KR101543530B1 - Electrolyte compositions for dye-sensitized solar cells - Google Patents
Electrolyte compositions for dye-sensitized solar cells Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 36
- 239000012046 mixed solvent Substances 0.000 claims description 17
- -1 polymethylene Polymers 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
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- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- IKQCDTXBZKMPBB-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;iodide Chemical compound [I-].CCN1C=C[N+](C)=C1 IKQCDTXBZKMPBB-UHFFFAOYSA-M 0.000 description 1
- WWVMHGUBIOZASN-UHFFFAOYSA-N 1-methyl-3-prop-2-enylimidazol-1-ium Chemical compound CN1C=C[N+](CC=C)=C1 WWVMHGUBIOZASN-UHFFFAOYSA-N 0.000 description 1
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical compound [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 description 1
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 229940107816 ammonium iodide Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 150000002466 imines Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 1
- DMFMZFFIQRMJQZ-UHFFFAOYSA-N pyrrolidin-1-ium;iodide Chemical compound [I-].C1CC[NH2+]C1 DMFMZFFIQRMJQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- 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
-
- 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
Abstract
Description
본 발명은 염료감응 태양전지의 장기 안정성을 높이기 위한 전해질 조성물 및 이를 이용한 염료감응 태양전지에 관한 것이다.The present invention relates to an electrolyte composition for improving the long-term stability of a dye-sensitized solar cell and a dye-sensitized solar cell using the same.
염료감응 태양전지는 광감응 염료가 가시광을 흡수하여 전자를 발생시키는 광기전효과를 이용한 광화학 전지로 광음극, 상대전극, 및 전해질로 구성된다. 이 중 전해질은 염료감응 태양전지의 효율 및 내구성을 좌우하는 핵심소재로 해당 기술의 상용화에 걸림돌이 되는 가장 큰 기술적 문제점을 가지고 있다.A dye-sensitized solar cell is a photochemical cell using a photoconductive effect in which a photosensitive dye absorbs visible light and generates electrons. The dye-sensitized solar cell is composed of a photocathode, a counter electrode, and an electrolyte. Among them, the electrolyte is a key material which determines the efficiency and durability of the dye-sensitized solar cell, and it has the biggest technical problems that are hindering commercialization of the technology.
종래에 사용되고 있는 아세토니트릴 기반의 휘발성 액체전해질은 높은 광전변환 효율을 얻을 수 있지만 누액 및 휘발로 인해 염료감응 태양전지의 장기 내구성을 저하시키는 주요원인으로 지적되고 있다. A. Fukui 등(A. Fukui et al., Solar Energy Materials & Solar Cells, 90 (2006) 649-658)은, 휘발성 유기용매인 아세토니트릴에 다른 도너 수(donor number)를 갖는 용매를 혼합하여 단락전류와 개방전압 특성을 조절할 수 있음을 실험적으로 확인하였다. 그러나, 위 실험에서 용매의 휘발성은 고려되지 않았으며, 염료감응 태양전지의 내구성도 검토가 이루어지지 않았다. 따라서, 종래의 아세토니트릴 기발의 액체전해질과 동등 수준의 광전변환 효율을 가지며 동시에 휘발성을 억제하는 기술이 필요한 실정이다. Conventional acetonitrile-based volatile liquid electrolytes can attain high photoelectric conversion efficiency, but they are pointed out as a main cause of deterioration of long-term durability of dye-sensitized solar cells due to leakage and volatilization. A. Fukui et al., Solar Energy Materials & Solar Cells, 90 (2006) 649-658) have found that by mixing a volatile organic solvent, acetonitrile, with a solvent having a different donor number, It is experimentally confirmed that current and open-circuit voltage characteristics can be controlled. However, the volatility of the solvent was not considered in the above experiment, and the durability of the dye-sensitized solar cell was not examined. Therefore, there is a need for a technique for suppressing the volatility at the same time as having a photoelectric conversion efficiency equivalent to that of a conventional liquid electrolyte of acetonitrile.
또한, 주로 수직으로 세워 사용하는 건물통합형 발전의 특성상 액체 전해질의 누액이 일어나기 쉬우므로, 전해질을 고체 또는 준고체화 하는 기술도 필요하다. 그러나, 고체 또는 준고체 전해질은 대면적 모듈에 주입이 어려운 문제점을 가지고 있다. Also, since the leakage of the liquid electrolyte tends to occur due to the characteristics of the integrated power generation of the building, which is mainly used vertically, it is necessary to make the electrolyte solid or semi-solid. However, solid or semi-solid electrolytes have difficulty in injecting into large-area modules.
따라서 본 발명은 높은 비점 및 적절한 점도 특성을 가지면서도 종래의 액체전해질과 동등 수준의 광전변환 효율을 발휘하는 염료감응 태양전지용 전해질 조성물을 제공하는 것을 목적으로 한다. 또한, 본 발명은 상기 전해질 조성물을 이용한 염료감응 태양전지를 제공하는 것을 목적으로 한다.Accordingly, it is an object of the present invention to provide an electrolyte composition for a dye-sensitized solar cell which exhibits a photoelectric conversion efficiency equivalent to that of a conventional liquid electrolyte while having a high boiling point and suitable viscosity characteristics. It is another object of the present invention to provide a dye-sensitized solar cell using the electrolyte composition.
상기 목적을 달성하기 위하여, 본 발명은 140 ℃ 이상의 비점을 갖는 발레로니트릴(valeronitrile) 및 디메틸아세트아마이드(dimethylacetamide) 혼합용매를 포함하는 염료감응 태양전지용 전해질 조성물을 제공한다. In order to accomplish the above object, the present invention provides an electrolyte composition for a dye-sensitized solar cell comprising valeronitrile and dimethylacetamide mixed solvent having a boiling point of 140 ° C or higher.
본 발명의 일실시예에 있어서, 상기 혼합용매는 1.2 cP 이하, 바람직하게는 0.8 이상 1.2 cP 이하의 점도를 나타낼 수 있으나, 이에 제한되는 것은 아니다. 본 발명의 일실시예에 있어서, 상기 혼합용매는 20 이상 35 이하의 유전상수를 갖는 것이 바람직하나, 이에 제한되는 것은 아니다. In one embodiment of the present invention, the mixed solvent may exhibit a viscosity of 1.2 cP or less, preferably 0.8 or more and 1.2 cP or less, but is not limited thereto. In one embodiment of the present invention, the mixed solvent preferably has a dielectric constant of 20 or more and 35 or less, but is not limited thereto.
본 발명의 일실시예에 있어서, 상기 조성물은 폴리에틸렌 옥사이드(PEO) 및 폴리메틸렌 옥사이드(PMO)를 추가로 포함할 수 있다. 본 발명의 일실시예에 있어서, 상기 폴리에틸렌 옥사이드(PEO)과 폴리메틸렌 옥사이드(PMO)는 3:1의 중량비로 포함될 수 있으나, 이에 제한되는 것은 아니다.In one embodiment of the present invention, the composition may further comprise polyethylene oxide (PEO) and polymethylene oxide (PMO). In one embodiment of the present invention, the polyethylene oxide (PEO) and the polymethylene oxide (PMO) may be contained in a weight ratio of 3: 1, but are not limited thereto.
본 발명의 일실시예에 있어서, 상기 폴리에틸렌 옥사이드(PEO) 및 폴리메틸렌 옥사이드(PMO)는 전체 조성물에 대하여 1 내지 5 중량% 로 포함될 수 있으며, 각각 폴리에틸렌 옥사이드(PEO)는 전체 조성물에 대하여 3 중량%로, 폴리메틸렌 옥사이드(PMO)는 전체 조성물에 대하여 1 중량%로 포함될 수 있으나, 이에 제한되는 것은 아니다.In one embodiment of the present invention, the polyethylene oxide (PEO) and the polymethylene oxide (PMO) may be included in an amount of 1 to 5 wt% based on the total composition, and each polyethylene oxide (PEO) %, The polymethylene oxide (PMO) may be included in an amount of 1% by weight based on the total composition, but is not limited thereto.
본 발명의 일실시예에 있어서, 상기 발레로니트릴과 디메틸아세트아마이드는 6:4 내지 8:2 의 부피비로 포함될 수 있으나, 이에 제한되는 것은 아니다. In one embodiment of the present invention, the valeronitrile and dimethylacetamide may be contained in a volume ratio of 6: 4 to 8: 2, but are not limited thereto.
본 발명의 일실시예에 있어서, 상기 조성물은 필수적으로 요오드염을 포함한다.In one embodiment of the present invention, the composition essentially comprises an iodide salt.
또한, 본 발명은 상기 조성물을 포함하는 염료감응 태양전지를 제공한다.The present invention also provides a dye-sensitized solar cell comprising the composition.
본 발명에 따른 전해질 조성물은 140 ℃ 이상의 비점을 갖는 혼합 유기용매 혼합물을 포함하기 때문에 물리적 휘발성이 낮고, 소량의 고분자 첨가물로 인해 액체 주입 후 겔화되는 특성을 갖는다. 또한, 종래의 휘발성 액체전해질과 동등 수준 또는 그 이상의 광전변환 효율을 발휘하기 때문에 염료감응 태양전지에 유용하게 사용될 수 있다.Since the electrolyte composition according to the present invention includes a mixed organic solvent mixture having a boiling point of 140 ° C or higher, it has low physical volatility and has a characteristic of being gelled after injecting a liquid due to a small amount of a polymer additive. In addition, since it exhibits photoelectric conversion efficiency equal to or higher than that of a conventional volatile liquid electrolyte, it can be usefully used in a dye-sensitized solar cell.
도 1은 본 발명의 조성물의 겔화 특성을 나타낸다.
도 2 내지 도 4는 본 발명의 조성물의 광전변환 효율을 나타내는 전류-전압 곡선이다(도면에 기재된 ‘실시예’는 ‘제조예’를 의미함).
도 5는 고온(85 ℃) 내구성 가속 평가 결과를 나타낸다.
도 6은 본 발명에 따른 혼합용매의 유전상수 범위를 결정하기 위한 실험 결과이다.Figure 1 shows the gelling properties of the composition of the present invention.
FIGS. 2 to 4 are current-voltage curves showing the photoelectric conversion efficiency of the composition of the present invention (the "Examples" shown in the drawings denote "Production Examples").
Figure 5 shows the results of a high temperature (85 캜) endurance acceleration evaluation.
FIG. 6 shows experimental results for determining the dielectric constant range of the mixed solvent according to the present invention.
본 발명자는 140 ℃ 이상의 비점을 갖는 용매들을 대상으로 용매의 비점, 점도, 유전상수, 도너 수(donor number) 등의 물리화학적 특성이 염료감응 태양전지의 광전변환 효율 및 내구성에 미치는 영향을 조사하고 다음과 같은 결과를 얻게 되었다.The present inventors investigated the effect of physicochemical properties such as boiling point, viscosity, dielectric constant and donor number of a solvent on the photoelectric conversion efficiency and durability of a dye-sensitized solar cell in a solvent having a boiling point of 140 ° C or higher The following results were obtained.
용매의 비점은 높을수록 휘발성이 낮으므로 염료감응 태양전지의 내구성을 증가시킬 수 있다. 통상적으로 실외에서 사용되는 태양전지의 표면온도가 최대 80 ℃ 이상인 것을 감안할 때 140 ℃ 이상의 비점을 갖는 용매를 사용해야 충분한 내구성을 나타낼 수 있을 것으로 판단된다. 또한 통상적인 실링을 통한 기초실험을 통해 약 140 ℃ 이상의 비점을 갖는 용매의 경우, 85 ℃ 에서 1,000 시간 동안 무게 변화가 거의 없는 것을 확인하였다. The higher the boiling point of the solvent, the lower the volatility, which can increase the durability of the dye-sensitized solar cell. Considering that the surface temperature of a solar cell generally used in outdoor is at most 80 ° C or higher, it is considered that a solvent having a boiling point of 140 ° C or higher should be used to exhibit sufficient durability. In addition, it was confirmed through a basic experiment through ordinary sealing that the weight change of the solvent having a boiling point of about 140 ° C or more was not changed for 1,000 hours at 85 ° C.
또한, 점도가 낮을수록 매질의 저항이 낮아져 이온전도도가 높아지므로 가능한 낮은 점도의 용매의 사용이 바람직하다. 그러나 점도가 낮을수록 용매의 휘발성도 높아지므로 이온전도도와 휘발성을 동시에 고려하여 적절한 점도 범위의 용매를 선택해야 한다. 유전상수는 염의 해리 특성과 관련이 있으며 유전상수가 높을수록 염의 해리 특성이 우수하다. 그러나 유전상수가 높을수록 매질의 점성 또한 높아지므로 이온전도도를 저하시킬 수가 있다. 따라서 유전상수도 염의 해리와 점성의 증가를 고려하여 적절한 범위를 고려해야 한다. 즉, 점도는 이온전도도에 영향을 미치므로 낮을수록 유리하지만 유전상수 또한 염의 해리와 관련하여 이온전도도에 영향을 미치므로 반드시 점도가 낮다고 이온전도도가 높은 것은 아니다. 따라서, 점도와 유전상수가 적정범위에 있어야만 최적화된 이온전도도를 얻을 수 있음을 알 수 있다. 그러나, 단일 용매로는 상기조건을 만족시킬 수 없으며, 점도 및 유전상수가 낮은 용매와 점도 및 유전상수가 높은 용매를 적정비로 혼합하여 최적화된 이온전도도 특성을 얻을 수 있다. 본 발명의 일실시예에 있어서, 상기 혼합용매는 1.2 cP 이하, 바람직하게는 0.8 이상 1.2 cP 이하의 점도를 나타낼 수 있으나, 이에 제한되는 것은 아니다. 본 발명의 일실시예에 있어서, 상기 혼합용매는 20 이상 35 이하의 유전상수를 갖는 것이 바람직하나, 이에 제한되는 것은 아니다. Further, the lower the viscosity, the lower the resistance of the medium and the higher the ionic conductivity, so it is preferable to use a solvent having a viscosity as low as possible. However, the lower the viscosity, the higher the volatility of the solvent. Therefore, it is necessary to select a solvent having an appropriate viscosity range considering ion conductivity and volatility at the same time. The dielectric constant is related to the dissociation property of the salt. The higher the dielectric constant, the better the dissociation property of the salt. However, the higher the dielectric constant, the higher the viscosity of the medium, which may lower the ionic conductivity. Therefore, consideration should be given to the appropriate range in consideration of the dissociation of the dielectric water salt and the increase in viscosity. That is, since viscosity affects ionic conductivity, lower ionic conductivity is not advantageous because lower dielectric constant also affects ionic conductivity with respect to dissociation of salt, so that viscosity is not necessarily high. Therefore, it can be seen that optimized ion conductivity can be obtained only when the viscosity and the dielectric constant are in an appropriate range. However, a single solvent can not satisfy the above conditions, and a solvent having a low viscosity and a low dielectric constant and a solvent having a high viscosity and a high dielectric constant can be mixed at an appropriate ratio to obtain optimized ion conductivity characteristics. In one embodiment of the present invention, the mixed solvent may exhibit a viscosity of 1.2 cP or less, preferably 0.8 or more and 1.2 cP or less, but is not limited thereto. In one embodiment of the present invention, the mixed solvent preferably has a dielectric constant of 20 or more and 35 or less, but is not limited thereto.
본 발명에 따른 조성물의 점도, 유전상수, 이온전도도, 광전변환 효율 등의 특성을 만족하는 한, 어떠한 용매라도 혼합이 가능하다. 점도 및 유전상수가 낮은 용매로는 발레로니트릴, 테트라히드로퓨란, 선형 카보네이트 류 (dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC)), methyl nonafluorobutyl ether (MNFBE), 1,3-dioxilane (1,3-DOL) 등을 선택할 수 있으나, 이에 한정된 것은 아니다. 점도 및 유전상수가 높은 용매로는 N,N’-dimethylformamide (DMF), N,N’-Dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO) 등을 선택할 수 있으나, 이에 한정된 것은 아니다. 본 발명의 일실시예에 있어서, 상기 점도가 낮은 용매는 발레로니트릴일 수 있으며, 점도가 높은 용매는 디메틸아세트아마이드일 수 있다. 본 발명의 일실시예에 있어서, 발레로니트릴과 디메틸아세트아마이드의 혼합용매는, 발레로니트릴과 디메틸아세트아마이드가 6:4 내지 8:2 의 부피비로 혼합된 것일 수 있다.Any solvent can be mixed as long as the composition of the present invention satisfies the properties such as viscosity, dielectric constant, ionic conductivity, photoelectric conversion efficiency, and the like. Solvents with low viscosity and dielectric constant include valeronitrile, tetrahydrofuran, linear carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl nonafluorobutyl ether (MNFBE) 3-dioxilane (1,3-DOL), and the like. N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) can be selected as the solvent having a high viscosity and dielectric constant. no. In one embodiment of the present invention, the lower viscosity solvent may be valeronitrile, and the higher viscosity solvent may be dimethylacetamide. In one embodiment of the present invention, the mixed solvent of valeronitrile and dimethylacetamide may be a mixture of valeronitrile and dimethylacetamide in a volume ratio of 6: 4 to 8: 2.
또한, 용매의 유전상수가 높을수록 염의 해리 및 이온전도에 유리하지만, 높은 유전상수는 점도가 높아지는 문제뿐만 아니라 고온에서 광음극에 결합되어 있는 광감응 염료를 탈착시키는 문제를 야기한다. 본 발명자는 유전상수가 40을 넘는 경우에 85 이상의 고온 조건에서 광음극에 결합되어 있는 광감응 염료의 탈착이 가속화되어 염료감응 태양전지의 광전변환 효율이 크게 저하됨을 실험을 통해 확인하였다. 따라서, 혼합용매의 유전상수는 최대 40 이 넘지 않도록 조절하는 것이 바람직하다.In addition, the higher the dielectric constant of the solvent is, the better the salt dissociation and ion conduction. However, the higher dielectric constant raises the problem of desorption of the photo-sensitive dye bonded to the photocathode at high temperature as well as the viscosity. The present inventors have experimentally confirmed that the photoelectric conversion efficiency of the dye-sensitized solar cell is greatly reduced by accelerating the desorption of the photo-sensitive dye bonded to the photo-cathode at a high temperature of 85 or more when the dielectric constant exceeds 40. Therefore, it is preferable to control the dielectric constant of the mixed solvent so as not to exceed 40 at the maximum.
또한, 본 발명의 조성물은 극성 리간드를 포함하는 고분자 물질을 포함할 수 있다. 상기 극성 리간드를 포함하는 고분자 물질은 염료감응 태양전지의 광전변환 효율을 향상시키면서 동시에 상온에서 서서히 겔화되도록 하는 역할을 한다. 상기 "극성리간드" 의 예로는, 에테르 (ether), 아민 (amine), 이민 (imine), 니트릴 (nitrile), 설파이드 (sulfide), 아미드 (amide) 등이 있으나, 이에 한정되는 것은 아니다. 상기 극성 리간드를 포함하는 고분자의 예로는, 폴리에틸렌 옥사이드 (PEO), 폴리메틸렌 옥사이드 (PMO), 폴리프로필렌 옥사이드 (PPO), 폴리에틸렌 이민 (PEI), 폴리알킬렌 설파이드 (PAS), 폴리에틸렌 숙시네이트 (PES), 폴리아크릴로 니트릴 (PAN) 및 이로부터 파생된 고분자 들이 있으나, 이에 한정되는 것은 아니다. 본 발명의 일실시예에 있어서, 상기 고분자는 특정 분자량의 폴리에틸렌 옥사이드(PEO)와 폴리메틸렌 옥사이드(PMO)일 있다. 본 발명의 일실시예에 있어서, 상기 폴리에틸렌 옥사이드 (PEO) 의 분자량은 30M g/mol 이고, 폴리메틸렌 옥사이드 (PMO) 의 분자량은 5M g/mol 일 수 있다. 상기 PEO 고분자는 염료감응 태양전지의 전압특성을 향상시키며 PMO 고분자는 전류특성을 크게 향상시키므로, 양자를 혼합하여 사용하면 전압과 전류 특성을 동시에 향상시킬 수 있다. 또한, 상기 고분자는 전해질을 서서히 겔화시킬 수 있다. 이 경우, 겔화되더라도 고분자 프레임에 액체전해질이 충진되어 있는 상태로 이온전도가 주로 액체상에서 일어나므로 이온전도도에는 큰 영향이 없으며 동시에 누액을 효과적으로 방지할 수 있다. In addition, the composition of the present invention may comprise a polymeric material comprising a polar ligand. The polymeric material including the polar ligand serves to improve the photoelectric conversion efficiency of the dye-sensitized solar cell and to gradually gel it at room temperature. remind Examples of "polar ligands" include, but are not limited to, ether, amine, imine, nitrile, sulfide, amide and the like. Examples of the polymer including the polar ligand include polyethylene oxide (PEO), polymethylene oxide (PMO), polypropylene oxide (PPO), polyethyleneimine (PEI), polyalkylene sulfide (PAS), polyethylene succinate ), Polyacrylonitrile (PAN), and polymers derived therefrom, but are not limited thereto. In one embodiment of the present invention, the polymer is polyethylene oxide (PEO) and polymethylene oxide (PMO) having specific molecular weights. In one embodiment of the present invention, the molecular weight of the polyethylene oxide (PEO) may be 30M g / mol and the molecular weight of polymethylene oxide (PMO) may be 5M g / mol. The PEO polymer improves the voltage characteristics of the dye-sensitized solar cell and the PMO polymer greatly improves the current characteristics. Therefore, when both are mixed, the voltage and current characteristics can be improved at the same time. In addition, the polymer can slowly gel the electrolyte. In this case, even if gelation occurs, ion conduction occurs mainly in the liquid phase in the state that the polymer frame is filled with the liquid electrolyte, so that the ion conductivity is not greatly affected and the leakage can be effectively prevented.
염료감응 태양전지에 사용하기 위하여 본 발명의 조성물에는 요오드염이 포함된다. 요오드염은 요오드 (I2) 와 함께 첨가되어 산화-환원 쌍으로써의 기능을 한다. 요오드염을 전해질 필수 구성요소로 요오드 (I2) 와 함께 전해질에 용해시키면, I-/I3 - 산화-환원쌍을 형성하게 되고 가역적인 산화-환원 반응에 의해 염료감응 태양전지를 구동시키는 역할을 한다. 즉, I- 이온이 염료의 기저상태에 전자를 전달하여 (산화) 염료를 재생하고 생성된 I3 - 는 상대전극에서 환원되어 다시 I- 이온으로 전환된다. 상기 요오드염의 예로는, 1-부틸-3-메틸이미다졸륨 아이오다이드(1-butyl-3-methylimidazolium iodide; BMI), 1-에틸-3-메틸이미다졸륨 아이오다이드(1-ethyl-3-methylimidazolium iodide; EMI), 1-알릴-3-메틸이미다졸륨 아이오다이드(1-allyl-3-methylimidazolium iodide; AMI), 1-프로필-3-메틸이미다졸륨 아이오다이드(1-propyl-3-methylimidazolium iodide; PMI), 1,3-디메틸이미다졸륨 아이오다이드(1,3-dimethylimidazolium iodide; DMI), 1-헥실-2,3-디메틸이미다졸륨 아이오다이드(1-hexyl-2,3-dimethylimidazolium iodide; HDMI) 와 같은 이미다졸륨 요오드염, 4차 암모늄 요오드 (quaternary ammonium iodide), 피리디늄 요오드 (pyridinium iodide), 피롤리디늄 요오드 (pyrrolidinium iodide), 알칼리 금속 요오드 (LiI, NaI, KI, CsI) 등이 있으나, 이에 한정되는 것은 아니다.
For use in dye-sensitized solar cells, the compositions of the present invention include iodide salts. The iodine salt is added together with iodine (I 2 ) to function as an oxidation-reduction pair. When the iodine salt is dissolved in the electrolyte together with iodine (I 2 ) as an essential component of the electrolyte, it forms an I - / I 3 - oxidation - reduction pair and drives the dye - sensitized solar cell by reversible oxidation - reduction reaction . That is, the I - ion transfers electrons to the base state of the dye (oxidizes) and regenerates the dye, and the generated I 3 - is reduced at the counter electrode and converted back to I - ion. Examples of the iodide salt include 1-butyl-3-methylimidazolium iodide (BMI), 1-ethyl-3-methylimidazolium iodide, 3-methylimidazolium iodide (EMI), 1-allyl-3-methylimidazolium iodide (AMI), 1 -propyl-3-methylimidazolium iodide propyl-3-methylimidazolium iodide (PMI), 1,3-dimethylimidazolium iodide (DMI), 1-hexyl-2,3-dimethylimidazolium iodide such as imidazolium iodide, quaternary ammonium iodide, pyridinium iodide, pyrrolidinium iodide, and alkali metal iodide, such as hexyl-2,3-dimethylimidazolium iodide (HDMI) LiI, NaI, KI, CsI), but the present invention is not limited thereto.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
<실시예 1>≪ Example 1 >
전해질의 제조Preparation of electrolyte
[비교예][Comparative Example]
아세토니트릴(Acetonitile; ACN) 용매에 1-부틸-3-메틸이미다졸륨 아이오다이드(1-butyl-3-methylimidazolium iodide; BMI) 0.62 M, 아이오딘 (iodine; I2) 0.12 M, t-부틸피리딘(t-butylpyridine) 0.5 M을 용해시켜 액체전해질을 제조하였다.
To the acetonitrile (ACN) solvent, 1-butyl-3-methylimidazolium iodide (BMI) 0.62 M, iodine (I2) 0.12 M, t-butyl 0.5 M of t-butylpyridine was dissolved to prepare a liquid electrolyte.
[제조예 1][Production Example 1]
발레로니트릴(valeronitrile; VN) 과 디메틸아세트아마이드(dimethylacetamide; DMA)의 비율을 각각 6:4, 7:3, 8:2 (부피비) 로 조절하여 혼합용매를 제조하였다. 상기 혼합용매를 이용한 것을 제외하고 상기 비교예와 동일한 조성으로 액체전해질을 제조하였다. Mixed solvents were prepared by controlling the ratios of valeronitrile (VN) and dimethylacetamide (DMA) to 6: 4, 7: 3 and 8: 2 (volume ratio), respectively. A liquid electrolyte was prepared with the same composition as the comparative example except that the mixed solvent was used.
상기 혼합용매의 비점, 점도 및 유전상수 들은 단독 용매들의 고유 물성치들의 가중치 평균값으로부터 결정될 수 있다(표 1). The boiling point, viscosity and dielectric constant of the mixed solvent can be determined from the weighted average value of the intrinsic physical properties of the single solvent (Table 1).
[표 1] [Table 1]
[제조예 2][Production Example 2]
발레로니트릴(VN) 과 디메틸아세트아마이드(DMA)의 비율을 7:3 (부피비) 으로 조절하여 혼합용매를 제조하였다. 상기 혼합용매를 이용한 것을 제외하고 비교예 및 제조예 1과 동일한 조성으로 액체전해질을 제조하였다. 제조된 액체전해질에 폴리에틸렌 옥사이드(polyethylene oxide) (Mw = 30M g/mol) 를 1, 2, 3, 4, 5 중량% 로 각각 첨가하여 고분자 조성물이 첨가된 전해질을 제조하였다.
A mixed solvent was prepared by controlling the ratio of valeronitrile (VN) to dimethylacetamide (DMA) to 7: 3 (volume ratio). A liquid electrolyte was prepared with the same composition as Comparative Example and Production Example 1, except that the mixed solvent was used. Polyethylene oxide (Mw = 30M g / mol) was added to the prepared liquid electrolyte at 1, 2, 3, 4, and 5 wt%, respectively, to prepare an electrolyte added with the polymer composition.
[제조예 3][Production Example 3]
상기 제조예 2와 동일한 조성으로 액체전해질을 제조하고 폴리메틸렌 옥사이드(polymethylene oxide) (Mw = 5M g/mol)를 1, 2, 3, 4, 5 중량% 로 각각 첨가하여 고분자 조성물이 첨가된 전해질을 제조하였다.
A liquid electrolyte was prepared in the same manner as in Preparation Example 2, and polymethylene oxide (Mw = 5M g / mol) was added at 1, 2, 3, 4 and 5 wt% .
[제조예 4][Production Example 4]
상기 제조예 2와 동일한 조성으로 액체전해질을 제조하고, 폴리에틸렌 옥사이드 (Mw = 30M g/mol) 를 3 중량% 로 고정하고, 폴리메틸렌 옥사이드 (Mw = 5M g/mol) 를 1, 2, 3 중량% 로 각각 첨가하여 혼합 고분자 조성물이 첨가된 전해질을 제조하였다.
(Mw = 30M g / mol) was fixed at 3% by weight, and polymethylene oxide (Mw = 5M g / mol) was added to 1, 2 and 3 wt% %, Respectively, to prepare an electrolyte to which the mixed polymer composition was added.
<실시예 2>≪ Example 2 >
염료감응 태양전지의 제조Manufacture of dye-sensitized solar cell
본 발명의 전해질을 포함하는 염료감응 태양전지의 제조방법은 다음과 같다. 불소 함유 산화주석(FTO) 기판 (두께 2.3 mm) 위에 TiO2 페이스트(PST-18NR, JGC C&C, Japan)를 스크린 인쇄를 통해 12 ㎛ 두께로 도포하고 500 ℃ 온도에서 30 분간 소성하였고, 이어 산란입자 페이스트(400C, JGC C&C, Japan)를 동일한 방법으로 인쇄 및 소성하여 (소성 후 약 4 ㎛) 광음극을 제조하였다. 제조된 광음극은 염료용액 (0.2 mM Z907/에탄올) 에 침적하여 24시간 방치하였다. 그리고 상대전극은 FTO 기판에 25 mM H2PtCl6/이소프로필알콜 용액을 스핀 코팅(2,000 rpm/15 sec)하고, 400 ℃ 온도에서 30 분간 소성하여 준비하였다. 준비된 전극을 에탄올을 이용하여 세척하고 건조한 후 열가소성 수지 필름(Bynel, DuPont, 두께 60 ㎛)을 광음극과 홀이 형성된 상대전극 사이에 삽입한 후 핫 프레스(hot press)를 이용하여 열접착(130 ℃/15 sec)하였다. 상기 비교예 및 제조예들에 따라 제조된 전해질을 상대전극에 형성된 홀을 통하여 주입하고 열가소성 수지 필름과 커버 글라스를 이용하여 주입구를 봉지하였다.
A method of manufacturing a dye-sensitized solar cell including the electrolyte of the present invention is as follows. TiO2 paste (PST-18NR, JGC C & C, Japan) was applied on the fluorine-containing tin oxide (FTO) substrate (thickness: 2.3 mm) by screen printing to a thickness of 12 탆 and fired at 500 캜 for 30 minutes. (400 C, JGC C & C, Japan) were printed and fired by the same method (about 4 탆 after firing) to produce photo-cathodes. The photocathode was immersed in a dye solution (0.2 mM Z907 / ethanol) and allowed to stand for 24 hours. The counter electrode was prepared by spin coating (2,000 rpm / 15 sec) of 25
<실시예 3>≪ Example 3 >
전해질의 이온전도도 및 겔화 특성 평가Evaluation of Ionic Conductivity and Gelation Characteristics of Electrolyte
<3-1> 이온전도도<3-1> Ionic conductivity
상기 비교예 및 제조예에 따라 제조된 전해질은 실험실에서 제작한 4-포인트 프로브(4-point probe) 전도도셀을 이용하여 상온 임피던스를 측정함으로써 이온전도도 평가를 실시하였다. 전해질의 이온전도도는 아래와 같은 식에 의해 계산되었다.The electrolytes prepared according to Comparative Examples and Preparation Examples were evaluated for ionic conductivity by measuring impedance at room temperature using a 4-point probe conductivity cell manufactured in a laboratory. The ionic conductivity of the electrolyte was calculated by the following equation.
[계산식][formula]
상기 계산식에서 σ는 이온전도도 (mS/cm2), │Z│ 는 측정 임피던스 (mΩ), l 은 센서전극 간의 거리 (cm), A 는 전해질의 단면적 (cm2) 이다.
In the above equation,? Is the ionic conductivity (mS / cm 2 ), | Z | is the measured impedance (m?), L is the distance between the sensor electrodes (cm) and A is the cross-sectional area (cm 2 ) of the electrolyte.
아래 표 2에 비교예 및 제조예 1-4에 따라 제조된 전해질의 이온전도도를 나타내었다. 비점이 높은 본 발명의 혼합용매 액체전해질은 휘발성 아세토니트릴 액체전해질에 비해 약 3배 정도 낮은 상온 이온전도도를 나타내었다. 이는 용매의 점도가 증가하였기 때문으로 해석되며 이온전도도만으로 염료감응 태양전지의 광전변환이 결정되지는 않는 점을 간과해서는 안 된다. 또한, 제조예 1-4의 전해질을 비교한 결과, 액체전해질에 고분자가 소량 첨가되면 전해질 내 점도의 증가로 다소 이온전도도가 감소하는 경향을 나타내었지만 제조예 4의 경우 액체전해질과 동등 수준의 이온전도도를 나타내었다. Table 2 below shows the ionic conductivities of the electrolytes prepared according to Comparative Examples and Production Examples 1-4. The mixed solvent liquid electrolyte of the present invention having a high boiling point showed a room temperature ionic conductivity of about 3 times lower than that of a volatile acetonitrile liquid electrolyte. This is interpreted as an increase in the viscosity of the solvent, and it should not be overlooked that the photoelectric conversion of the dye-sensitized solar cell is not determined solely by the ionic conductivity. Further, as a result of comparing the electrolytes of Production Example 1-4, it was found that when a small amount of polymer was added to the liquid electrolyte, the ion conductivity tended to decrease due to an increase in the viscosity in the electrolyte. In Production Example 4, Conductivity was shown.
[표 2] [Table 2]
<3-2> 겔화 특성<3-2> Gelation characteristics
도 1과 같이 PEO 와 PMO 고분자를 단독으로 첨가하였을 때는 겔화 특성은 관찰되지 않았다. 통상적으로 고분자를 첨가하여 물리적인 겔화를 이루기 위해서는 10~20 중량비 이상의 고분자를 첨가하여야 가능하다. 그러나 PEO 와 PMO 고분자를 함께 혼합한 경우에는 적은 첨가량에도 불구하고 상온에서 겔화가 진행되었다. 이는 PEO 와 PMO 고분자가 특정한 상호침투 구조를 이루며 3차원적인 구조를 형성하기 때문으로 해석할 수 있으며 이 경우 액체전해질과 고분자 간의 일정한 상분리가 일어나기 때문에 이온전도도의 증가를 기대할 수 있다. 즉, 고분자 사슬이 랜덤하게 풀어져 있는 경우 이온전도에 방해요소로 작용하지만 고분자 사슬과 액체상 간에 상분리가 일어나 채널이 형성되면 액체상을 통한 이온전도가 방해를 받지 않는다. 상기 이온전도도 결과도 이러한 사실을 뒷받침하고 있다.
As shown in FIG. 1, no gelation characteristics were observed when PEO and PMO polymer alone were added. Generally, in order to achieve physical gelation by adding a polymer, it is necessary to add a polymer having a weight ratio of 10 to 20 or more. However, when PEO and PMO polymer were mixed together, the gelation proceeded at room temperature despite the small addition amount. It can be interpreted that PEO and PMO polymers form a specific interpenetrating structure and form a three-dimensional structure. In this case, ion conductivity can be expected to increase because a phase separation occurs between the liquid electrolyte and the polymer. That is, when the polymer chain is randomly released, it functions as an obstacle to ion conduction, but when the channel is formed between the polymer chain and the liquid phase, the ion conduction through the liquid phase is not hindered. This ion conductivity result also supports this fact.
<실시예 4><Example 4>
광전변환 효율 평가Evaluation of photoelectric conversion efficiency
<4-1><4-1>
실시예 2에 따라 제작된 셀에 대하여 표준측정 조건(AM1.5G, 100 mW/cm2)에서 전류-전압 곡선을 평가하였으며 광전변환효율 및 충밀계수는 다음 계산식에 의해 결정되었다.The current-voltage curves of the cells fabricated according to Example 2 were evaluated under the standard measurement conditions (AM1.5G, 100 mW / cm2), and the photoelectric conversion efficiency and the packing coefficient were determined by the following equations.
[계산식][formula]
상기 계산식에서, J 는 전류밀도 (mA/cm2), V 는 전압 (V) 을 나타내며 Jmax 와 Vmax 는 최대전력치에서의 전류밀도와 전압을 나타낸다. 또한 Jsc 와 Voc 는 각각 단락전류밀도와 개방전압을 나타내며 Pinput 은 솔라시뮬레이터에서 인가한 광원의 세기를 나타낸다 (100 mW/cm2).
In the above equation, J represents the current density (mA / cm 2 ), V represents the voltage (V), and J max and V max represent the current density and voltage at the maximum power value. J sc and V oc are the short circuit current density and open voltage, respectively, and P input is the intensity of the light source applied by the solar simulator (100 mW / cm 2 ).
<4-2><4-2>
상기 비교예 및 제조예 1 및 2의 전해질을 주입한 염료감응 태양전지의 광전변환 특성을 측정한 결과를 하기 도 2 및 표 3에 정리하였다. The results of measurement of the photoelectric conversion characteristics of the dye-sensitized solar cell in which the electrolyte of Comparative Example and Production Examples 1 and 2 were injected are summarized in FIG. 2 and Table 3. FIG.
[표 3] [Table 3]
휘발성 ACN 액체전해질 대비 혼합용매 액체전해질을 주입한 경우 상대적으로 낮은 이온전도도로 인해 전류밀도 및 충밀계수가 다소 낮게 측정됨을 알 수 있으나 전압특성은 상대적으로 우수하였다. 또한, 제조예 2에서 PEO 고분자 첨가량이 증가할 수록 전류 및 전압특성이 향상되는 경향을 나타내었다. 전류밀도는 약 3 중량% 첨가 시까지 증가하다가 이후 감소하는 경향을 나타내었으나 전압은 계속 증가하는 특성을 나타내었다. 이는 PEO 고분자의 극성리간드 (-O-, 에테르 산소 (ether oxygen)) 가 TiO2 표면에서 전자밀도를 높여주는 역할을 하여 TiO2 전도대에서의 전자 확산을 촉진시키고 동시에 페르미 준위 (Fermi level) 을 네거티브한 (negative) 방향으로 전이시켜 염료감응 태양전지의 개방전압을 증가시키는 것으로 해석할 수 있다. 그러나 PEO 고분자의 함량이 증가할수록 이온전도도를 저하시켜 3 중량% 이상에서는 단락전류가 감소하게 되는 것으로 사료되며 따라서 PEO 고분자의 최적 첨가량은 3 중량% 로 판단되었다.
When the liquid electrolyte was injected into the mixed ACN liquid electrolyte compared to the volatile ACN liquid electrolyte, the current density and the reduction coefficient were measured to be slightly lower due to the relatively low ionic conductivity, but the voltage characteristics were relatively good. In addition, as the addition amount of the PEO polymer increased in Production Example 2, the current and voltage characteristics tended to be improved. The current density increased until the addition of about 3 wt%, but then decreased, but the voltage continued to increase. This is because the polar ligand (-O-, ether oxygen) of the PEO polymer enhances the electron density at the TiO2 surface, promotes the electron diffusion in the TiO2 conduction band, and at the same time the Fermi level is negative negative direction, thereby increasing the open-circuit voltage of the dye-sensitized solar cell. However, as the content of PEO polymer increases, the ionic conductivity decreases and the short - circuit current decreases at more than 3 wt%. Therefore, the optimal amount of PEO polymer was determined to be 3 wt%.
<4-3><4-3>
비교예, 제조예 1 및 3의 전해질을 주입한 염료감응 태양전지의 광전변환 특성을 측정한 결과를 도 3 및 표 4에 정리하였다. The results of measurement of the photoelectric conversion characteristics of the dye-sensitized solar cell in which the electrolytes of Comparative Examples and Preparation Examples 1 and 3 were injected are shown in FIG. 3 and Table 4.
[표 4][Table 4]
제조예 3에서 PMO 고분자의 함량을 증가시킬수록 상기 제조예 2와 상이한 결과를 얻을 수 있었다. 즉, PMO 고분자의 함량이 증가할수록 전압은 낮아지고 전류는 증가하는 경향을 나타내었다. 이는 PEO 고분자와 PMO 고분자의 구조적인 차이로 설명될 수 있다. 즉, PMO 는 PEO 와 비교하여 매우 유사한 분자구조를 가지고 있으나 극성리간드의 밀도가 높아 PEO 에 비해 훨씬 강한 친핵체로 작용할 수 있다. 따라서 TiO2 표면에서 강하게 전자를 밀어주는 역할을 하여 광전전류를 증가시키는 역할을 하는 것으로 사료되며 전압특성의 저하는 TiO2 전도대의 전자밀도 및 전자확산 속도가 증가함에 따라 전자재결합 속도도 함께 증가하기 때문으로 사료된다.
As the content of PMO polymer was increased in Preparative Example 3, results different from those of Preparative Example 2 were obtained. That is, as the content of PMO polymer increases, the voltage decreases and the current tends to increase. This can be explained by the structural difference between PEO polymer and PMO polymer. That is, PMO has a very similar molecular structure as PEO, but it has a higher density of polar ligands and can act as a stronger nucleophile than PEO. Therefore, it seems that it plays a role of increasing the photoelectric current by strongly pushing electrons from the TiO2 surface. The degradation of the voltage characteristics is due to the increase of the electron recombination speed as the electron density and electron diffusion rate of the TiO2 conduction band increase .
<4-4><4-4>
비교예, 제조예 1 및 4의 전해질을 주입한 염료감응 태양전지의 광전변환 특성을 측정한 결과를 도 4 및 표 5에 정리하였다. The results of measurement of the photoelectric conversion characteristics of the dye-sensitized solar cell in which the electrolytes of Comparative Examples 1 and 4 were injected are summarized in FIG. 4 and Table 5.
[표 5] [Table 5]
제조예 4에서는 실시예 2 와 3 의 결과를 토대로 PEO 와 PMO 고분자를 혼합하여 전류와 전압 특성을 동시에 최적화하고자 하였다. PEO 3 중량% 와 PMO 1 중량% 를 혼합 첨가한 경우 전류와 전압이 동시에 향상되었으며 비교예의 ACN 액체전해질과 동등 수준의 효율특성을 나타내었다.
In Production Example 4, based on the results of Examples 2 and 3, the current and voltage characteristics were simultaneously optimized by mixing PEO and PMO polymer. When 3 wt% of PEO and 1 wt% of PMO were mixed, the current and voltage were improved at the same time, and the efficiency characteristics were equivalent to those of ACN liquid electrolyte of Comparative Example.
<4-5><4-5>
도 5에 비교예와 제조예 4의 전해질을 주입한 염료감응 태양전지의 고온 내구성 가속 평가 결과를 나타내었다. 비교예의 휘발성 전해질은 누액 및 휘발로 인해 급격히 효율이 감소하는데 반해 제조예 4의 혼합용매 겔 전해질은 1,000 시간 이후 85% 이상의 우수한 효율유지율을 나타내었다.
FIG. 5 shows the result of evaluating accelerated durability of the dye-sensitized solar cell in which the electrolyte of Comparative Example and Production Example 4 was injected. The volatile electrolytes of the comparative example rapidly decreased in efficiency due to leakage and volatilization, whereas the mixed solvent gel electrolyte of Production Example 4 showed an excellent efficiency maintenance rate of 85% or more after 1,000 hours.
이제까지 본 발명에 대하여 그 바람직한 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.
Claims (9)
폴리에틸렌 옥사이드(PEO)와 폴리메틸렌 옥사이드(PMO)는 3:1의 중량비로 포함되는 것을 특징으로 하는 조성물.The method according to claim 1,
Wherein the polyethylene oxide (PEO) and the polymethylene oxide (PMO) are included in a weight ratio of 3: 1.
상기 폴리에틸렌 옥사이드(PEO) 및 폴리메틸렌 옥사이드(PMO)는 전체 조성물에 대하여 1 내지 5 중량% 로 포함하는 것을 특징으로 하는 조성물.The method according to claim 1,
Wherein the polyethylene oxide (PEO) and the polymethylene oxide (PMO) are present in an amount of 1 to 5% by weight based on the total composition.
상기 폴리에틸렌 옥사이드(PEO)는 전체 조성물에 대하여 3 중량%로 포함되고, 폴리메틸렌 옥사이드(PMO)는 전체 조성물에 대하여 1 중량%로 포함되는 것을 특징으로 하는 조성물.5. The method of claim 4,
Wherein the polyethylene oxide (PEO) is included in an amount of 3 wt% based on the total composition, and the polymethylene oxide (PMO) is included in an amount of 1 wt% based on the total composition.
발레로니트릴과 디메틸아세트아마이드는 6:4 내지 8:2 의 부피비로 포함되는 것을 특징으로 하는 조성물.The method according to claim 1,
Valeronitrile and dimethylacetamide are contained in a volume ratio of 6: 4 to 8: 2.
상기 혼합용매는 1.2 cP 이하의 점도, 및 20 이상 35 이하의 유전상수를 갖는 것을 특징으로 하는 조성물.The method according to claim 1,
Wherein the mixed solvent has a viscosity of 1.2 cP or less and a dielectric constant of 20 or more and 35 or less.
상기 조성물은 요오드염을 포함하는 것을 특징으로 하는 조성물.The method according to claim 1,
Wherein the composition comprises an iodide salt.
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