KR101366390B1 - Method of manufaturing paste including carbon black for solar cell and the paste thereof and method of manufacturing electrode using the paste and the electrode thereof and solar cell with the electrode - Google Patents
Method of manufaturing paste including carbon black for solar cell and the paste thereof and method of manufacturing electrode using the paste and the electrode thereof and solar cell with the electrode Download PDFInfo
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- KR101366390B1 KR101366390B1 KR1020110111684A KR20110111684A KR101366390B1 KR 101366390 B1 KR101366390 B1 KR 101366390B1 KR 1020110111684 A KR1020110111684 A KR 1020110111684A KR 20110111684 A KR20110111684 A KR 20110111684A KR 101366390 B1 KR101366390 B1 KR 101366390B1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000006229 carbon black Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000002003 electrode paste Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 11
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 11
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 11
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- 239000000975 dye Substances 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 239000006230 acetylene black Substances 0.000 description 7
- 238000000149 argon plasma sintering Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- LBFFBPOOIMGQOV-UHFFFAOYSA-M 1-ethyl-1-methylpyrrolidin-1-ium;iodide Chemical compound [I-].CC[N+]1(C)CCCC1 LBFFBPOOIMGQOV-UHFFFAOYSA-M 0.000 description 1
- WSUWIPJXQXYVNR-UHFFFAOYSA-J 2-(4-carboxylatopyridin-2-yl)pyridine-4-carboxylate;ruthenium(4+);dithiocyanate Chemical compound [Ru+4].[S-]C#N.[S-]C#N.[O-]C(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 WSUWIPJXQXYVNR-UHFFFAOYSA-J 0.000 description 1
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
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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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
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Abstract
본 발명은 태양전지 전극 페이스트의 제조방법, 그 페이스트, 그 페이스트를 이용한 전극의 제조방법, 그 전극 및 그 전극을 포함하는 태양전지를 제공한다.
본 발명에 따르는 태양전지 전극 페이스트의 제조방법, 그 페이스트, 그 페이스트를 이용한 전극의 제조방법, 그 전극 및 그 전극을 포함하는 태양전지는 티타늄아이소프로폭사이드, 아세트산 및 계면활성제를 알콜용매에 가하여 혼합하는 S1단계와, 상기 혼합물에 카본블랙을 가하고 물을 이용하여 젤화물로 상변화시키는 S2단계와, 상기 젤화물을 열처리하는 S3단계 및 상기 열처리된 젤화물에서 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 혼합하여 페이스트를 제조하는 S4단계를 포함하는 것을 특징으로 하는데, 이에 의할 때, 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하고 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 광변환효율이 극대화될 수 있다.The present invention provides a method for producing a solar cell electrode paste, a paste, a method for producing an electrode using the paste, the electrode, and a solar cell including the electrode.
The manufacturing method of the solar cell electrode paste which concerns on this invention, the paste, the manufacturing method of the electrode using this paste, the electrode, and the solar cell containing this electrode are adding titanium isopropoxide, an acetic acid, and surfactant to an alcohol solvent. Step S1 of mixing, adding carbon black to the mixture and step S2 of phase change to gelate using water, step S3 of heat treating the gelling and removing the solvent from the heat treated gelling, ethanol, terpinol And S4 step of preparing a paste by adding and mixing at least one selected from the group consisting of ethyl cellulose, whereby it may occur when forming a photoelectrode with a conventional titanium dioxide face. Prevents cracking defects and forms large pores of sufficient surface area, so dye adsorption is effective Go is a light conversion efficiency can be maximized.
Description
본 발명은 태양전지 전극 페이스트의 제조방법, 그 페이스트, 그 페이스트를 이용한 전극의 제조방법, 그 전극 및 그 전극을 포함하는 태양전지에 관한 것으로 더욱 상세하게는, 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하고 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 광전변환효율이 극대화될 수 있는 태양전지 전극 페이스트의 제조방법, 그 페이스트, 그 페이스트를 이용한 전극의 제조방법, 그 전극 및 그 전극을 포함하는 태양전지에 관한 것이다.The present invention relates to a method for producing a solar cell electrode paste, a paste, a method for producing an electrode using the paste, the electrode, and a solar cell including the electrode, and more particularly, a photoelectrode with a conventional titanium dioxide face. Manufacturing method of a solar cell electrode paste which prevents crack defects that may occur when forming and forms large pores of sufficient surface area, so that dye adsorption is effective, thereby maximizing photoelectric conversion efficiency. The present invention relates to a method for producing an electrode using a paste, a solar cell including the electrode and the electrode.
종래 태양전지 중 광전기화학형 태양전지는 반도체 접합 태양전지와는 달리 광합성 원리를 이용한 태양전지이다. 지금까지 알려진 광전기화학형 태양전지 중 대표적인 예로는 스위스의 그라첼(Gratzel)에 의하여 발표된 염료감응 태양전지이다. Of the conventional solar cells, photoelectrochemical solar cells are solar cells using the photosynthesis principle, unlike semiconductor junction solar cells. A representative example of the photoelectrochemical solar cells known to date is a dye-sensitized solar cell published by Gratzel of Switzerland.
그라첼 등에 의해 발표된 염료감응 태양전지는 표면에 루테늄계 염료 분자가 이온결합한 TiO2 전극에 태양 빛 (가시광선)이 흡수되면 염료분자는 전자-홀 쌍을 생성하며, 전자는 반도체 산화물의 전도띠로 주입된다. The dye-sensitized solar cell disclosed by Gratell et al., When the sunlight (visible light) is absorbed by the TiO 2 electrode, which is ion-bonded to the ruthenium dye molecules on the surface, the dye molecules generate electron- Lt; / RTI >
반도체 산화물 전극으로 주입된 전자는 나노입자간 계면을 통하여 투명 전도성막으로 전달되어 전류를 발생시키게 된다. 이 염료감응 태양전지는 기존의 실리콘 태양전지에 비해 제조과정이 단순하고, 전력당 제조단가가 저렴한 장점이 있어 실리콘 태양전지를 대체할 수 있는 가능성이 있기 때문에 많은 주목을 받아왔다. Electrons injected into the semiconductor oxide electrode are transferred to the transparent conductive film through the interface between the nanoparticles to generate a current. This dye-sensitized solar cell has been attracting much attention because it has a simple manufacturing process and low manufacturing cost per unit compared with the conventional silicon solar cell, which can replace silicon solar cells.
대체로 광전극은 TiO2 페이스트를 스크린 프린팅법으로 코팅하고 열처리 한 후 염료가 녹아 있는 용액에 담지하여 염료를 흡착시켜 제조하였다.Generally, the photoelectrode was prepared by coating the TiO 2 paste by screen printing method, heat treating it, and then supporting it in a solution containing the dye to adsorb the dye.
그런데 TiO2 페이스트를 코팅할 때 염료흡착양을 늘이기 위해서 15 내지 20㎛ 두께로 두껍게 코팅하는데, 이렇게 두껍게 코팅된 전극의 표면을 SEM사진이나 현미경으로 보면 표면에 갈라진 틈(크랙)이 발생되어는 문제가 있었고, 반대로, 이러한 틈이 발생하지 않는 경우에도 오히려 치밀한 구조때문에 전해질용액이 두꺼운 코팅층 안쪽까지 침투가 어려워서 광전변환효율이 낮아지는 문제가 있었다.By the way TiO 2 In order to increase the amount of dye adsorption when the paste is coated, it is thickly coated with a thickness of 15 to 20 μm. When the surface of the thick coated electrode is observed by SEM photograph or microscope, there is a problem of cracks on the surface. On the contrary, even when such a gap does not occur, there is a problem in that the electrolyte solution is difficult to penetrate into the thick coating layer due to the compact structure, thereby lowering the photoelectric conversion efficiency.
따라서, 본 발명이 해결하고자 하는 첫번째 기술적 과제는 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하면서 두꺼운 광전극을 형성하는 동시에 카본 불순물을 저감시키고, 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 충분한 광산란에 의한 광변환효율이 극대화될 수 있는 태양전지 전극 페이스트의 제조방법을 제공하는 것이다.Therefore, the first technical problem to be solved by the present invention is to reduce the carbon impurities at the same time to form a thick photoelectrode while preventing crack defects that can occur when forming a photoelectrode with a conventional titanium dioxide face, The present invention provides a method of manufacturing a solar cell electrode paste, in which large pores having a sufficient surface area are formed to effectively absorb dyes, thereby maximizing light conversion efficiency due to sufficient light scattering.
본 발명이 해결하고자 하는 두번째 기술적 과제는 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하면서 두꺼운 광전극을 형성하는 동시에 카본 불순물을 저감시키고, 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 충분한 광산란에 의한 광변환효율이 극대화될 수 있는 태양전지 전극 페이스트를 제공하는 것이다.The second technical problem to be solved by the present invention is to reduce the carbon impurities while forming a thick photoelectrode while preventing crack defects that may occur when forming the photoelectrode with a conventional titanium dioxide face, and sufficient surface area It is to provide a solar cell electrode paste that can form a large pore of the dye is effective in the dye adsorption to maximize the light conversion efficiency by sufficient light scattering.
본 발명이 해결하고자 하는 세번째 기술적 과제는 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하면서 두꺼운 광전극을 형성하는 동시에 카본 불순물을 저감시키고, 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 충분한 광산란에 의한 광변환효율이 극대화될 수 있는 태양전지 전극의 제조방법을 제공하는 것이다.The third technical problem to be solved by the present invention is to form a thick photoelectrode while reducing the carbon impurity while preventing a crack defect that may occur when forming a photoelectrode with a conventional titanium dioxide face, while reducing the carbon impurities, sufficient surface area It is to provide a method of manufacturing a solar cell electrode that can form a large pore of the dye adsorption is effective, so that the light conversion efficiency by sufficient light scattering can be maximized.
본 발명이 해결하고자 하는 네번째 기술적 과제는 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하면서 두꺼운 광전극을 형성하는 동시에 카본 불순물을 저감시키고, 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 충분한 광산란에 의한 광변환효율이 극대화될 수 있는 태양전지 전극을 제공하는 것이다.The fourth technical problem to be solved by the present invention is to form a thick photoelectrode while reducing the carbon impurity while preventing a crack defect that may occur when forming a photoelectrode with a conventional titanium dioxide face, while reducing the carbon impurities, sufficient surface area It is to provide a solar cell electrode that can form a large pore of the dye is effective absorption of the dye can be maximized light conversion efficiency by sufficient light scattering.
본 발명이 해결하고자 하는 다섯번째 기술적 과제는 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하면서 두꺼운 광전극을 형성하는 동시에 카본 불순물을 저감시키고, 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 충분한 광산란에 의한 광변환효율이 극대화될 수 있는 태양전지를 제공하는 것이다.The fifth technical problem to be solved by the present invention is to reduce the carbon impurities while forming a thick photoelectrode while preventing crack defects that may occur when forming a photoelectrode with a conventional titanium dioxide face. It is to provide a solar cell that can be maximized the light conversion efficiency by sufficient light scattering because the surface area is formed by the large pores of the dye is effective.
본 발명은 상술한 첫번째 기술적 과제를 달성하기 위하여,The present invention to achieve the first technical problem described above,
티타늄아이소프로폭사이드, 아세트산 및 계면활성제를 알콜용매에 가하여 혼합하는 S1단계와, 상기 혼합물에 카본블랙을 가하고 물을 이용하여 젤화물로 상변화시키는 S2단계와, 상기 젤화물을 열처리하는 S3단계 및 상기 열처리된 젤화물에서 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 혼합하여 페이스트를 제조하는 S4단계를 포함하는 것을 특징으로 하는 태양전지 전극 페이스트의 제조방법을 제공한다.S1 step of adding titanium isopropoxide, acetic acid and surfactant to an alcohol solvent and mixing, S2 step of adding carbon black to the mixture and converting the phase into gelate using water, and S3 step of heat treating the gelate. And a step S4 of removing the solvent from the heat-treated gelate and adding and mixing at least one selected from the group consisting of ethanol, terpinol and ethyl cellulose to prepare a paste. to provide.
본 발명의 일실시예에 의하면, 상기 S1단계, S2단계 또는 S4단계에 균일한 혼합을 위하여 초음파 분산하는 공정을 더 포함할 수 있다.According to an embodiment of the present invention, the step of S1, S2 or S4 may further comprise the step of ultrasonic dispersion for uniform mixing.
본 발명의 다른 실시예에 의하면, 상기 열처리는 온도 150 내지 250℃, 압력 5 내지 20 bar 환경에서 수행될 수 있다.According to another embodiment of the present invention, the heat treatment may be performed at a temperature of 150 to 250 ℃, pressure 5 to 20 bar environment.
본 발명은 상술한 두번째 기술적 과제를 달성하기 위하여, 상기한 제조방법에 의하여 제조되는 태양전지 전극 페이스트를 제공한다.The present invention provides a solar cell electrode paste prepared by the above-described manufacturing method in order to achieve the second technical problem described above.
본 발명은 상기 세번째 기술적 과제를 달성하기 위하여, 상기 페이스트를 전도성산화물층이 형성된 투명기판의 상부로 1차코팅하는 단계 및 상기 1차 코팅된 투명기판을 열처리하여 티탄늄산화물층에 존재하는 복수개의 기공을 평균크기 50 내지 1000㎚으로 형성하는 단계를 포함하는 것을 특징으로 하는 태양전지 전극의 제조방법을 제공한다.In order to achieve the third technical problem, the present invention includes the steps of: first coating the paste onto an upper portion of a transparent substrate on which a conductive oxide layer is formed, and heat treating the first coated transparent substrate to form a plurality of titanium oxide layers present in the titanium oxide layer. It provides a method for producing a solar cell electrode comprising the step of forming the pores to an average size of 50 to 1000nm.
본 발명의 일실시예에 의하면, 상기 열처리 후에 염료를 흡착하여 태양전지용 광전극을 제조할 수 있다.According to one embodiment of the present invention, a photoelectrode for a solar cell may be manufactured by adsorbing a dye after the heat treatment.
본 발명의 다른 실시예에 의하면, 상기 열처리 공정에 이어 1차코팅된 티탄늄산화물층의 상부에 2차코팅하여 열처리하는 A단계를 더 포함할 수 있다.According to another embodiment of the present invention, after the heat treatment process may further comprise a step of performing a second coating on the upper portion of the titanium oxide oxide layer first coated.
본 발명의 또 다른 실시예에 의하면, 상기 A단계는 반복적으로 수행될 수 있다.According to another embodiment of the present invention, step A may be repeatedly performed.
본 발명의 또 다른 실시예에 의하면, 상기 2차코팅에 사용되는 페이스트는 금속산화물입자를 함유할 수 있다.According to another embodiment of the present invention, the paste used for the secondary coating may contain metal oxide particles.
본 발명의 또 다른 실시예에 의하면, 상기 열처리는 500 내지 600℃일 수 있다.According to another embodiment of the present invention, the heat treatment may be 500 to 600 ℃.
본 발명은 상기 네번째 기술적 과제를 달성하기 위하여, 상기 제조방법에 의하여 제조되는 태양전지 전극을 제공한다.The present invention provides a solar cell electrode manufactured by the manufacturing method in order to achieve the fourth technical problem.
본 발명은 상기 다섯번째 기술적 과제를 달성하기 위하여, 상기 태양전지 전극을 포함하는 것을 특징으로 하는 태양전지을 제공한다.The present invention provides a solar cell comprising the solar cell electrode, in order to achieve the fifth technical problem.
본 발명에 따르면, 종래의 이산화티탄 페이스로 광전극을 형성하는 경우에 발생될 수 있는 크랙(갈라짐) 불량을 방지하면서 두꺼운 광전극을 형성하는 동시에 카본 불순물을 저감시키고, 충분한 표면적의 거대 기공이 형성되어 염료의 흡착이 효과적이어서 충분한 광산란에 의한 광전변환효율이 극대화될 수 있는 될 수 있다.According to the present invention, while forming a thick photoelectrode while preventing cracking defects that may occur when forming a photoelectrode with a conventional titanium dioxide face, carbon impurities are reduced and a large pore of sufficient surface area is formed. Since the adsorption of the dye is effective, the photoelectric conversion efficiency by sufficient light scattering can be maximized.
도 1은 본 발명의 페이스트를 제조하는 단계에 대한 순서도이고,
도 2는 본 발명의 실시예와 비교예에 의한 태양전지 광전극의 전자주사현미경사진(SEM)이며,
도 3은 본 발명에 따르는 전극을 열분석한 그래프이다. 1 is a flow chart for the step of preparing the paste of the present invention,
2 is an electron scanning micrograph (SEM) of the photovoltaic cell electrode according to the embodiment of the present invention and a comparative example,
Figure 3 is a graph of the thermal analysis of the electrode according to the present invention.
이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
그러나, 이하에서 기재되는 실시예는 본 발명을 설명하는데에 필요한 적절한 내용으로 본 발명에 이에 의하여 한정되게 해석되어서는 아니되며, 당업자의 용이하게 수정, 치환, 변경할 수 있는 범위내에 본 발명이 있음은 자명하다.However, the embodiments described below are not necessarily limited to the present invention as appropriate contents necessary to explain the present invention, and the present invention is within the range that can be easily modified, replaced, changed by those skilled in the art. Self-explanatory
본 발명에 따르는 태양전지 전극 페이스트의 제조방법은 티타늄아이소프로폭사이드, 아세트산 및 계면활성제를 알콜용매에 가하여 혼합하는 S1단계, 상기 혼합물에 카본블랙을 가하고 물을 이용하여 젤화물로 상변화시키는 S2단계, 상기 젤화물을 열처리하는 S3단계 및 상기 열처리된 젤화물에서 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 혼합하여 페이스트를 제조하는 S4단계를 포함하는 특징이 있다.In the method of manufacturing the solar cell electrode paste according to the present invention, step S1 of adding titanium isopropoxide, acetic acid and a surfactant to an alcohol solvent and mixing the same, S2 adding carbon black to the mixture and converting the phase into a gelate using water Step, S3 step of heat-treating the gelling and S4 step of removing the solvent from the heat-treated gelled and added by mixing at least one selected from the group consisting of ethanol, terpinol and ethyl cellulose to prepare a paste. have.
첨부된 도 1을 통하여 본 발명을 설명한다. 도 1은 본 발명의 페이스트를 제조하는 순서도인데, 이를 참조한다.The present invention will be described with reference to FIG. 1. 1 is a flow chart for preparing the paste of the present invention, see this.
먼저, S1단계를 보면, 티타늄아이소프로폭사이드, 아세트산 및 계면활성제를 알콜용매에 가하여 혼합하는 단계이다. 여기서 상기 티타늄아이소프로폭사이드는 Titanium isopropoxide로 표기될 수 있으며, 나노 티타늄옥사이드(TiO2) 입자의 공급원(source)으로 사용되며 그 평균입도는 수 내지 수백㎚ 정도로 평가된다.First, in the step S1, titanium isopropoxide, acetic acid and a surfactant are added to the alcohol solvent and mixed. The titanium isopropoxide may be represented as Titanium isopropoxide, and is used as a source of nano titanium oxide (TiO 2 ) particles, and its average particle size is estimated to be several to several hundred nm.
또한, 상기 계면활성제는 알콜용매에서 혼합물이 균일하게 분산될 수 있다면 특별하게 한정하여 사용할 것은 아니며, 바람직하게는 비이온성을 사용할 수 있다.In addition, the surfactant is not particularly limited as long as the mixture can be uniformly dispersed in an alcohol solvent, preferably nonionic.
상기 알콜용매 역시 상기 혼합물이 균일하게 분산되어 공정을 진행할 수 있는 한 특별하게 한정하여 사용할 것은 아니나, 2-프로판올을 사용할 수 있다.The alcohol solvent is not particularly limited as long as the mixture can be uniformly dispersed to proceed with the process, but 2-propanol may be used.
아울러, 상기 S1단계에서 균일한 혼합을 위하여 초음파 분산을 이용할 수 있음은 물론이며, 이때 사용되는 초음파의 범위는 통상 초음파외에도 메가소닉, 울트라소닉, 슈퍼울트라소닉으로 불리는 정도의 초음파를 필요에 따라 사용할 수 있다.In addition, of course, the ultrasonic dispersion may be used for uniform mixing in the step S1, and the range of ultrasonic waves used in this case may be used in addition to the ultrasonic waves, such as megasonic, ultrasonic, and superultrasonic, as necessary. Can be.
다음으로, S2단계를 보면, 상기 혼합물에 카본블랙을 가하고 물을 이용하여 젤화물로 상변화시키는 단계이다.Next, look at the step S2, the carbon black is added to the mixture and is a step of phase change to gelate using water.
상기 S1단계에서 준비된 균일한 혼합물에 카본블랙을 가하고 물로 젤화시키게 되는데, 여기서 사용되는 카본블랙은 본 발명의 범위에 있는 이산화티탄에 의한 기공의 효과적으로 형성하기 위하여 사용되는 것으로 특별하게 한정할 것은 아니나, 아세틸렌블랙을 사용할 수 있다. 상기 아세틸렌블랙은 잘 발달된 솜털과 유사한 구조의 입자(fluffy)로서 다공(porous) 구조 내에 잘 흡착될 수 있고, 균일한 분산이 잘 되며, 이후 공정인 열처리시 잘 산화되어 잔류카본을 남기지 않는 한 사용할 수 있다.Carbon black is added to the uniform mixture prepared in the step S1 and gelled with water, but the carbon black used herein is not particularly limited to being used to effectively form pores by titanium dioxide in the scope of the present invention. Acetylene black can be used. The acetylene black is a well-developed fluffy-like structure (fluffy) that can be adsorbed well in the porous structure, uniform dispersion is good, and is well oxidized during the subsequent heat treatment process does not leave residual carbon Can be used.
상기 물은 증류수와 같이 미네랄이 제거되었는지 여부에 상관없이 상기 혼합물과 카본블랙을 젤리(jelly)화 시킬 수 있는 한 특별하게 제한하여 사용할 것은 아니다.The water is not particularly limited as long as it can jellyate the mixture and carbon black regardless of whether minerals such as distilled water are removed.
여기서도 앞서 언급한 초음파 공정을 이용하여 젤리상의 이산화티탄 소스의 균일성을 확보할 수 있다.Here, the uniformity of the jelly-like titanium dioxide source can be ensured using the aforementioned ultrasonic process.
다음으로 S3단계를 보면, 상기 젤화물을 열처리하는 단계이다.Next, look at the step S3, the step of heat-treating the gelled.
상기 열처리는 상기 젤화물에 균일하게 분포하는 이산화티탄입자들의 성장을 유도하고 불순물을 제거하기 위하여 필요한 것으로, 그 온도 150 내지 250℃, 압력 5 내지 20 bar 환경에서 수행될 수 있다.The heat treatment is necessary to induce growth of titanium dioxide particles uniformly distributed in the gelate and to remove impurities, and may be performed at a temperature of 150 to 250 ° C. and a pressure of 5 to 20 bar.
만일 , 상기 온도와 압력이 하한치 미만이면, 이산화티탄(TiO2) 입자가 나노 스케일로 형성되지 않을 수 있으며, 반대로, 상한치를 초과하면, 이산화티탄 입자가 전에 언급한 평균입도 범위를 넘어 성장할 수 있다.If the temperature and pressure are less than the lower limit, the titanium dioxide (TiO 2 ) particles may not be formed on the nanoscale, on the contrary, if the upper limit is exceeded, the titanium dioxide particles may grow beyond the aforementioned average particle size range. .
다음으로, S4단계를 보면, 상기 열처리된 젤화물에서 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 혼합하여 페이스트를 제조하는 단계이다.Next, in the step S4, the solvent is removed from the heat-treated gelate, and at least one selected from the group consisting of ethanol, terpinol and ethyl cellulose is added to mix to prepare a paste.
상기 열처리 후에 회전증발과 같은 공정으로 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 이산화티탄입자를 균일하게 분산시켜 페이스트를 제조한다.After the heat treatment, the solvent is removed by a process such as rotary evaporation, and at least one selected from the group consisting of ethanol, terpinol and ethyl cellulose is added to uniformly disperse the titanium dioxide particles to prepare a paste.
여기서도 앞서 언급한 초음파 공정을 이용하여 페이스트사이 나노 이산화티탄 입자의 균일성을 확보할 수 있다.Here, the uniformity of the nano-titanium dioxide particles between the pastes may be secured by using the aforementioned ultrasonic process.
한편, 본 발명에 따르는 태양전지 전극의 제조방법은 상기한 방법으로 제조된 페이스트를 전도성산화물층이 형성된 투명기판의 상부로 1차코팅하는 단계 및 상기 1차 코팅된 투명기판을 열처리하여 티탄늄산화물층에 존재하는 복수개의 기공을 평균크기 50 내지 1000㎚으로 형성하는 단계를 포함하는 특징이 있다.On the other hand, the manufacturing method of the solar cell electrode according to the present invention is a step of first coating the paste prepared by the above method to the upper portion of the transparent substrate on which the conductive oxide layer is formed and heat treatment of the primary coated transparent substrate titanium oxide And forming a plurality of pores present in the layer with an average size of 50 to 1000 nm.
먼저, 상기한 방법으로 제조된 페이스트를 전도성산화물층이 형성된 투명기판의 상부로 1차코팅하는 단계를 보면,First, when the paste prepared by the above method is first coated onto the transparent substrate on which the conductive oxide layer is formed,
상기 전도성산화물층이 형성된 투명기판은 통상 투명도가 95 내지 99.9% 정도인 유리 소재의 기판(substrate)의 상부에 ITO, ZTO, FTO 와 같은 전도성산화물이 스퍼터와 같은 증착방법으로 수㎚ 내지 수십㎛ 두께로 증착되어 형성된 층을 말하며, 통상 전기 전도성이 확보된 투명전극으로 사용된다.The transparent substrate on which the conductive oxide layer is formed has a thickness of several nm to several tens of micrometers by depositing conductive oxides such as ITO, ZTO, and FTO on a substrate of a glass material having a transparency of about 95 to 99.9%. It refers to a layer formed by depositing, and is commonly used as a transparent electrode ensuring electrical conductivity.
또한, 상기 전도성산화물층의 상부로 상기 페이스트를 1차코팅하는데, 이는 코팅된 표면이나 그 내부에서 기공에 채워진(filled) 카본블랙, 에탄올, 터핀올 또는 에틸셀룰로오스가 후공정인 열처리를 통하여 외부로 원활하게 제거될 수 있는 두께를 확보하기 위한 공정이다.In addition, the paste is first coated on top of the conductive oxide layer, which is carbon black, ethanol, terpinol or ethyl cellulose filled into the pores on the coated surface or inside thereof to the outside through a post-process heat treatment. It is a process to secure the thickness that can be removed smoothly.
다음으로, 상기 1차코팅 층을 열처리하여 앞서 언급한 바와 같이, 카본블랙, 에탄올, 터핀올 또는 에틸셀룰로오스는 물론 잔류하는 탄소를 제거하여 평균입도 50 내지 1000㎚인 티타늄산화물층을 형성하는 공정이다.Next, as described above by heat-treating the primary coating layer, the carbon black, ethanol, terpinol or ethyl cellulose is removed to remove the remaining carbon as well as to form a titanium oxide layer having an average particle size of 50 to 1000nm. .
여기서 열처리전의 티타늄산화물층의 두께는 1차코팅된 페이스트의 농도, 점도와 같은 물성에 의하여 변할 수 있는 것으로 제조에서 요구하는 두께보다 낮거나 적을 수 있어서, 이후 상기 열처리 공정에 이어 1차코팅된 티탄늄산화물층의 상부에 2차코팅을 하여 열처리를 수행할 수 있으며(A단계), 이러한 반복 코팅 및 열처리는 두께가 두꺼워질 필요에 따라 복수회 반복할 수 있음은 물론이다.Here, the thickness of the titanium oxide layer before the heat treatment may be changed by physical properties such as the concentration and viscosity of the primary coated paste, which may be lower or less than the thickness required in the manufacture, and then the titanium coated first after the heat treatment process. Heat treatment may be performed by performing a secondary coating on the upper portion of the nium oxide layer (step A), and such repeated coating and heat treatment may be repeated a plurality of times as necessary to increase the thickness.
이러한 열처리는 500 내지 600℃일 수 있는데, 이러한 범위에서 용매, 카본블랙, 기타 잔류탄소의 제거가 원활하여 효과적인 열처리가 이루어질 수 있다.The heat treatment may be 500 to 600 ℃, in this range, the removal of the solvent, carbon black, and other residual carbon can be smoothly effective heat treatment.
이러한 공정은 1번에 완료되기 어려운 불리함이 있으나, 상기 카본블랙, 에탄올, 터핀올 또는 에틸셀룰로오스는 물론 잔류하는 탄소까지 제거될 수 있도록 충분한 그 기체상의 경로(path)를 제공할 수 있는 이점이 있다.This process is disadvantageous in that it is difficult to complete in one step, but it has the advantage of providing a gaseous path sufficient to remove the carbon black, ethanol, terpinol or ethyl cellulose as well as the remaining carbon. have.
아울러, 상기 2차코팅에 사용되는 페이스트는 본 발명에 따르는 페이스트는 물론 통상의 페이스트나, 티티늄이 아닌 다른종류의 금속산화물 입자를 포함하거나, 특정요구(조절된 농도, 입도와 같은 물성을 가진 금속산화물 페이스트)를 수행하는 페이스트 등을 사용할 수 있다.In addition, the paste used in the secondary coating may include a paste according to the present invention as well as a conventional paste or other kinds of metal oxide particles other than titanium, or have specific requirements (such as controlled concentration and particle size). Or a paste for carrying out a metal oxide paste).
상기 열처리후 태양전지 전극에 사용되는 염료를 흡착시켜 광전극을 제조할 수 있다.After the heat treatment, the dye used for the solar cell electrode may be adsorbed to manufacture a photoelectrode.
상기 염료는 상기 티타늄산화물층이나 금속산화물층에 흡착되어 광경로를 제공할 수 있는 한 특별하게 한정할 것은 아니다.The dye is not particularly limited as long as it can adsorb to the titanium oxide layer or the metal oxide layer to provide an optical path.
한편, 상기 열처리를 마친 태양전지 전극에 염료를 흡착하여 광전극을 형성하고, 통상의 상대전극 제조, 밀봉, 전해질 주입 등의 공정을 거쳐 본 발명에 따르는 태양전지를 제조할 수 있다.Meanwhile, a photoelectrode is formed by adsorbing a dye to the solar cell electrode after the heat treatment, and a solar cell according to the present invention may be manufactured through a process of preparing a counter electrode, sealing, and electrolyte injection.
실시예 1: 태양전지 전극 페이스트의 제조Example 1 Preparation of Solar Cell Electrode Paste
티타늄아이소프로폭사이드(Titanium isopropoxide), 아세트산(acetic acid), 계면활성제(triton X-100; non-ionic surfactant)를 프로판올(2-propanol) (200g) 에 284g: 60g: 3g의 비율로 녹여서, 여기에 아세틸렌 블랙을 5.4g 가하여 아세틸렌 블랙의 농도가 1wt%로 되게하였다. 다음으로 균일한 분산을 하며 60분간 증류수를 방울방울 적하하여 젤화시켰다. 다음으로, 이를 수열합성기(autoclave)에 투입하여 공정온도 200℃, 공정압력15 bar에서 15시간 동안 열처리하였다. 다음으로, 생성된 에멀젼을 회전증발기를 이용하여 용매를 증발시키고 에탄올(ethanol), 터핀올(terpinol), 에틸셀룰로오즈(ethyl cellulose)를 가하여 25 wt%가 되도록 혼합하고, 초음파분산기로 40분동안 분산시켜 1wt%의 아세틸렌블랙이 혼입된 본 발명에 따르는 이산화티탄 페이스트를 제조하였다.Titanium isopropoxide, acetic acid and surfactant (triton X-100; non-ionic surfactant) were dissolved in 2-propanol (200 g) at a ratio of 284 g: 60 g: 3 g, 5.4 g of acetylene black was added thereto so that the concentration of acetylene black was 1 wt%. Next, uniform dispersion was carried out and gelled by dropwise dropping of distilled water for 60 minutes. Next, it was put into an autoclave and heat-treated at a process temperature of 200 ° C. and a process pressure of 15 bar for 15 hours. Next, the resulting emulsion was evaporated using a rotary evaporator, ethanol, terpinol and ethyl cellulose were added and mixed to 25 wt%, and dispersed by an ultrasonic disperser for 40 minutes. Titanium dioxide according to the present invention incorporating 1 wt% of acetylene black Paste was prepared.
실시예 2: 태양전지 전극 페이스트의 제조Example 2: Preparation of Solar Cell Electrode Paste
아세틸렌블랙을 2.7g을 가하여 그 농도가 0.5wt%로 되게 한 것을 제외하고는 실시예 1과 동일하게 하여 이산화티탄 페이스트를 제조하였다.Titanium dioxide in the same manner as in Example 1 except that 2.7 g of acetylene black was added to make the concentration 0.5 wt%. Paste was prepared.
실시예 3: 태양전지의 제조Example 3: Fabrication of Solar Cell
실시예 1에 의한 이산화티탄 페이스트를 불소가 도핑된 틴 옥사이드가 증착된 유리기판(FTO-유리)에 닥터블레이드방법으로 코팅하여 550 ℃, 30분 동안 열처리하여 평균 8 ㎛ 두께의 코팅층을 얻었다. 다음으로, 상기 코팅층의 상부에 이산화티탄 페이스트을 2차코팅하고 550 ℃, 30분 동안 열처리하여 평균두께 15μm인 금속산화물층을 형성하였다. 다음으로 0.2 mM의 루테늄 디티오시아네이트 2,2′-비피리딜-4,4′-디카르복실레이트가 에탄올에 녹아있는 염료용액을 준비하여, 여기에 상기 금속산화물층이 형성된 유리기판을 24시간 동안 담지한 후 건조시켜 광전극을 제조하였다. 다음으로, 다른 FTO 유리기판에 육염화백금산(H2PtCl6)이 녹아있는 2-프로판올 용액을 적하하고, 450 ℃, 30분 동안 열처리하여 백금층을 형성시켜 상대전극을 제조하였다. 다음으로, 상기 광전극과 배금층이 서로 대향하도록 배치하되, 그 테투리 부위에 서린(SURLYN; Du Pont사 제조)으로 60㎛두께의 열가소성 고분자층을 형성하고 130℃, 2분 동안 유지하여 두 전극을 이격된 상태로 테투리만 부착하였다. 다음으로, 광전극과 상대전극을 관통하는 미세 홀을 형성하고 이 홀을 통해 이격된 두 전극 사이의 공간에 3-Methoxypropionitrile 용매에 0.1M LiI, 0.05M I2, 0.5M 4-tert-butylpyridine과 이온성액체인 0.6M 1-Ethyl-1-methylpyrrolidinium iodide을 녹여서 제조한 전해질 용액을 주입하고 상기 홀을 접착제로 봉하여 본 발명에 따르는 태양전지를 제조하였다.Titanium Dioxide according to Example 1 The paste was coated on a glass substrate (FTO-glass) on which fluorine-doped tin oxide was deposited by a doctor blade method, and heat-treated at 550 ° C. for 30 minutes to obtain a coating layer having an average thickness of 8 μm. Next, titanium dioxide on top of the coating layer The paste was second coated and heat-treated at 550 ° C. for 30 minutes to form a metal oxide layer having an average thickness of 15 μm. Next, a dye solution in which 0.2
실시예 4: 태양전지의 제조Example 4: Fabrication of Solar Cells
실시예 2에 의한 이산화티탄 페이스트를 사용한 것을 제외하고는 실시예 3과 동일하게 실시하여 본 발명에 따르는 태양전지를 제조하였다.Titanium Dioxide according to Example 2 A solar cell according to the present invention was prepared in the same manner as in Example 3 except that the paste was used.
비교예Comparative Example
TiO2 페이스트(스위스 솔라로닉 사, D-paste)를 불소가 도핑된 틴 옥사이드가 증착된 유리기판(FTO-유리)에 닥터블레이드방법으로 코팅하여 610 ℃, 50분 동안 열처리하여 평균 15 ㎛ 두께의 코팅층을 제조하고, 이후에 염료 코팅, 상대전극 준비, 밀봉 및 전해질 주입은 위 실시예 3과 동일한 방법으로 하여 태양전지를 제조하였다.TiO 2 paste (D-paste, Swiss Solar, Inc.) was coated on a glass substrate (FTO-glass) on which fluorine-doped tin oxide was deposited by a doctor blade method and heat-treated at 610 ° C. for 50 minutes to average 15 μm in thickness. After the coating layer was prepared, dye coating, counter electrode preparation, sealing, and electrolyte injection were performed in the same manner as in Example 3, to prepare a solar cell.
시험예Test Example
상기 실시예 3 및 비교예에서 제조한 태양전지의 광전변환 효율을 평가하기 위하여 하기와 같은 방법으로 광전압 및 광전류를 측정하여 광전기적 특성을 관찰하고, 이를 통하여 얻어진 전류밀도(Isc), 전압(Voc), 및 충진계수(fillfactor, ff)를 이용하여 광전변환 효율(ne)를 하기 수학식 1로 계산하였다. In order to evaluate the photoelectric conversion efficiency of the solar cell manufactured in Example 3 and Comparative Example, the photovoltaic characteristics were observed by measuring the photovoltage and photocurrent as follows, and the current density (I sc ) Photoelectric conversion efficiency (n e ) was calculated by Equation 1 using (V oc ), and a fill factor (ff).
<수학식 1>&Quot; (1) "
ne = (Voc × Isc × ff) / (Pine)n e = (V oc x I sc x ff) / (P ine )
상기 수학식 1에서, (Pine)는 100 ㎽/㎠(1 sun)을 나타낸다. In Equation (1), (P ine ) represents 100 mW / cm 2 (1 sun).
상기와 같이 측정된 값들을 하기 표 1에 나타내었다. The measured values are shown in Table 1 below.
이때, 광원으로는 제논 램프(Xenon lamp, Oriel)를 사용하였으며, 상기 제논 램프의 태양조건(AM 1.5)은 표준 태양전지를 사용하여 보정하였다. At this time, a Xenon lamp (Oriel) was used as a light source, and the solar condition (AM 1.5) of the Xenon lamp was corrected using a standard solar cell.
상기 표 1에 나타난 바와 같이, 비교예와 대비하여, 본 발명에 따르는 실시예 3에 의한 태양전지의 효율이 상대적으로 1% 정도 높음을 알 수 있다. 도 2를 통하여 확인할 수 있는 것처럼, 본 발명에 따른 태양전지의 광전극은 비교예에 의한 것보다 복수개의 거대기공(pore)이 잘 형성됨을 알 수 있다. 이를 통하여 전해질이 이산화티탄 층 내부로 잘 침투하게되고 투입되는 태양광의 광산란 역시 원활해진다. As shown in Table 1, compared with the comparative example, it can be seen that the efficiency of the solar cell according to Example 3 according to the present invention is relatively high by about 1%. As can be seen through Figure 2, the photoelectrode of the solar cell according to the present invention can be seen that a plurality of pores (pore) is formed better than the comparative example. Through this, the electrolyte penetrates well into the titanium dioxide layer and the light scattering of the injected sunlight is also smoothed.
아울러, 도 2에서 알 수 있는 바와 같이, 본 발명에 따르는 전극에 존재하는 잔류탄소의 양이 거의 없음을 알 수 있다.In addition, as can be seen in Figure 2, it can be seen that there is almost no amount of residual carbon present in the electrode according to the present invention.
이는 열처리시 아세틸렌 블랙이 연소하면서 이산화티탄 표면의 온도를 상승시켜 잔류탄소의 양을 감소시키는 것으로 보인다.This appears to reduce the amount of residual carbon by raising the temperature of the titanium dioxide surface as acetylene black burns during heat treatment.
시료명Analysis item
Name of sample
Claims (15)
상기 혼합물에 카본블랙을 가하고 물을 이용하여 젤화물로 상변화시키는 S2단계;
상기 젤화물을 열처리하는 S3단계; 및
상기 열처리된 젤화물에서 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 혼합하여 페이스트를 제조하는 S4단계;를 포함하는 것을 특징으로 하는 태양전지 전극 페이스트의 제조방법.
Step S1 of adding titanium isopropoxide, acetic acid and a surfactant to an alcohol solvent and mixing them;
S2 step of adding carbon black to the mixture and phase change to a gelate using water;
S3 step of heat-treating the gelled; And
Removing the solvent from the heat-treated gelate and adding at least one selected from the group consisting of ethanol, terpinol, and ethyl cellulose to mix and prepare a paste to prepare a paste.
상기 S1단계, S2단계 또는 S4단계에 균일한 혼합을 위하여 초음파 분산하는 공정을 더 포함하는 것을 이용하는 것을 특징으로 하는 태양전지 전극 페이스트의 제조방법.
The method of claim 1,
Method for producing a solar cell electrode paste, characterized in that further comprising the step of ultrasonic dispersion for uniform mixing in the step S1, S2 or S4.
상기 열처리는 온도 150 내지 250℃, 압력 5 내지 20 bar 환경에서 수행되는 것을 특징으로 하는 태양전지 전극 페이스트의 제조방법.
The method of claim 1,
The heat treatment is a method of manufacturing a solar cell electrode paste, characterized in that carried out in a temperature of 150 to 250 ℃, pressure 5 to 20 bar environment.
The solar cell electrode paste manufactured by the manufacturing method of any one of Claims 1-3.
상기 혼합물에 카본블랙을 가하고 물을 이용하여 젤화물로 상변화시키는 S2단계;
상기 젤화물을 열처리하는 S3단계;
상기 열처리된 젤화물에서 용매를 제거하고 에탄올, 터핀올 및 에틸셀룰로오스로 이루어진 군에서 선택된 적어도 하나를 가하여 혼합하여 페이스트를 제조하는 S4단계;
상기 페이스트를 전도성산화물층이 형성된 투명기판의 상부로 1차코팅하는 단계; 및
상기 1차 코팅된 투명기판을 열처리하여 티타늄산화물층에 존재하는 복수개의 기공을 평균크기 50 내지 1000㎚으로 형성하는 단계;를 포함하는 것을 특징으로 하는 태양전지 전극의 제조방법.
Step S1 of adding titanium isopropoxide, acetic acid and a surfactant to an alcohol solvent and mixing them;
S2 step of adding carbon black to the mixture and phase change to a gelate using water;
S3 step of heat-treating the gelled;
Step S4 of removing the solvent from the heat-treated gelled material and adding and mixing at least one selected from the group consisting of ethanol, terpinol and ethyl cellulose to prepare a paste;
Firstly coating the paste onto the transparent substrate on which the conductive oxide layer is formed; And
Heat treating the primary coated transparent substrate to form a plurality of pores present in the titanium oxide layer with an average size of 50 to 1000 nm.
상기 S1단계, S2단계 또는 S4단계에 균일한 혼합을 위하여 초음파 분산하는 공정을 더 포함하는 것을 이용하는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 5, wherein
Method for producing a solar cell electrode, characterized in that further comprising the step of ultrasonic dispersion for uniform mixing in the step S1, S2 or S4 step.
상기 열처리는 온도 150 내지 250℃, 압력 5 내지 20 bar 환경에서 수행되는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 5, wherein
The heat treatment is a method of manufacturing a solar cell electrode, characterized in that carried out in a temperature of 150 to 250 ℃, pressure 5 to 20 bar environment.
상기 열처리 후에 염료를 흡착하여 태양전지용 광전극을 제조하는 단계;를 더 포함하는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 5, wherein
Manufacturing a solar cell photoelectrode by adsorbing a dye after the heat treatment.
상기 열처리 공정에 이어 1차코팅된 티탄늄산화물층의 상부에 2차코팅하여 열처리하는 A단계를 더 포함하는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 5, wherein
And a second step of performing a second coating on the upper portion of the first titanium coated oxide layer, followed by heat treatment.
상기 A단계는 반복적으로 수행되는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 9,
The step A is a method of manufacturing a solar cell electrode, characterized in that it is carried out repeatedly.
상기 2차코팅에 사용되는 페이스트는 금속산화물입자를 함유하는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 9,
The paste used in the secondary coating method of manufacturing a solar cell electrode, characterized in that it contains metal oxide particles.
상기 열처리는 500 내지 600℃ 온도 범위에서 수행되는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 5, wherein
The heat treatment is a manufacturing method of a solar cell electrode, characterized in that carried out in a temperature range of 500 to 600 ℃.
상기 열처리는 500 내지 600℃ 온도 범위에서 수행되는 것을 특징으로 하는 태양전지 전극의 제조방법.
The method of claim 9,
The heat treatment is a manufacturing method of a solar cell electrode, characterized in that carried out in a temperature range of 500 to 600 ℃.
The solar cell electrode manufactured by the manufacturing method of any one of claims 5 to 13.
상기 태양전지 전극을 포함하는 것을 특징으로 하는 태양전지.15. The method of claim 14,
A solar cell comprising the solar cell electrode.
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| KR100398747B1 (en) * | 1999-10-07 | 2003-09-19 | 한국화학연구원 | A Thin Film Photo Electrode of Novel Ion added Titanium Oxide Compound, and Preparation Therefor and Generation Method of Producing Photo Current by Use of the Same |
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| KR20090123197A (en) * | 2008-05-27 | 2009-12-02 | 한국에너지기술연구원 | Preparation method of titanium dioxide powder doped with erbium ion and ytterbium ion and its application to dye-sensitized solar cell as scattering layer |
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| KR100398747B1 (en) * | 1999-10-07 | 2003-09-19 | 한국화학연구원 | A Thin Film Photo Electrode of Novel Ion added Titanium Oxide Compound, and Preparation Therefor and Generation Method of Producing Photo Current by Use of the Same |
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