KR20130015086A - Electrolyte for dye-sensitized solarcell comprising polydiacetylene, preparation method thereof and dye-sensitized solarcell comprising the same - Google Patents
Electrolyte for dye-sensitized solarcell comprising polydiacetylene, preparation method thereof and dye-sensitized solarcell comprising the same Download PDFInfo
- Publication number
- KR20130015086A KR20130015086A KR1020110076912A KR20110076912A KR20130015086A KR 20130015086 A KR20130015086 A KR 20130015086A KR 1020110076912 A KR1020110076912 A KR 1020110076912A KR 20110076912 A KR20110076912 A KR 20110076912A KR 20130015086 A KR20130015086 A KR 20130015086A
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- KR
- South Korea
- Prior art keywords
- group
- dye
- sensitized solar
- imidazolium
- electrolyte
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 59
- 229920000015 polydiacetylene Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 37
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 27
- -1 polyethylene- monomethylene Polymers 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 7
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 6
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- 125000002883 imidazolyl group Chemical group 0.000 claims description 6
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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 claims description 5
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- XREPTGNZZKNFQZ-UHFFFAOYSA-M 1-butyl-3-methylimidazolium iodide Chemical compound [I-].CCCCN1C=C[N+](C)=C1 XREPTGNZZKNFQZ-UHFFFAOYSA-M 0.000 claims 2
- PMUFNPCDXAPFKN-UHFFFAOYSA-N 3-hexyl-1h-imidazol-3-ium;iodide Chemical compound [I-].CCCCCC[N+]=1C=CNC=1 PMUFNPCDXAPFKN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L49/00—Compositions of homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
Description
본 발명은 폴리다이아세틸렌을 포함하는 염료감응 태양전지용 전해질, 이의 제조방법 및 이를 포함하는 염료감응 태양전지에 관한 것으로서, 더욱 상세하게는 높은 이온전도도와 향상된 기계적 물성을 제공하는 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머와 산화-환원 유도체를 포함하는 염료감응 태양전지용 전해질, 이의 제조방법 및 이를 포함하는 에너지 변환 효율이 높은 염료감응 태양전지에 관한 것이다. The present invention relates to an electrolyte for a dye-sensitized solar cell including polydiacetylene, a method for manufacturing the same, and a dye-sensitized solar cell including the same, and more particularly, both ends of imidazolium providing high ionic conductivity and improved mechanical properties. The present invention relates to a dye-sensitized solar cell electrolyte comprising a diacetylene monomer substituted with an ethylene oxide-based oligomer or a polymer and an oxidation-reducing derivative, a method for preparing the same, and a dye-sensitized solar cell having high energy conversion efficiency.
1991년 오레건과 마이클 그라첼의 선구적인 연구로 탄생한 염료감응 태양전지는 가시광선영역대의 파장을 흡수하여 전자-홀 쌍을 생성하는 감광성 염료분자와 그로부터 생성된 전자를 전달하는 나노결정성 산화티타늄 입자로 만든 산화물 반도체 전극을 이용한 광전기화학적 태양전지이다(미국 특허공보 제4,927,721호 및 동 제5,350,644호). 색소증감형 태양전지 또는 습식 태양전지로도 지칭되는 염료감응 태양전지는 실리콘형 태양전지에 비해 상대적으로 간단한 제조공정과 저렴한 제조비용으로 인해 이와 관련한 많은 연구가 진행되고 있다.Dye-sensitized solar cells, born in 1991 by Oregon and Michael Gratzel's pioneering work, are nanocrystalline titanium oxides that absorb photosensitive dye molecules that absorb wavelengths in the visible range and produce electron-hole pairs and transfer electrons from them. Photoelectrochemical solar cells using oxide semiconductor electrodes made of particles (US Pat. Nos. 4,927,721 and 5,350,644). Dye-sensitized solar cells, also referred to as dye-sensitized solar cells or wet solar cells, have been studied in this regard due to their relatively simple manufacturing process and low manufacturing cost.
종래의 액체 전해질을 적용한 염료감응 태양전지(한국공개특허 제2001-0030478호 등)는 높은 에너지 변환 효율을 보이는 동시에 전해액 누수 및 용매 증발로 인한 성능의 저하 등의 안정성 문제와 유기 용매 사용으로 환경오염 문제를 야기하는데, 이는 염료감응 태양전지의 상업화의 가장 큰 문제점으로 인식되고 있다. 이 같은 문제를 해결하고자 다양한 연구가 진행되고 있으며, 특히 염료감응 태양전지의 내구성과 안정성 개선을 통해 태양전지의 수명을 늘릴 수 있는 준고체 전해질 또는 고체 전해질을 적용한 염료감응 태양전지 개발이 진행되고 있다.Dye-sensitized solar cells using a conventional liquid electrolyte (Korea Patent Publication No. 2001-0030478, etc.) exhibit high energy conversion efficiency and environmental problems due to stability problems such as electrolyte leakage and deterioration of performance due to solvent evaporation and the use of organic solvents. It causes a problem, which is recognized as the biggest problem of commercialization of dye-sensitized solar cells. In order to solve this problem, various researches are being conducted. In particular, development of dye-sensitized solar cells using a semi-solid electrolyte or a solid electrolyte that can extend the life of the solar cell through improving the durability and stability of the dye-sensitized solar cell is underway. .
상술한 액체 전해질의 문제점을 개선하기 위한 개발의 예로 이온성 액체 전해질을 적용한 염료감응 태양전지가 있다(한국공개특허 제2009-0022383호 등). 종래 유기용매를 사용한 염료감응 태양전지 전해질에 비하여 낮은 증기압으로 용매 증발을 근본적으로 차단하여 이를 적용한 염료감응 태양전지는 우수한 내구성과 안정성을 보인다. 하지만 액체 상을 가지는 상기 전해질은 염료감응 태양전지의 완벽한 실링(sealing)을 하지 못했을 시 전해액의 누수로 인한 염료감응 태양전지의 성능의 저하 등의 안정성 문제를 해결하는데 어려움을 보인다.An example of development to improve the above-mentioned problems of the liquid electrolyte is a dye-sensitized solar cell to which an ionic liquid electrolyte is applied (Korea Patent Publication No. 2009-0022383, etc.). The dye-sensitized solar cell applied to the dye-sensitized solar cell using the organic solvent is fundamentally blocked evaporation at a lower vapor pressure than the conventional organic solvent using the organic solvent shows excellent durability and stability. However, the electrolyte having a liquid phase has difficulty in solving stability problems such as deterioration of the performance of the dye-sensitized solar cell due to leakage of the electrolyte when the sealing of the dye-sensitized solar cell is not completed.
또한, 이온성 액체 전해질 이외의 또 다른 예로는 고체 고분자 전해질을 들 수 있다. 고체 고분자 전해질은 낮은 가격과 제조공정상 편의를 제공하는 특징과 우수한 기계적 강도를 제공함으로써 우수한 내구성과 안정성을 나타내는 염료감응 태양전지를 제공할 수 있다(논문 [M.S. Kang, J. H. Kim, Y. J. Kim, J. G. Won, N. G. Park, Y. S. Kang, Chem. Commun., 2005, 889~891] 등). 하지만 태양전지 내에서 이온전도도가 낮고, 전해질과 염료가 흡착된 산화티타늄 전극이 불완전하게 접촉하는 등의 단점이 있다.In addition, another example other than the ionic liquid electrolyte may be a solid polymer electrolyte. The solid polymer electrolyte can provide a dye-sensitized solar cell exhibiting excellent durability and stability by providing features with low cost and convenience in manufacturing process and excellent mechanical strength (paper [MS Kang, JH Kim, YJ Kim, JG Won] , NG Park, YS Kang, Chem. Commun., 2005, 889-891, etc.). However, there are disadvantages such as low ion conductivity in the solar cell and incomplete contact between the electrolyte and the titanium oxide electrode adsorbed with the dye.
이와 같이, 종래의 방법으로는 염료감응 태양전지의 내구성과 안정성을 기대하기 힘들며, 태양전지의 광 변환 효율 향상에 한계를 보인다. 이온성 액체 전해질의 특징과 고체 고분자 전해질의 장점을 모두 가지며, 동시에 염료가 흡착된 산화티타늄 전극과 전해질 사이의 우수한 접촉을 통하여 태양전지 에너지 변환 효율을 향상시키는 것이 관건이며, 그러한 태양전지의 개발에 대한 요구는 지속되고 있다.As such, it is difficult to expect the durability and stability of the dye-sensitized solar cell by the conventional method, and shows a limitation in improving the light conversion efficiency of the solar cell. It is important to improve the efficiency of solar cell energy conversion through excellent contact between the dye-adsorbed titanium oxide electrode and the electrolyte, which has both the characteristics of the ionic liquid electrolyte and the advantages of the solid polymer electrolyte. The demand for it continues.
본 발명의 목적은 종래의 염료감응 태양전지용 전해질에 비하여 높은 이온전도도와 보다 향상된 기계적 물성을 제공하면서 에너지 변환 효율이 높은 염료감응 태양전지용 전해질을 제공하는 것이다.It is an object of the present invention to provide a dye-sensitized solar cell electrolyte having high energy conversion efficiency while providing higher ionic conductivity and improved mechanical properties compared to conventional dye-sensitized solar cell electrolytes.
본 발명의 다른 목적은 상기 염료감응 태양진지용 전해질의 제조방법을 제공하는 것이다. It is another object of the present invention to provide a method for preparing the dye-sensitized solar electrolyte.
본 발명의 또 다른 목적은 상기 염료감응 태양전지용 전해질을 포함하는 에너지 변환 효율이 높은 염료감응 태양전지를 제공하는 것이다. Still another object of the present invention is to provide a dye-sensitized solar cell having high energy conversion efficiency including the dye-sensitized solar cell electrolyte.
상기 목적을 달성하기 위해, 본 발명은 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체를 중합시킨 폴리다이아세틸렌, 에틸렌 옥사이드 계열 올리고머 또는 폴리머 및 산화-환원 유도체를 포함하는 염료감응 태양전지용 전해질을 제공한다.In order to achieve the above object, the present invention provides a dye-sensitized solar cell electrolyte comprising a polydiacetylene, an ethylene oxide-based oligomer or a polymer and an oxidation-reduction derivative polymerized with a diacetylene monomer substituted at both ends with imidazolium. do.
또한, 본 발명은 광전극, 대향 전극 및 상기 광전극과 대향 전극 사이에, 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체를 중합시킨 폴리다이아세틸렌, 에틸렌 옥사이드 계열 올리고머 또는 폴리머, 및 산화-환원 유도체를 포함하는 염료감응 태양전지용 전해질을 포함하는 것을 특징으로 하는 염료감응 태양전지를 제공한다. In addition, the present invention is a polydiacetylene, ethylene oxide-based oligomers or polymers polymerized with a photoelectrode, a counter electrode and a diacetylene monomer substituted at both ends with imidazolium between the photoelectrode and the counter electrode, and an oxidation-reduction It provides a dye-sensitized solar cell comprising a dye-sensitized solar cell electrolyte comprising a derivative.
또한, 본 발명은 (S1) 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 혼합하여 균일 용액을 제조하는 단계; (S2) 상기 균일 용액에 자외선 노광하여 폴리다이아세틸렌 혼합 용액을 제조하는 단계; 및 (S3) 상기 폴리다이아세틸렌 혼합 용액에 산화-환원 유도체를 첨가하는 단계를 포함하는 염료감응 태양전지용 전해질의 제조방법을 제공한다.In addition, the present invention (S1) is a step of preparing a uniform solution by mixing a diacetylene monomer and ethylene oxide-based oligomer or polymer substituted at both ends with imidazolium; (S2) ultraviolet exposure to the homogeneous solution to prepare a polydiacetylene mixed solution; And (S3) provides a method for producing a dye-sensitized solar cell electrolyte comprising the step of adding an oxidation-reduction derivative to the polydiacetylene mixed solution.
또한, 본 발명은 염료감응 태양전지용 전해질 제조에 사용될 수 있는 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체로서 화학식 1로 표시되는 신규 다이아세틸렌 단량체를 제공한다.In addition, the present invention provides a novel diacetylene monomer represented by the formula (1) as a diacetylene monomer substituted at both terminals with imidazolium that can be used in the preparation of the dye-sensitized solar cell electrolyte.
[화학식 1][Formula 1]
A-(CH2)c-(L1)d-(CH2)e-C≡C-C≡C-(CH2)f-(L2)g-(CH2)h-BA- (CH 2 ) c- (L 1 ) d- (CH 2 ) e -C≡CC≡C- (CH 2 ) f- (L 2 ) g- (CH 2 ) h -B
상기 화학식 1에서, In Formula 1,
A 및 B는 서로 동일하거나 상이한 이미다졸륨이고, 상기 이미다졸륨은 이미다졸 고리의 1번 질소가 주쇄의 탄소와 결합되고, 3번 질소 위치에서 알킬기로 치환되며, 상기 알킬기는 탄소 수가 1 내지 5의 선형 또는 분지형 탄화수소로서, C1 -10 알킬기, 할로겐, 히드록시기, 니트로기, 아미노기, 시아노기, C1 -10 알콕시기, 아미디노기, 히드라진기 또는 카르복실기로 치환될 수 있고, A and B are the same or different imidazolium from each other, wherein the imidazolium is the nitrogen of the imidazole ring bonded to the carbon of the main chain and substituted with an alkyl group at the nitrogen position of 3, wherein the alkyl group has 1 to a linear or branched hydrocarbon group of 5, and may be substituted with a C 1 -10 alkyl group, a halogen, a hydroxy group, a nitro group, an amino group, a cyano group, C 1 -10 alkoxy group, amidino group, a hydrazine group or a carboxyl group,
c+e 및 f+h는 8 내지 50의 정수이고 서로 동일하거나 상이하고,c + e and f + h are integers from 8 to 50, the same as or different from each other,
L1 및 L2는 하나 이상의 에틸렌 옥사이드기, 아민기, 카르보닐기, 에스테르기, 우레탄기 또는 요소기이고 서로 동일하거나 상이하고, L 1 and L 2 are at least one ethylene oxide group, amine group, carbonyl group, ester group, urethane group or urea group and are the same as or different from each other,
d 및 g는 0 내지 20이고 서로 동일하거나 상이하다.d and g are 0 to 20 and are the same as or different from each other.
본 발명에 따른 염료감응 태양전지용 전해질은 다이아세틸렌단량체에 자외선 노광하여 중합된 폴리다이아세틸렌(Polydiacetylene, PDA) 주쇄를 따라 양말단의 치환기들이 배열되는 구조를 가지기 때문에 배열된 치환구조를 따라 염료감응 태양전지에 필수적으로 포함되는 산화-환원 유도체가 배열되어 이온채널(ion-channel)을 형성하여 우수한 이온전도도를 보유하고, 고분자 전해질의 낮은 증기압 특성을 통해 용매 증발을 근본적으로 차단함으로써 기존 이온성 액체 전해질이 가지는 장점을 제공할 수 있는 동시에, 낮은 가격과 제조공정상 편의를 제공하며 우수한 기계적 강도를 나타냄으로써 고체 고분자 전해질이 가지는 장점도 제공할 수 있다. 따라서, 본 발명에 따른 염료감응 태양전지용 전해질을 적용한 염료감응 태양전지의 내구성과 안정성을 향상시킬 수 있으며 염료감응 태양전지의 광변환 효율을 높일 수 있다. The dye-sensitized solar cell electrolyte according to the present invention has a structure in which substituents of the distal end are arranged along a polydiacetylene (PDA) backbone polymerized by ultraviolet exposure to a die acetylene monomer, thus the dye-sensitized solar cell is arranged along the substitution structure. Redox derivatives, which are essentially included in the battery, are arranged to form ion-channels to maintain excellent ion conductivity and to fundamentally block solvent evaporation through the low vapor pressure characteristics of the polymer electrolytes. This can provide the advantages of the solid polymer electrolyte by providing a low cost, convenience in the manufacturing process and excellent mechanical strength. Therefore, the durability and stability of the dye-sensitized solar cell applying the electrolyte for the dye-sensitized solar cell according to the present invention can be improved and the light conversion efficiency of the dye-sensitized solar cell can be improved.
도 1은 실시예에서 제조한 염료감응 태양전지의 광전류-전압의 상관관계 곡선을 나타낸 그래프이다.
도 2는 본 발명의 다이아세틸렌 단량체(식중, R1 및 R2는 본 발명의 다이아세틸렌의 말단의 치환기를 간략화하여 표시한 것임)가 자외선 노광에 따라 중합되어 폴리다이아세틸렌이 형성되는 과정을 간략하게 도시화한 것이다.
도 3은 본 발명의 폴리다이아세틸렌 혼합 용액 내 폴리다이아세틸렌과 에틸렌 옥사이드 계열 올리고머 또는 폴리머가 배치되어 있는 형태를 간략하게 도시화한 것이다. 1 is a graph showing the correlation curve of the photocurrent-voltage of the dye-sensitized solar cell prepared in Example.
2 is a simplified diagram of a process in which a polyacetylacetylene is formed by polymerizing a diacetylene monomer of the present invention (wherein R 1 and R 2 are simplified representations of the substituents of the terminal end of the diacetylene of the present invention) by ultraviolet exposure. It is urbanized.
Figure 3 is a simplified illustration of the form in which the polydiacetylene and ethylene oxide-based oligomers or polymers are disposed in the polydiacetylene mixed solution of the present invention.
이하, 본 발명을 자세하게 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명의 하나의 구체예에 따르면, 본 발명의 염료감응 태양전지용 전해질은 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체를 중합시킨 폴리다이아세틸렌; 에틸렌 옥사이드 계열 올리고머 또는 폴리머; 및 산화-환원 유도체를 포함한다. According to one embodiment of the present invention, the dye-sensitized solar cell electrolyte of the present invention is a polydiacetylene polymerized by diacetylene monomer substituted at both ends with imidazolium; Ethylene oxide based oligomers or polymers; And redox derivatives.
본 발명의 염료감응 태양전지용 전해질에 포함되는 폴리다이아세틸렌은 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체를 중합시켜 제조한 것을 특징으로 한다. 본 발명에 따른 폴리다이아세틸렌은 양 말단이 이미다졸륨의 이온성 치환기로 배열되기 때문에 배열된 치환 구조에 따라 산화-환원 유도체가 배열되어 생성된 이온채널(ion-channel)을 통해 이온전도도를 향상시킬 수 있다. The polydiacetylene included in the dye-sensitized solar cell electrolyte of the present invention is characterized by being prepared by polymerizing a diacetylene monomer whose both ends are substituted with imidazolium. In the polydiacetylene according to the present invention, since both ends are arranged with ionic substituents of imidazolium, the ion-conductivity is improved through ion-channels formed by arranging redox derivatives according to the arranged substitution structure. You can.
구체적으로, 본 발명의 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체는 하기 화학식 1로 표시될 수 있으나, 반드시 이에 한정되는 것은 아니다.
Specifically, the diacetylene monomer in which both terminals of the present invention are substituted with imidazolium may be represented by the following Chemical Formula 1, but is not necessarily limited thereto.
[화학식 1][Formula 1]
A-(CH2)c-(L1)d-(CH2)e-C≡C-C≡C-(CH2)f-(L2)g-(CH2)h-BA- (CH 2 ) c- (L 1 ) d- (CH 2 ) e -C≡CC≡C- (CH 2 ) f- (L 2 ) g- (CH 2 ) h -B
상기 화학식 1에서, In Formula 1,
A 및 B는 서로 동일하거나 상이한 이미다졸륨이고, 상기 이미다졸륨은 이미다졸 고리의 1번 질소가 주쇄의 탄소와 결합되고, 3번 질소 위치에서 알킬기로 치환되며, 상기 알킬기는 탄소 수가 1 내지 5의 선형 또는 분지형 탄화수소로서, C1 -10 알킬기, 할로겐, 히드록시기, 니트로기, 아미노기, 시아노기, C1 -10 알콕시기, 아미디노기, 히드라진기 또는 카르복실기로 치환될 수 있고, A and B are the same or different imidazolium from each other, wherein the imidazolium is the nitrogen of the imidazole ring bonded to the carbon of the main chain and substituted with an alkyl group at the nitrogen position of 3, wherein the alkyl group has 1 to a linear or branched hydrocarbon group of 5, and may be substituted with a C 1 -10 alkyl group, a halogen, a hydroxy group, a nitro group, an amino group, a cyano group, C 1 -10 alkoxy group, amidino group, a hydrazine group or a carboxyl group,
c+e 및 f+h는 8 내지 50의 정수이고 서로 동일하거나 상이하고,c + e and f + h are integers from 8 to 50, the same as or different from each other,
L1 및 L2는 하나 이상의 에틸렌 옥사이드기, 아민기, 카르보닐기, 에스테르기, 우레탄기 또는 요소기이고 서로 동일하거나 상이하고, L 1 and L 2 are at least one ethylene oxide group, amine group, carbonyl group, ester group, urethane group or urea group and are the same as or different from each other,
d 및 g는 0 내지 20이고 서로 동일하거나 상이하다.
d and g are 0 to 20 and are the same as or different from each other.
상기 화학식 1에서, 이미다졸륨의 치환기인 알킬기의 구체적인 예로는 선형 또는 분지형의 메틸, 에틸, 프로필, 이소부틸, sec-부틸, tert-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있고, 바람직하게는 메틸이다.
In Formula 1, specific examples of the alkyl group which is a substituent of imidazolium include linear or branched methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. And preferably methyl.
본 발명의 에틸렌 옥사이드 계열 올리고머 또는 폴리머는 분자량이 200 내지 8000 g/mol의, 폴리에틸렌글라이콜, 폴리에틸렌-모노메틸렌 에테르, 폴리에틸렌-다이메틸렌 에테르, 폴리에틸렌-모노에틸렌 에테르, 폴리에틸렌- 다이에틸렌 에테르 등을 사용할 수 있으나 반드시 이에 한정되는 것은 아니다. 특히 바람직하게는 폴리에틸렌 글리콜-다이메틸렌 에테르를 사용할 수 있다. 에틸렌 옥사이드 계열 올리고머 또는 폴리머는 전해질 내에서 분자사슬의 운동을 통해 산화-환원 유도체의 확산(diffusion) 운동을 촉진하는 역할을 한다. 특히 에틸렌 옥사이드 계열 올리고머 또는 폴리머의 무정형(amorphous) 부분에서 더욱 활발하게 분자 사슬의 운동이 일어나 산화-환원 유도체의 물리적 확산(Physical diffusion) 운동을 촉진한다. 또한, 에틸렌 옥사이드 계열 올리고머 또는 폴리머의 산소원자의 비공유결합 전자와 전해질 내의 양이온이 이온결합에 의해 에틸렌 옥사이드 계열 올리고머 또는 폴리머의 산소원자를 따라 양이온이 배열된다. 이 양이온 주변에 음전기를 띄는 산화-환원 유도체가 다시 배열되고 이를 통해 산화-환원 유도체의 교환반응(exchange reaction)을 통해 그로터스 메카니즘 확산 (Grothuss mechanism diffusion)을 한다. 이는 물리적 확산(Physical diffuion)보다 빠른 확산으로 전해질의 이온전도도 향상에 기여한다.
Ethylene oxide-based oligomers or polymers of the present invention include polyethylene glycol, polyethylene-monomethylene ether, polyethylene-dimethylene ether, polyethylene-monoethylene ether, polyethylene-diethylene ether, etc., having a molecular weight of 200 to 8000 g / mol. Can be used, but is not necessarily limited thereto. Particular preference is given to using polyethylene glycol-dimethylene ethers. Ethylene oxide-based oligomers or polymers serve to promote the diffusion (diffusion) movement of the redox derivatives through the movement of the molecular chain in the electrolyte. In particular, the movement of the molecular chain occurs more actively in the amorphous portion of the ethylene oxide-based oligomer or polymer to promote the physical diffusion of the redox derivatives. In addition, cations are arranged along the oxygen atoms of the ethylene oxide-based oligomer or polymer by the ionic bond between the non-covalent electron of the oxygen atom of the ethylene oxide-based oligomer or polymer and the cation in the electrolyte. The negatively charged redox derivatives are rearranged around the cation and through this, a Grotusus mechanism diffusion is carried out through an exchange reaction of the redox derivatives. This contributes to the improvement of the ionic conductivity of the electrolyte with faster diffusion than physical diffuion.
본 발명에 따른 산화-환원 유도체는 전해질에서 산화-환원 반응을 유도하는 작용체로서, 특별하게 한정되지 않는다. 산화-환원 유도체는 요오드 이온 또는 브롬 이온 등의 할로겐족 음이온 및 상대 금속 양이온으로 구성된다. 산화-환원 유도체로는 이에 제한되지는 않으나, 요오드화 리튬(LiI), 요오드화 나트륨(NaI), 요오드화 칼륨(KI), 브롬화 리튬(LiBr), 브롬화 나트륨(NaBr) 또는 브롬화 칼륨(KBr)의 할로겐화 알칼리 금속 및 DMPII(1,1-디메틸-3-프로필 이미다졸륨 요오드염), HMII(1-메틸-3-헥실 이미다졸륨 요오드염), EMII(1-에틸-3-메틸 이미다졸륨 요오드염) 또는 MBII(1-메틸-3-부틸 이미다졸륨 요오드염) 등의 이미다졸륨계 요오드염을 1종 이상 사용할 수 있다. 상기 산화-환원 유도체는 상기 대향 전극으로부터 전달받은 전자에 의해 산화-환원 반응을 수행하며, 그 전자를 기저 상태의 유기 염료에 전달함으로써 계속해서 전류가 발생하도록 한다.
The redox derivative according to the present invention is not particularly limited as an agent that induces a redox reaction in the electrolyte. The redox derivatives are composed of halogenated anions such as iodine ions or bromine ions and counter metal cations. Redox derivatives include, but are not limited to, halogenated alkalis of lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), lithium bromide (LiBr), sodium bromide (NaBr) or potassium bromide (KBr) Metals and DMPII (1,1-dimethyl-3-propyl imidazolium iodine salt), HMII (1-methyl-3-hexyl imidazolium iodine salt), EMII (1-ethyl-3-methyl imidazolium iodine salt) ) Or one or more kinds of imidazolium-based iodine salts such as MBII (1-methyl-3-butyl imidazolium iodine salt). The redox derivative performs the redox reaction by the electrons received from the counter electrode, and the current is continuously generated by transferring the electrons to the organic dye in the ground state.
본 발명의 염료감응 태양전지용 전해질은 상온에서 점도가 매우 큰 액체이거나 치환체에 따라 고체 상태로 존재할 수 있다. 따라서 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머와 산화-환원 유도체의 구성비를 적절히 조절하거나 각 다이아세틸렌 단량체의 중합정도를 조절하거나 에틸렌 옥사이드 계열 올리고머 또는 폴리머의 분자량을 조절하여 이온전도도 및 전해질의 점도를 조절 할 수 있는 것이 특징이다. 예를 들어 에틸렌 옥사이드 계열 올리고머 또는 폴리머의 분자량이 커질수록 점도가 커지고 분자량이작은 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 사용할 수록 전해질의 점도가 작아진다. 치환체와 상대이온간의 결합력, 에틸렌 옥사이드 계열의 올리고머 또는 폴리머에 있는 산소원자의 비공유 전자쌍과 전해질내의 양이온간의 이온결합력이 커짐에 따라 전해질의 점도를 크게 할 수 있다. 또는 반대의 경우도 가능하다.
The electrolyte for dye-sensitized solar cells of the present invention may be a liquid having a very high viscosity at room temperature or exist in a solid state depending on substituents. Therefore, the composition ratio of the diacetylene monomer and the ethylene oxide-based oligomer or polymer and the oxidation-reduction derivative substituted at both ends with imidazolium is properly adjusted, the degree of polymerization of each diacetylene monomer is adjusted or the molecular weight of the ethylene oxide-based oligomer or polymer is adjusted. It is characterized by the ability to adjust the ionic conductivity and the viscosity of the electrolyte by adjusting. For example, the higher the molecular weight of the ethylene oxide-based oligomer or polymer, the higher the viscosity, and the smaller the molecular weight of the ethylene oxide-based oligomer or polymer, the smaller the viscosity of the electrolyte. As the bonding force between the substituent and the counterion, the ionic bonding force between the unshared electron pair of the oxygen atom in the ethylene oxide-based oligomer or polymer and the cation in the electrolyte, the viscosity of the electrolyte can be increased. Or vice versa.
본 발명의 다른 구체예에 따르면, 염료감응 태양전지의 에너지 변환 효율을 효과적으로 증대시키기 위해 염기성 작용기를 포함하는 화합물, 바람직하게는 4-tert-부틸피리딘을 더 포함할 수 있다. 염기성 작용기를 포함하는 화합물은 전해질 속에 있는 전자 재결합을 잘하는 요오드와 반응하여 염을 생성함으로써 전자 재결합 속도를 줄여 태양전지의 에너지 변환 효율을 향상시킬 수 있다.
According to another embodiment of the present invention, a compound containing a basic functional group, preferably 4-tert-butylpyridine, may be further included to effectively increase the energy conversion efficiency of the dye-sensitized solar cell. Compounds containing basic functional groups can react with iodine, which is good at electron recombination in the electrolyte, to form salts, thereby reducing the rate of electron recombination, thereby improving the energy conversion efficiency of the solar cell.
본 발명의 또 다른 구체예에 따르면, 실리카 나노입자를 더 포함할 수 있다. 실리카 나노입자는 전해질을 안정화하여 고체화 속도를 증가시킬 수 있다.
According to another embodiment of the present invention, it may further comprise silica nanoparticles. Silica nanoparticles can stabilize the electrolyte and increase the rate of solidification.
또한, 본 발명은 본 발명의 염료감응 태양전지용 전해질이 적용된 염료감응 태양전지를 제공한다. 염료감응 태양전지를 구성하는 세부 구성의 기능, 재료, 구조 등과 함께 이의 제조방법 등은 특별히 한정되는 것은 아니며, 종래에 알려져 있는 것을 제한 없이 사용할 수 있다. The present invention also provides a dye-sensitized solar cell to which the electrolyte for dye-sensitized solar cells of the present invention is applied. The function, the material, the structure, and the like of the detailed configuration constituting the dye-sensitized solar cell are not particularly limited, and conventionally known ones can be used without limitation.
본 발명에 따른 광전극은 기판 위에 전도성 물질이 코팅된 투명전극, 염료가 흡착된 금속산화물로 구성되는 금속산화물층으로 구성된다. 본 발명의 광전극은 기판 위에 전도성 물질이 코팅되어 투명전극으로 형성된다. 상기 기판으로는 투명성을 갖고 있는 것이면 특별히 한정되지 않으며 석영 및 유리와 같은 투명 무기 기판 또는 폴리에틸렌테레프탈레이트 (PET; polyethylene terephthalate), 폴리에틸렌나프탈레이트(PEN; polyethylenenaphathalate), 폴리카보네이트, 폴리스티렌, 폴리프로필렌 등의 투명 플라스틱 기판을 사용할 수 있다. 또한, 상기 기판 상에 코팅되는 전도성 물질로는 인듐틴 옥사이드(ITO), 플로린 도핑된 틴 옥사이드(FTO), ZnOGa2O3,ZnO-Al2O3, SnO2-Sb2O3 등을 예로 들 수 있으나, 반드시 이들로 제한되는 것은 아니다. The photoelectrode according to the present invention includes a transparent electrode coated with a conductive material on a substrate, and a metal oxide layer composed of a metal oxide adsorbed with a dye. In the photoelectrode of the present invention, a conductive material is coated on a substrate to form a transparent electrode. The substrate is not particularly limited as long as it has transparency, and transparent inorganic substrates such as quartz and glass or polyethylene terephthalate (PET), polyethylenenaphathalate (PEN), polycarbonate, polystyrene, polypropylene, etc. A transparent plastic substrate can be used. In addition, examples of the conductive material coated on the substrate include indium tin oxide (ITO), florine doped tin oxide (FTO), ZnOGa 2 O 3 , ZnO-Al 2 O 3 , SnO 2 -Sb 2 O 3 , and the like. But it is not necessarily limited thereto.
본 발명의 광전극에서 금속산화물층은 금속산화물과 금속산화물의 표면에 흡착된 염료로 구성된다. 이러한 금속산화물층은 염료감응 태양전지 작동에서 고효율을 얻기 위해서 태양광 에너지를 최대한 많이 흡수하여야 하므로, 다공성의 금속산화물을 사용하여 표면적을 증대시켜 그 내부에 보다 많은 염료를 흡착시킨다. 상기 금속산화물은 예를 들어 티타늄산화물, 텅스텐 산화물, 니오븀 산화물, 하프늄 산화물, 인듐 산화물, 주석 산화물 및 아연 산화물로 이루어진 군에서 선택된 하나 이상을 사용할 수 있으나, 반드시 이들로 제한되는 것은 아니다. 상기 금속산화물들은 단독으로 사용되거나 또는 2가지 또는 그 이상을 혼합하여 사용할 수 있다. 바람직한 금속산화물의 예로는 TiO2, SnO2, ZnO, WO3, Nb2O5, TiSrO3 등을 들 수 있고, 특히 아나타제형(anatase)의 TiO2가 좋다.In the photoelectrode of the present invention, the metal oxide layer is composed of a metal oxide and a dye adsorbed on the surface of the metal oxide. Since the metal oxide layer must absorb as much solar energy as possible in order to obtain high efficiency in dye-sensitized solar cell operation, porous metal oxide is used to increase the surface area to adsorb more dye therein. The metal oxide may be, for example, one or more selected from the group consisting of titanium oxide, tungsten oxide, niobium oxide, hafnium oxide, indium oxide, tin oxide and zinc oxide, but is not necessarily limited thereto. The metal oxides may be used alone or in combination of two or more thereof. Examples of preferred metal oxides include TiO 2 , SnO 2 , ZnO, WO 3 , Nb 2 O 5 , TiSrO 3 , and the like, and in particular, anatase TiO 2 is preferable.
본 발명에서 염료로서는 태양전지 분야에서 일반적으로 사용되는 것이라면 아무 제한 없이 사용할 수 있으나, 루테늄 착물이 바람직하다. 전하 분리기능을 갖고 광감응 작용을 나타내는 것이면 특별히 한정되지 않으며, 루테늄 착물 이외에도 로다민 B, 로즈벤갈, 에오신, 에리스로신 등의 크산틴계 염료, 퀴노시아닌, 크립토시아닌 등의 시아닌계 염료, 페노사프라닌, 카르비블루, 티오신, 메틸렌블루 등의 염기성 염료, 클로로필, 아연 포르피린, 마그네슘 포르피린 등의 포르피린계 화합물, 기타 아조 염료, 프탈로시아닌 화합물, 루테늄 트리스비피리딜 등의 착화합물, 안트라퀴논계 염료, 다환퀴논계 염료 등을 들 수 있다. 그러나 반드시 이들로 제한되는 것은 아니다. 상기 염료는 단독으로 사용되거나 또는 2가지 또는 그 이상을 혼합하여 사용할 수 있다. 상기 루테늄 착물로서는 RuL2(SCN)2, RuL2(H2O)2, RuL3, RuL2 등을 사용할 수 있다(식 중,L은 2,2'-비피리딜-4,4'-디카르복실레이트 등을 나타낸다).In the present invention, if the dye is generally used in the solar cell field can be used without any limitation, ruthenium complex is preferred. It is not particularly limited as long as it has a charge separation function and exhibits photosensitivity. In addition to the ruthenium complex, xanthine-based dyes such as rhodamine B, rosebengal, eosin, and erythrosine, cyanine-based dyes such as quinocyanine and cryptocyanine, Basic dyes such as nosapranin, carbiblue, thiocin and methylene blue, porphyrin compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, other azo dyes, phthalocyanine compounds, complexes such as ruthenium trisbipyridyl, and anthraquinones And dyes and polycyclic quinone dyes. However, it is not necessarily limited to these. The dyes may be used alone or in combination of two or more thereof. As the ruthenium complex, RuL 2 (SCN) 2 , RuL 2 (H 2 O) 2 , RuL 3 , RuL 2 , and the like can be used (wherein L is 2,2′-bipyridyl-4,4′-). Dicarboxylate and the like).
본 발명에서 대향전극은 도전성 물질이면 어느 것이나 사용가능하다. 또 절연성 물질이라도 투명전극에 마주보고 있는 측에 도전층이 설치되어 있으면 이것도 사용 가능하다. 단, 전극으로서 바람직하게 사용하려면 전기화학적으로 안정한 재료를 선택하는 것이 중요하며, 구체적으로는 백금, 금 및 카본, 카본 나노튜브, 그래파이트, 그래핀 등을 사용하는 것이 바람직하다. 또한, 투명전극과 마주보고 있는 측은 미세구조로 표면적이 증대될 시 산화환원의 촉매 효과를 향상시킬 수 있는 바람직한 방법이며, 특히 백금이면 백금흑 상태로, 카본이면 다공질 상태로 되어 있는 것이 바람직하다.In the present invention, any counter electrode may be used as long as it is a conductive material. Moreover, even if it is an insulating substance, if a conductive layer is provided in the side facing a transparent electrode, this can also be used. However, in order to use preferably as an electrode, it is important to select an electrochemically stable material, and it is preferable to specifically use platinum, gold, and carbon, carbon nanotubes, graphite, graphene, etc. In addition, the side facing the transparent electrode is a preferred method for improving the catalytic effect of the redox when the surface area is increased due to the microstructure, in particular, it is preferable that the platinum is in the platinum black state, and the carbon is in the porous state.
본 발명의 염료감응 태양전지는 다음과 같이 동작한다. 투명전극을 투과하여 금속산화물층에 도달한 빛을 금속산화물층의 표면에 흡착된 염료가 그 빛을 흡수한다. 이에 염료는 광을 흡수함으로써 기저상태에서 여기 상태로 전자 전이하고 여기된 전자는 전자-홀 쌍을 이루게 되며, 여기 상태의 전자는 상기 금속산화물의 전도대로 주입된 후 전극으로 이동하여 기전력을 발생시킨다. 염료에서 광여기되어 생성된 전자가 금속산화물의 전도대로 이동하면, 전자를 잃은 염료는 전해질층의 홀 전달 물질로부터 전자를 제공받고 원래의 기저 상태로 복원되면서 염료감응 태양전지의 사이클이 완성된다.
The dye-sensitized solar cell of the present invention operates as follows. Dye adsorbed on the surface of the metal oxide layer absorbs the light that has passed through the transparent electrode and reaches the metal oxide layer. The dye thus absorbs light, which causes electron transition from the ground state to the excited state, and the excited electrons form an electron-hole pair, and the excited state is injected into the conduction band of the metal oxide and then moves to the electrode to generate an electromotive force. . When the electrons generated by photo-excitation in the dye move to the conduction band of the metal oxide, the dye-lost dye receives electrons from the hole transport material of the electrolyte layer and is restored to its original ground state, thereby completing the cycle of the dye-sensitized solar cell.
또한, 본 발명은 (S1) 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 혼합하여 균일 용액을 제조하는 단계; (S2) 상기 균일 용액에 자외선 노광하여 폴리다이아세틸렌 혼합 용액을 제조하는 단계; 및 (S3) 상기 폴리다이아세틸렌 혼합 용액에 산화-환원 유도체를 첨가하는 단계를 포함하는 염료감응 태양전지용 전해질의 제조방법을 제공한다.
In addition, the present invention (S1) is a step of preparing a uniform solution by mixing a diacetylene monomer and ethylene oxide-based oligomer or polymer substituted at both ends with imidazolium; (S2) ultraviolet exposure to the homogeneous solution to prepare a polydiacetylene mixed solution; And (S3) provides a method for producing a dye-sensitized solar cell electrolyte comprising the step of adding an oxidation-reduction derivative to the polydiacetylene mixed solution.
S1 단계에서는, 양 말단이 이미다졸륨으로 치환된 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 혼합하여 균일 용액을 제조하는 것을 특징으로 한다. 이때, 본 발명의 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 1:1000 내지 1:1의 중량비로 물리적으로 혼합하는 것이 바람직한 데, 상기 중량비의 범위 내에서 양 말단이 이미다졸륨으로 치환된 다이아세틸렌을 중합시켜 제조한 폴리다이아세틸렌 주쇄를 따라 양 말단이 이미다졸륨의 이온성 치환기가 배열되기 때문에 배열된 치환 구조에 따라 산화-환원 유도체가 배열되어 생성된 이온채널(ion-channel)을 통해 높은 이온전도도를 제공할 수 있기 때문이다. 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 과하게 첨가할 시 상기전해질이 가지는 폴리다이아세틸렌의 이온채널에 의한 그로터스 매커니즘 확산을 통한 이온전도도의 향상 기여도가 줄어들게 된다. 반대로 폴리다이아세틸렌의 비율이 과할때는 전해질 점도의 향상으로 에틸렌 옥사이드 계열 올리고머 또는 폴리머에 의한 물리적 확산의 기여도가 줄어들어 전체적인 이온전도도가 떨어 질 수 있다. 따라서 적절한 비율인 1:1000 내지 1:1의 중량비로 혼합하여야 한다.
In the step S1, it is characterized in that a homogeneous solution is prepared by mixing a diacetylene monomer substituted at both ends with imidazolium and an ethylene oxide-based oligomer or polymer. In this case, it is preferable to physically mix the diacetylene monomer and the ethylene oxide-based oligomer or polymer of the present invention in a weight ratio of 1: 1000 to 1: 1, and both ends of the die substituted with imidazolium within the weight ratio range Since the ionic substituents of imidazolium are arranged at both ends along the polydiacetylene backbone prepared by polymerizing acetylene, redox derivatives are arranged according to the substitution structure arranged through ion-channels. This is because high ion conductivity can be provided. When the ethylene oxide-based oligomer or polymer is added excessively, the contribution of the ion conductivity through the diffusion of the grotus mechanism by the ion channel of the polydiacetylene of the electrolyte is reduced. On the contrary, when the ratio of polydiacetylene is excessive, the contribution of physical diffusion by the ethylene oxide-based oligomer or polymer may be reduced due to the improvement of the electrolyte viscosity, thereby reducing the overall ionic conductivity. Therefore, it should be mixed in a weight ratio of 1: 1000 to 1: 1, which is an appropriate ratio.
본 발명의 다이아세틸렌 단량체는 하기 화학식 1로 표시될 수 있으나, 반드시 이에 한정되는 것은 아니다. The diacetylene monomer of the present invention may be represented by the following Chemical Formula 1, but is not necessarily limited thereto.
[화학식 1][Formula 1]
A-(CH2)c-(L1)d-(CH2)e-C≡C-C≡C-(CH2)f-(L2)g-(CH2)h-BA- (CH 2 ) c- (L 1 ) d- (CH 2 ) e -C≡CC≡C- (CH 2 ) f- (L 2 ) g- (CH 2 ) h -B
상기 화학식 1에서, In Formula 1,
A 및 B는 서로 동일하거나 상이한 이미다졸륨이고, 상기 이미다졸륨은 이미다졸 고리의 1번 질소가 주쇄의 탄소와 결합되고, 3번 질소 위치에서 알킬기로 치환되며, 상기 알킬기는 탄소 수가 1 내지 5의 선형 또는 분지형 탄화수소로서 C1 -10 알킬기, 할로겐, 히드록시기, 니트로기, 아미노기, 시아노기, C1 -10 알콕시기, 아미디노기, 히드라진기 또는 카르복실기로 치환될 수 있고, A and B are the same or different imidazolium from each other, wherein the imidazolium is the nitrogen of the imidazole ring bonded to the carbon of the main chain and substituted with an alkyl group at the nitrogen position of 3, wherein the alkyl group has 1 to a linear or branched hydrocarbon of 5 may be substituted by C 1 -10 alkyl group, a halogen, a hydroxy group, a nitro group, an amino group, a cyano group, C 1 -10 alkoxy group, amidino group, a hydrazine group or a carboxyl group,
c+e 및 f+h는 8 내지 50의 정수이고 서로 동일하거나 상이하고,c + e and f + h are integers from 8 to 50, the same as or different from each other,
L1 및 L2는 하나 이상의 에틸렌 옥사이드기, 아민기, 카르복닐기, 에스테르기, 우레탄기 또는 요소기이고 서로 동일하거나 상이하고, L 1 and L 2 are at least one ethylene oxide group, amine group, carboxyl group, ester group, urethane group or urea group and are the same as or different from each other,
d 및 g는 0 내지 20이고 서로 동일하거나 상이하다.
d and g are 0 to 20 and are the same as or different from each other.
본 발명의 에틸렌 옥사이드 계열 올리고머 또는 폴리머는 분자량이 200 내지 8000 g/mol의, 폴리에틸렌글라이콜, 폴리에틸렌-모노메틸렌 에테르, 폴리에틸렌-다이메틸렌 에테르, 폴리에틸렌-모노에틸렌 에테르, 폴리에틸렌- 다이에틸렌 에테르 등을 사용할 수 있으나 반드시 이에 한정되는 것은 아니다. 특히 바람직하게는 폴리에틸렌 글리콜-다이메틸렌 에테르를 사용할 수 있다. Ethylene oxide-based oligomers or polymers of the present invention include polyethylene glycol, polyethylene-monomethylene ether, polyethylene-dimethylene ether, polyethylene-monoethylene ether, polyethylene-diethylene ether, etc., having a molecular weight of 200 to 8000 g / mol. Can be used, but is not necessarily limited thereto. Particular preference is given to using polyethylene glycol-dimethylene ethers.
S2 단계에서는, S1 단계에서 제조한 균일 용액에 자외선 노광하여 폴리다이아세틸렌 혼합 용액을 제조하는 것을 특징으로 한다. 자외선 노광에 의해 본 발명의 다이아세틸렌 단량체가 중합되어 폴리다이아세틸렌이 형성된 폴리아세틸렌 혼합 용액이 제조된다. 즉, 폴리다이아세틸렌 혼합 용액에는 폴리다이아세틸렌과 본 발명의 에틸렌 옥사이드 계열 올리고머 또는 폴리머가 포함된다. 이때, 자외선 노광은 220~300㎚, 바람직하게는 254 ㎚의 자외선을 1분 내지 5분간 조사하여 수행하는 것이 바람직하다.
In step S2, the polydiacetylene mixed solution is prepared by ultraviolet exposure to the uniform solution prepared in step S1. The ultraviolet light exposure polymerizes the diacetylene monomer of this invention, and the polyacetylene mixed solution in which polydiacetylene was formed is manufactured. That is, the polydiacetylene mixed solution includes polydiacetylene and the ethylene oxide-based oligomer or polymer of the present invention. In this case, the ultraviolet exposure is preferably performed by irradiating the ultraviolet light of 220 ~ 300nm, preferably 254nm for 1 minute to 5 minutes.
S3 단계에서는, S2 단계에서 제조된 폴리다이아세틸렌 혼합 용액에 산화-환원 유도체를 첨가한다. 본 단계에서 사용되는 산화-환원 유도체는 상기 정의한 바와 같고, 특히 바람직하게는 요오드화 리튬, 요오드화 나트륨, 요오드화 칼륨, 브롬화 리튬, 브롬화 나트륨, 브롬화 칼륨, DMPII(1,1-디메틸-3-프로필 이미다졸륨 요오드염), HMII(1-메틸-3-헥실 이미다졸륨 요오드염), EMII(1-에틸-3-메틸 이미다졸륨 요오드염) 및 MBII(1-메틸-3-부틸 이미다졸륨 요오드염)으로 이루어지는 군으로부터 선택되는 것을 사용할 수 있다.
In step S3, the redox derivative is added to the polydiacetylene mixed solution prepared in step S2. The redox derivatives used in this step are as defined above, particularly preferably lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, DMPII (1,1-dimethyl-3-propyl imida) Zolium iodide salt), HMII (1-methyl-3-hexyl imidazolium iodide salt), EMII (1-ethyl-3-methyl imidazolium iodide salt) and MBII (1-methyl-3-butyl imidazolium iodine Salts) can be used.
이하, 실시예를 통해 본 발명을 구체적으로 설명하지만, 이러한 실시예는 본 발명을 좀 더 명확하게 이해하기 위하여 제시되는 것일 뿐 본 발명의 범위를 제한하는 목적으로 제시하는 것은 아니며, 본 발명은 후술하는 특허청구범위의 기술적 사상의 범위 내에서 정해질 것이다.
Hereinafter, the present invention will be described in detail with reference to examples, but these examples are only presented to more clearly understand the present invention, and are not intended to limit the scope of the present invention. It will be determined within the scope of the technical spirit of the claims.
실시예Example
본 발명의 다이아세틸렌 단량체 중 상기 화학식의 화합물(DCDDA-imidazolium iodide) 0.33g(0.000386몰)을 폴리에틸렌글리콜-다이메틸렌에테르(Mn～500, 1.00 g(0.00182몰)와 혼합하여 균일한 용액을 제조한 뒤, 자외선을 노광하여 폴리아세틸렌 혼합 용액을 제조하였다. 상기 제조된 용액에 1-메틸-3-프로필 이미다졸륨 요오드(MPII) 0.0458g(0.000182몰)과 요오드(I2) 0.00462g(0.0000182몰)을 넣고, 12시간 교반하여 균일한 혼합물을 만들었다. 다음으로, 염료(제조원:Swiss, solaronix사 N719)를 tert-부탄올 및 아세토니트릴 혼합용매에 녹인 용액에 불소가 첨가된 인듐옥사이드(FTO) 기판 위에 산화티타늄(TiO2) 전도성 물질이 코팅된 투명 전극을 24시간 담궈 흡착시키고 백금으로로 구성된 대향 전극을 결합한 뒤 그사이에 제조된 전해질을 60℃로 올려 주입하고, 전해질 침투시간을 유지한 후 다시 상온으로 내려 염료감응 태양전지를 제조하였다.
0.33 g (0.000386 mol) of the compound of the above formula (DCDDA-imidazolium iodide) in the diacetylene monomer of the present invention is mixed with polyethylene glycol dimethyl ether (M n ~ 500, 1.00 g (0.00182 mol) to prepare a uniform solution The mixture was then exposed to UV light to prepare a mixed solution of polyacetylene, in which 0.0458 g (0.000182 mol) of 1-methyl-3-propyl imidazolium iodine (MPII) and 0.00462 g (0.0000182) of iodine (I 2 ) were prepared. Mole), and stirred for 12 hours to form a uniform mixture Next, indium oxide (FTO) in which fluorine was added to a solution obtained by dissolving a dye (manufactured by Swiss, solaronix N719) in a tert-butanol and acetonitrile mixed solvent The transparent electrode coated with titanium oxide (TiO 2 ) conductive material was immersed on the substrate for 24 hours to adsorb, and the opposing electrode composed of platinum was combined, and the electrolyte prepared therebetween was injected at 60 ° C. to maintain the electrolyte penetration time. Then back to room temperature to prepare a dye-sensitized solar cell.
실시예에서 제조한 소자의 광전효율을 측정하기 위해 광전압 및 광전류를 측정하였다. 광원으로는 제논램프(Xenon lamp, Oriel, 01193)를 사용하였으며, 상기 제논 램프의 태양 조건(AM 1.5)은 표준 태양 전지(Furnhofer Institute Solare Engeriessysteme, Certificate No. C-ISE369, Type of material: Mono-Si + KG필터)를 사용하여 보정하였다. 측정된 광전류-전압의 상관관계 곡선을 도 1에 나타내었으며, 상기 곡선으로부터 계산된 단락전류밀도(Jsc, short-circuit current density), 개방전압(Voc, open-circuit voltage) 및 충진 계수(fill factor, FF)를 하기 광전환 효율 계산식을 통해 계산한 광전 효율(ηe)을 측정하였다.In order to measure the photoelectric efficiency of the device manufactured in Example, the photovoltage and photocurrent were measured. Xenon lamp (Oriel, 01193) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was a standard solar cell (Furnhofer Institute Solare Engeriessysteme, Certificate No. C-ISE369, Type of material: Mono-). Si + KG filter). The correlation curve of the measured photocurrent-voltage is shown in FIG. 1, and the short-circuit current density (Jsc), the open-circuit voltage (Voc) and the fill factor calculated from the curve are shown. , FF) was measured by the following light conversion efficiency calculation formula photoelectric efficiency (η e ).
ηe = (Voc·Isc·FF)/(Pinc)η e = (VocIsc · FF) / (P inc )
상기 식에서, Pin 는 100mW/cm2 (1sun)을 나타낸다.In the above formula, P in represents 100 mW / cm 2 (1 sun).
도 1에 나타난 바와 같이, 실시예의 태양전지는 11.6mA cm-2의 단락전류밀도(Jsc), 0.63V의 개방전압(Voc) 및 59.6%의 충진계수를 가지며, 이로부터 4.37%의 광변환 효율을 얻음으로써 준고체 전해질 분야에서 향상된 에너지 변환 효율을 가지고 있음을 알 수 있다.
As shown in FIG. 1, the solar cell of the embodiment has a short-circuit current density (Jsc) of 11.6 mA cm −2 , an open voltage (Voc) of 0.63 V, and a filling factor of 59.6%, from which the light conversion efficiency is 4.37%. It can be seen that has an improved energy conversion efficiency in the field of semi-solid electrolyte.
Claims (17)
에틸렌 옥사이드 계열 올리고머 또는 폴리머; 및
산화-환원 유도체를 포함하는 염료감응 태양전지용 전해질.Polydiacetylene polymerized with a diacetylene monomer substituted at both terminals with imidazolium;
Ethylene oxide based oligomers or polymers; And
Electrolyte for dye-sensitized solar cell comprising redox derivative.
상기 다이아세틸렌 단량체는 하기 화학식 1로 표시되는 다이아세틸렌 단량체인 것을 특징으로 하는 염료감응 태양전지용 전해질.
[화학식 1]
A-(CH2)c-(L1)d-(CH2)e-C≡C-C≡C-(CH2)f-(L2)g-(CH2)h-B
상기 화학식 1에서,
A 및 B는 서로 동일하거나 상이한 이미다졸륨이고, 상기 이미다졸륨은 이미다졸 고리의 1번 질소가 주쇄의 탄소와 결합되고, 3번 질소 위치에서 알킬기로 치환되며, 상기 알킬기는 탄소 수가 1 내지 5의 선형 또는 분지형 탄화수소로서, C1 -10 알킬기, 할로겐, 히드록시기, 니트로기, 아미노기, 시아노기, C1 -10 알콕시기, 아미디노기, 히드라진기 또는 카르복실기로 치환될 수 있고,
c+e 및 f+h는 8 내지 50의 정수이고 서로 동일하거나 상이하고,
L1 및 L2는 하나 이상의 에틸렌 옥사이드기, 아민기, 카르보닐기, 에스테르기, 우레탄기 또는 요소기이고 서로 동일하거나 상이하고,
d 및 g는 0 내지 20이고 서로 동일하거나 상이하다.The method of claim 1,
The diacetylene monomer is a dye-sensitized solar cell electrolyte, characterized in that the diacetylene monomer represented by the formula (1).
[Formula 1]
A- (CH 2 ) c- (L 1 ) d- (CH 2 ) e -C≡CC≡C- (CH 2 ) f- (L 2 ) g- (CH 2 ) h -B
In Chemical Formula 1,
A and B are the same or different imidazolium from each other, wherein the imidazolium is the nitrogen of the imidazole ring bonded to the carbon of the main chain and substituted with an alkyl group at the nitrogen position of 3, wherein the alkyl group has 1 to a linear or branched hydrocarbon group of 5, and may be substituted with a C 1 -10 alkyl group, a halogen, a hydroxy group, a nitro group, an amino group, a cyano group, C 1 -10 alkoxy group, amidino group, a hydrazine group or a carboxyl group,
c + e and f + h are integers from 8 to 50, the same as or different from each other,
L 1 and L 2 are at least one ethylene oxide group, amine group, carbonyl group, ester group, urethane group or urea group and are the same as or different from each other,
d and g are 0 to 20 and are the same as or different from each other.
상기 에틸렌 옥사이드 계열 올리고머 또는 폴리머는 분자량이 200 내지 8000 g/mol의, 폴리에틸렌글라이콜, 폴리에틸렌-모노메틸렌 에테르, 폴리에틸렌-다이메틸렌 에테르, 폴리에틸렌-모노에틸렌 에테르, 또는 폴리에틸렌- 다이에틸렌 에테르인 것을 특징으로 하는 염료감응 태양전지용 전해질.The method of claim 1,
The ethylene oxide-based oligomer or polymer is characterized in that the molecular weight of 200 to 8000 g / mol, polyethylene glycol, polyethylene- monomethylene ether, polyethylene- dimethylene ether, polyethylene- monoethylene ether, or polyethylene- diethylene ether Dye-sensitized solar cell electrolyte.
상기 산화-환원 유도체는 요오드화 리튬, 요오드화 나트륨, 요오드화 칼륨, 브롬화 리튬, 브롬화 나트륨, 브롬화 칼륨, DMPII(1,1-디메틸-3-프로필 이미다졸륨 요오드염), HMII(1-메틸-3-헥실 이미다졸륨 요오드염), EMII(1-에틸-3-메틸 이미다졸륨 요오드염) 및 MBII(1-메틸-3-부틸 이미다졸륨 요오드염)로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 염료감응 태양전지용 전해질.The method of claim 1,
The redox derivatives include lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, DMPII (1,1-dimethyl-3-propyl imidazolium iodide), HMII (1-methyl-3- Dye selected from the group consisting of hexyl imidazolium iodide salt), EMII (1-ethyl-3-methyl imidazolium iodide salt) and MBII (1-methyl-3-butyl imidazolium iodide salt) Electrolyte for sensitized solar cell.
상기 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 1:1000 내지 1:1의 중량비로 혼합시킨 것을 특징으로 하는 염료감응 태양전지용 전해질.The method according to claim 1 or 2,
The dye-sensitized solar cell electrolyte, characterized in that the diacetylene monomer and ethylene oxide-based oligomer or polymer is mixed in a weight ratio of 1: 1000 to 1: 1.
염기성 작용기를 포함하는 화합물을 더 포함하는 것을 특징으로 하는 염료감응 태양전지용 전해질.The method of claim 1,
An electrolyte for dye-sensitized solar cells, further comprising a compound containing a basic functional group.
상기 염기성 작용기를 포함하는 화합물이 4-tert-부틸피리딘인 것을 특징으로 하는 염료감응 태양전지용 전해질.The method according to claim 6,
The dye-sensitized solar cell electrolyte, characterized in that the compound containing the basic functional group is 4-tert-butylpyridine.
실리카 나노입자를 더 포함하는 것을 특징으로 하는 염료감응 태양전지용 전해질.The method of claim 1,
An electrolyte for dye-sensitized solar cells, further comprising silica nanoparticles.
대향전극; 및
상기 광전극과 대향전극 사이에 제1항의 염료감응 태양전지용 전해질을 포함하는 염료감응 태양전지. Photoelectrode;
Counter electrode; And
A dye-sensitized solar cell comprising the dye-sensitized solar cell electrolyte of claim 1 between the photoelectrode and the counter electrode.
(S2) 상기 균일 용액에 자외선 노광하여 폴리다이아세틸렌 혼합 용액을 제조하는 단계; 및
(S3) 상기 폴리다이아세틸렌 혼합 용액에 산화-환원 유도체를 첨가하는 단계
를 포함하는 염료감응 태양전지용 전해질의 제조방법.(S1) preparing a homogeneous solution by mixing a diacetylene monomer substituted at both terminals with imidazolium and an ethylene oxide-based oligomer or polymer;
(S2) ultraviolet exposure to the homogeneous solution to prepare a polydiacetylene mixed solution; And
(S3) adding a redox derivative to the polydiacetylene mixed solution
Method for producing a dye-sensitized solar cell electrolyte comprising a.
S1 단계에서, 상기 다이아세틸렌 단량체는 하기 화학식 1로 표시되는 다이아세틸렌 단량체인 것을 특징으로 하는 염료감응 태양전지용 전해질의 제조방법.
[화학식 1]
A-(CH2)c-(L1)d-(CH2)e-C≡C-C≡C-(CH2)f-(L2)g-(CH2)h-B
상기 화학식 1에서,
A 및 B는 서로 동일하거나 상이한 이미다졸륨이고, 상기 이미다졸륨은 이미다졸 고리의 1번 질소가 주쇄의 탄소와 결합되고, 3번 질소 위치에서 알킬기로 치환되며, 상기 알킬기는 탄소 수가 1 내지 5의 선형 또는 분지형 탄화수소로서 C1 -10 알킬기, 할로겐, 히드록시기, 니트로기, 아미노기, 시아노기, C1 -10 알콕시기, 아미디노기, 히드라진기 또는 카르복실기로 치환될 수 있고,
c+e 및 f+h는 8 내지 50의 정수이고 서로 동일하거나 상이하고,
L1 및 L2는 하나 이상의 에틸렌 옥사이드기, 아민기, 카르복닐기, 에스테르기, 우레탄기 또는 요소기이고 서로 동일하거나 상이하고,
d 및 g는 0 내지 20이고 서로 동일하거나 상이하다.The method of claim 10,
In step S1, the diacetylene monomer is a dye-sensitized solar cell electrolyte production method, characterized in that the diacetylene monomer represented by the formula (1).
[Formula 1]
A- (CH 2 ) c- (L 1 ) d- (CH 2 ) e -C≡CC≡C- (CH 2 ) f- (L 2 ) g- (CH 2 ) h -B
In Chemical Formula 1,
A and B are the same or different imidazolium from each other, wherein the imidazolium is the nitrogen of the imidazole ring bonded to the carbon of the main chain and substituted with an alkyl group at the nitrogen position of 3, wherein the alkyl group has 1 to a linear or branched hydrocarbon of 5 may be substituted by C 1 -10 alkyl group, a halogen, a hydroxy group, a nitro group, an amino group, a cyano group, C 1 -10 alkoxy group, amidino group, a hydrazine group or a carboxyl group,
c + e and f + h are integers from 8 to 50, the same as or different from each other,
L 1 and L 2 are at least one ethylene oxide group, amine group, carboxyl group, ester group, urethane group or urea group and are the same as or different from each other,
d and g are 0 to 20 and are the same as or different from each other.
S1 단계에서, 상기 에틸렌 옥사이드 계열 올리고머 또는 폴리머는 분자량이 200 내지 8000 g/mol의, 폴리에틸렌글라이콜, 폴리에틸렌-모노메틸렌 에테르, 폴리에틸렌-다이메틸렌 에테르, 폴리에틸렌-모노에틸렌 에테르, 또는 폴리에틸렌- 다이에틸렌 에테르인 것을 특징으로 하는 염료감응 태양전지용 전해질의 제조방법.The method of claim 10,
In step S1, the ethylene oxide-based oligomer or polymer has a molecular weight of 200 to 8000 g / mol, polyethylene glycol, polyethylene- monomethylene ether, polyethylene- dimethylene ether, polyethylene- monoethylene ether, or polyethylene- diethylene A method for producing an electrolyte for dye-sensitized solar cells, characterized in that the ether.
상기 S1 단계에서, 다이아세틸렌 단량체와 에틸렌 옥사이드 계열 올리고머 또는 폴리머를 1:1000 내지 1:1의 중량비로 혼합하는 것을 특징으로 하는 염료감응 태양전지용 전해질의 제조방법.The method of claim 10,
In the step S1, the method for producing a dye-sensitized solar cell electrolyte, characterized in that the diacetylene monomer and ethylene oxide-based oligomer or polymer is mixed in a weight ratio of 1: 1000 to 1: 1.
상기 S2 단계에서, 자외선 노광은 220~300㎚의 자외선을 1분 내지 5분간 조사하여 수행하는 것을 특징으로 하는 염료감응 태양전지용 전해질의 제조방법.The method of claim 10,
In the step S2, the ultraviolet exposure is a method for producing a dye-sensitized solar cell electrolyte, characterized in that carried out by irradiating ultraviolet light of 220 ~ 300nm for 1 minute to 5 minutes.
상기 S3 단계에서, 산화-환원 유도체는 요오드화 리튬, 요오드화 나트륨, 요오드화 칼륨, 브롬화 리튬, 브롬화 나트륨, 브롬화 칼륨, DMPII(1,1-디메틸-3-프로필 이미다졸륨 요오드염), HMII(1-메틸-3-헥실 이미다졸륨 요오드염), EMII(1-에틸-3-메틸 이미다졸륨 요오드염) 및 MBII(1-메틸-3-부틸 이미다졸륨 요오드염)로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 염료감응 태양전지용 전해질의 제조방법.The method of claim 10,
In the step S3, the redox derivative is lithium iodide, sodium iodide, potassium iodide, lithium bromide, sodium bromide, potassium bromide, DMPII (1,1-dimethyl-3-propyl imidazolium iodide), HMII (1- Methyl-3-hexyl imidazolium iodide salt), EMII (1-ethyl-3-methyl imidazolium iodide salt) and MBII (1-methyl-3-butyl imidazolium iodide salt) Method for producing a dye-sensitized solar cell electrolyte characterized in that.
[화학식 1]
A-(CH2)c-(L1)d-(CH2)e-C≡C-C≡C-(CH2)f-(L2)g-(CH2)h-B
상기 화학식 1에서,
A 및 B는 서로 동일하거나 상이한 이미다졸륨이고, 상기 이미다졸륨은 이미다졸 고리의 1번 질소가 주쇄의 탄소와 결합되고, 3번 질소 위치에서 알킬기로 치환되며, 상기 알킬기는 탄소 수가 1 내지 5의 선형 또는 분지형 탄화수소로서, C1 -10 알킬기, 할로겐, 히드록시기, 니트로기, 아미노기, 시아노기, C1 -10 알콕시기, 아미디노기, 히드라진기 또는 카르복실기로 치환될 수 있고,
c+e 및 f+h는 8 내지 50의 정수이고 서로 동일하거나 상이하고,
L1 및 L2는 하나 이상의 에틸렌 옥사이드기, 아민기, 카르보닐기, 에스테르기, 우레탄기 또는 요소기이고 서로 동일하거나 상이하고,
d 및 g는 0 내지 20이고 서로 동일하거나 상이하다.Diacetylene monomer represented by the following formula (1).
[Formula 1]
A- (CH 2 ) c- (L 1 ) d- (CH 2 ) e -C≡CC≡C- (CH 2 ) f- (L 2 ) g- (CH 2 ) h -B
In Chemical Formula 1,
A and B are the same or different imidazolium from each other, wherein the imidazolium is the nitrogen of the imidazole ring bonded to the carbon of the main chain and substituted with an alkyl group at the nitrogen position of 3, wherein the alkyl group has 1 to a linear or branched hydrocarbon group of 5, and may be substituted with a C 1 -10 alkyl group, a halogen, a hydroxy group, a nitro group, an amino group, a cyano group, C 1 -10 alkoxy group, amidino group, a hydrazine group or a carboxyl group,
c + e and f + h are integers from 8 to 50, the same as or different from each other,
L 1 and L 2 are at least one ethylene oxide group, amine group, carbonyl group, ester group, urethane group or urea group and are the same as or different from each other,
d and g are 0 to 20 and are the same as or different from each other.
상기 화학식 2로 표시되는 것을 특징으로 하는 다이아세틸렌 단량체.
[화학식 2]
Diacetylene monomer, characterized in that represented by the formula (2).
(2)
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