전변환효율을 조사하였다. 비교예로서는 Pt 음극을 이용하였으며, 상기 Pt 음극은 H2PtCl6 용액을 이용하여 전기 환원방법으로 제작된 태양전지를 이용하였다. The photoelectric conversion efficiency of the dye-sensitized solar cell using the PEDOT-PSSA anode of Example 1 was investigated. As a comparative example, a Pt negative electrode was used, and the Pt negative electrode used a solar cell manufactured by an electric reduction method using a H 2 PtCl 6 solution.
상기 광전변환효율은 solar simulator[Yamashita Denso Corp., model No.YSS-200A)] 장비를 이용하여 셀 효율을 평가하였다. AM 1.5 조건(100mW/㎠)의 빛을 셀에 조산한 후 하기 식에 의해 셀의 효율을 측정하였다. The photoelectric conversion efficiency was evaluated using a solar simulator (Yamashita Denso Corp., model No.YSS-200A) equipment. After the light of AM 1.5 condition (100mW / ㎠) to premature to the cell, the efficiency of the cell was measured by the following equation.
상기 표 1의 결과에서도 확인할 수 있듯이, 태양전지가 동일조건의 셀 구조에서 음극을 기존의 Pt 음극 사용하였을 경우 0.27%의 광전변환효율을 보였으며, 본 발명에서 제조된 복합층 음극을 사용하였을 경우 1.37%의 광전변환 효율을 확인할 수 있었으며, 이는 본 발명의 태양전지가 기존의 태양전지 보다 약 20% 이상의 고효율 태양전지인 것을 확인한 결과이기도 하다.As can be seen from the results of Table 1, the solar cell showed a photoelectric conversion efficiency of 0.27% when using the conventional Pt cathode in the cell structure of the same conditions, when using the composite layer anode prepared in the present invention Photoelectric conversion efficiency of 1.37% was confirmed, which is also a result of confirming that the solar cell of the present invention is about 20% or more high efficiency solar cell than the conventional solar cell.
Claims (7)
b) 상기 에멀젼에 암모늄퍼설페이트 5 내지 20 중량%를 첨가하여 PEDOT-PSSA 수분산 용액을 제조하는 단계;
c) 상기 PEDOT-PSSA 수분산 용액에 PVP(polyvinylpyrrolidone) 1 내지 10 중량% 및 실리카 표면처리제 1 내지 5 중량%를 첨가하여 PEDOT-PSSA 코팅액을 제조하는 단계; 및
d) 상기 PEDOT-PSSA 코팅액을 이용하여 슬릿다이 코팅, 롤 코팅, 바 코팅 및 그라비아 코팅으로부터 선택되는 1종 이상의 방법으로 기판상에 코팅하는 단계;
를 포함하는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법.a) preparing an emulsion by mixing 10-30 wt% of ethylene-2,3-dioxythiophene (EDOT), 10-20 wt% of polystyrene sulfonic acid (PSSA), and 60-80 wt% of water;
b) adding 5 to 20% by weight of ammonium persulfate to the emulsion to prepare a PEDOT-PSSA aqueous dispersion solution;
c) preparing a PEDOT-PSSA coating solution by adding 1 to 10 wt% of polyvinylpyrrolidone (PVP) and 1 to 5 wt% of silica surface treatment agent to the PEDOT-PSSA aqueous dispersion solution; And
d) coating onto the substrate using at least one method selected from slit die coating, roll coating, bar coating and gravure coating using the PEDOT-PSSA coating solution;
Method for producing a PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode comprising a.
상기 PEDOT-PSSA 복합층은 200 내지 800 ㎚의 두께를 가지는 것을 특징으로 하는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법.The method of claim 1,
The PEDOT-PSSA composite layer is a manufacturing method of the PEDOT-PSSA composite layer for dye-sensitized solar cell cathode, characterized in that having a thickness of 200 to 800 nm.
상기 PEDOT-PSSA 복합층은 면저항이 2 내지 100 ohm/sq인 것을 특징으로 하는 염료감응 태양전지 음극용 PEDOT-PSSA 복합층의 제조방법.The method of claim 2,
The PEDOT-PSSA composite layer has a sheet resistance of 2 to 100 ohm / sq. The method of manufacturing a PEDOT-PSSA composite layer for a dye-sensitized solar cell negative electrode.
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