WO2011115319A1 - 염료감응태양전지용 고분자전해질 및 이를 이용한 염료감응태양전지의 제조방법 - Google Patents
염료감응태양전지용 고분자전해질 및 이를 이용한 염료감응태양전지의 제조방법 Download PDFInfo
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- WO2011115319A1 WO2011115319A1 PCT/KR2010/001751 KR2010001751W WO2011115319A1 WO 2011115319 A1 WO2011115319 A1 WO 2011115319A1 KR 2010001751 W KR2010001751 W KR 2010001751W WO 2011115319 A1 WO2011115319 A1 WO 2011115319A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dye
- sensitized solar
- polymer electrolyte
- solar cells
- solar cell
- Prior art date
Links
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 239000000975 dye Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 16
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
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- 239000002105 nanoparticle Substances 0.000 description 11
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- 238000011161 development Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 229930003836 cresol Natural products 0.000 description 4
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 235000009518 sodium iodide Nutrition 0.000 description 2
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- CZSRXHJVZUBEGW-UHFFFAOYSA-N 1,2-thiazolidine Chemical class C1CNSC1 CZSRXHJVZUBEGW-UHFFFAOYSA-N 0.000 description 1
- JDLHQBAZAFNBPQ-UHFFFAOYSA-N 2-benzyl-5-methyl-1h-imidazole Chemical compound CC1=CNC(CC=2C=CC=CC=2)=N1 JDLHQBAZAFNBPQ-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- DJIHQRBJGCGSIR-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane-4,7-dione Chemical compound C1(CCC(=O)OC(=C)O1)=O DJIHQRBJGCGSIR-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- XGQUSGCBVBFRGX-UHFFFAOYSA-N 3-[4,5-bis(2-cyanoethoxymethyl)-2-phenylimidazol-1-yl]propanenitrile Chemical compound N#CCCN1C(COCCC#N)=C(COCCC#N)N=C1C1=CC=CC=C1 XGQUSGCBVBFRGX-UHFFFAOYSA-N 0.000 description 1
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002766 poly(epichlorohydrin-co-ethylene oxide) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a polymer electrolyte for a dye-sensitized solar cell and a method for manufacturing a dye-sensitized solar cell using the same, and more specifically, to prevent leakage of water, which is the biggest disadvantage of a dye-sensitized solar cell using a conventional liquid electrolyte.
- the polymer electrolyte for dye-sensitized solar cells which exhibits a high light conversion efficiency compared to the conventional polymer electrolyte, and can be applied to the manufacturing process of a large area dye-sensitized solar cell or a flexible dye-sensitized solar cell, and the like It relates to a method for producing a dye-sensitized solar cell used.
- the building integrated solar cell which is generated by using a building wall or a window, can efficiently generate electric power rather than a silicon solar cell. Therefore, even if silicon solar cells continue to generate power for large-scale power plants, dye-sensitized solar cells are expected to cover much of the solar power generation in buildings. In addition, due to eco-friendliness, transparency and colorability, and low efficiency in low light quantity, it is expected to be applicable to various electronic devices, small mobile devices, automobiles, and even clothing fields using indoor lighting. Many studies are being done.
- dye-sensitized solar cells are designed by Swiss Gratzel professor with ideas from photosynthesis of plants, working electrode, inorganic oxide layer such as titanium dioxide adsorbed with dye, liquid electrolyte, It consists of a counter electrode and a photoelectric conversion is performed by using a photoelectrochemical reaction between the electrodes.
- the working electrode is composed of a nano-sized oxide semiconductor with dye molecules attached to sunlight to emit electrons.
- the dye When external light hits the dye, electrons get energy from the dye and become high-energy electrons, which are then transferred to the outside by the oxide semiconductor. High-energy electrons flow through external circuits and consume their energy. Then, the counter electrode is reached again.
- the dye of the working electrode which emits electrons receives electrons again through the electrolyte, and the redox process of these dyes is continuously performed in the energy supply process through ion transfer in the electrolyte.
- the role of the electrolyte in which electrons are transferred through the ions is very important, and in particular, the contact area between the electrode and the electrolyte determines the amount of power produced. In other words, the larger the contact area, the faster the reaction and the larger the amount of dyes attached. Therefore, the nanoparticles are used as the material of each electrode. Due to the extreme increase, large amounts of dyes can be attached to the surface and speed up the electrochemical reaction between the electrode and the electrolyte.
- the titanium dioxide semiconductor oxide electrode forming the working electrode nanoparticles of 20 to 50nm level are coated with a thickness of 10 to 20 ⁇ m, and the dye is attached to the surface.
- the counter electrode is thinly coated with a platinum particle having a size of less than 10nm on the substrate.
- the solid or semi-solid electrolyte is researched and developed using organic polymers or inorganic hole transfer materials (HTM), and most of them are organic polymer electrolytes which are advantageous for commercialization.
- HTM organic polymers or inorganic hole transfer materials
- This provides flexibility because the shape of the dye-sensitized solar cell can be modified in the manufacture of the solid-state dye, and the thin film can be manufactured using a method such as spin coating. And it can maintain stable performance under thermal stress or light soaking compared to liquid electrolyte, contribute to the improvement of long-term stability, and there is an advantage that the manufacturing cost is cheap.
- PEO poly (propylene oxide)
- PPO poly (ethylene imine)
- PEI poly (ethylene imine)
- PES poly (ethylene sulphide)
- PVAc poly (vinyl acetate)
- PESc Ion transport in the polymer electrolyte is known to occur in the amorphous region due to the segmental movement of the polymer chain, and such polymers have been studied.
- the most widely studied polymer electrolyte is a complex of PEO and alkali metal salts.
- PEO exhibits various properties depending on molecular weight, and particularly, has excellent chemical stability, and has high mechanical strength compared to liquid electrolyte, and thus is applicable to solid dye-sensitized solar cells.
- PEO has a large array of regular oxygen atoms and is known to have a mechanism of ion conduction through which metal cations are transferred through the spiral structure formed by the polymer chain.
- it is preferable to be composed of a polymer having an alkali metal series such as LiI, KI, NaI and the like and a polar group capable of dissociating it. Therefore, the polymer should contain lone pair electrons that can give electrons such as oxygen (O) or nitrogen (N), and these polar groups are covalently bonded to metal cations to polymer-metal salt complexes. -metal salt complex).
- Korean Unexamined Patent Publication No. 2003-65957 describes a semi-solid polymer electrolyte as an example, and claimed that the semi-solid polymer electrolyte exhibits high ionic conductivity similar to liquid electrolyte at room temperature.
- Tg temperature of glass transition
- the process of manufacturing a battery is not only difficult because of its durability and semi-solid characteristics, but also due to the mixing of solvents. It is difficult to expect phosphorus leak prevention.
- the polymer electrolyte is mostly made of poly (ethylene oxide) PEO, and it is important to increase the amorphous region by lowering the crystallinity of the PEO. Crystallinity reduction and ionic conductivity improvement through copolymer formation or blending, crosslinking, and addition of nanoparticles for this purpose are the major research fields of polymer electrolytes, and additional performance improvement can be obtained by controlling the molecular weight and end groups of the polymer. have.
- the first dye-sensitized solar cell using a solvent-free polymer electrolyte was presented by a research group by Professor De Paoli, Brazil, in 2001, and a polymer electrolyte composed of poly (epichlorohydrin-co-ethylene oxide) / NaI / I 2 . was prepared and reported an efficiency of about 1.6% at 100 mW / cm 2 .
- the Flaras Group of Greece reported the result of reducing the crystallinity of PEO by incorporating titanium oxide nanoparticles into a highly crystalline PEO electrolyte.
- the Flavia Nogueira Group reported the same poly (epichlorohydrin-co- Using ethylene oxide) and titanium dioxide in the form of nanotubes (nano tube) to reduce the crystallinity reported a result that the light conversion efficiency reaches 3.5%.
- the present inventors have come up with a new polymer electrolyte and assembly process to overcome the limitations of the conventional polymer electrolyte based on PEO.
- Development of new transparent electrode, new semiconductor material and manufacturing technology, dye technology absorbing wide wavelength range, development of new material and manufacturing technology of counter electrode in manufacturing dye-sensitized solar cell are still liquid electrolyte.
- Given the prior art in the art that does not overcome the limitation of using the polymer electrolyte according to the present invention will be said to have a very large ripple effect in the art.
- Patent Document 1 Korean Unexamined Patent Publication No. 2003-65957
- Non-Patent Document 1 Kinetics study of imidazole-cured epoxy-phenol resins, Yi-Cheng Chen et al,: Polymer Chemistry, Vol 37, Issue 16, Pg3233-3242
- the present invention has been made to solve the above problems, the object of the present invention can not only prevent the leakage of the leakage, which is the biggest disadvantage of the dye-sensitized solar cell using a conventional liquid electrolyte, but also a conventional polymer electrolyte Compared with the high efficiency of the photoelectric conversion, it can be applied to the manufacturing process of a large area dye-sensitized solar cell or flexible dye-sensitized solar cell, and the production of a polymer electrolyte for dye-sensitized solar cell and a dye-sensitized solar cell using the same To provide a way.
- a polymer electrolyte for dye-sensitized solar cell comprising a thermosetting epoxy resin, an imidazole series curing accelerator, and a metal salt.
- the epoxy resin has a 2 to 8 functional group, characterized in that the molecular weight is 500 to 8000.
- the content of the imidazole-based curing accelerator is characterized in that 0.1 to 20% by weight per 100 parts by weight of the epoxy resin.
- the content of the metal salt is characterized in that 1 to 200 parts by weight per 100 parts by weight of the thermosetting epoxy resin.
- the viscosity of the polymer electrolyte for dye-sensitized solar cells is characterized in that 10cp (centi poise) to 8,000cp.
- the purpose is to use the dye-sensitized solar cell polymer electrolyte, using the dye-sensitized solar cell polymer electrolyte as an adhesive between the working electrode and the counter electrode, and the final bonding form of the dye-sensitized, characterized in that to maintain a solid phase It is achieved by a method for producing a dye-sensitized solar cell using a polymer electrolyte for solar cells.
- the bonding between the electrode substrate is characterized in that the hot melt bonding.
- the bonding between the electrode substrate is a continuous roll coating or a continuous roll hot melt bonding using a flexible substrate.
- the present invention it is possible not only to prevent leakage, which is the biggest disadvantage of the dye-sensitized solar cell using the conventional liquid electrolyte, but also to exhibit high light conversion efficiency as compared with the conventional polymer electrolyte, and to provide a large-area dye-sensitized solar cell. It has an excellent effect, such as being applicable to the manufacturing process of a battery or a flexible dye-sensitized solar cell.
- the present invention relates to a polymer electrolyte constituting dye-sensitized solar cells, wherein the polymer electrolyte is composed of a thermosetting epoxy resin and contains an imidazole-based curing accelerator and metal salts. It features. By doing so, it is possible not only to prevent leakage, which is the biggest disadvantage of the dye-sensitized solar cell using the conventional liquid electrolyte, but also to apply it to the manufacturing process of a large-area dye-sensitized solar cell or a flexible dye-sensitized solar cell. It is possible to provide an excellent solid polymer electrolyte for dye-sensitized solar cells.
- the inventors of the present invention have designed the following characteristics of polymer composition to solve the problem of liquid leakage of the conventional liquid electrolyte and to devise a new polymer electrolyte that can be applied to the manufacturing process of large area and flexible solar cells. It was.
- polymer composition capable of dissociating metal salts and transferring ions
- thermosetting epoxy resin as a new polymer electrolyte.
- the epoxy resin is limited in its use as an electrolyte under general knowledge used as an insulating material.
- Epoxy resin forms a three-dimensional network crosslinkable structure that can transfer metal cations
- epoxy resin has a large amount of polar groups capable of dissociating metal salts
- Epoxy resin has low molecular weight at the early stage of curing, so it is easy to penetrate into nano-sized titanium dioxide oxide layer during solar cell manufacturing process.
- the epoxy resin has excellent adhesive strength and durability after curing
- Epoxy resin can be manufactured in liquid-free, semi-solid and completely solid form without solvent, so that it can be used for film coating and hot melt bonding as well as solution coating during the manufacturing process of solar cells.
- the polymer electrolyte for dye-sensitized solar cells is a base polymer (matrix polymer) made of a thermosetting epoxy resin and contains metal salts as an imidazole-based curing accelerator and ion or charge transfer carrier. Characterized in that. Since the thermosetting epoxy resin has a large amount of regular oxygen atoms in the main chain, it is easy to dissociate metal salts and thus can be used as an electrolyte, and the electrolyte can be prepared from a low molecular weight liquid to a solid.
- the polymer electrolyte for dye-sensitized solar cells mixes the imidazole-based curing accelerator with a liquid or solid thermosetting epoxy resin, and then mixes the metal salt as an ion carrier according to the required content, and the mixing method is It is manufactured using conventional compounding techniques.
- a polar solvent such as ethyl methyl keton is used together to prepare a liquid form.
- the method for mixing the polymer electrolyte for dye-sensitized solar cells according to the present invention is not particularly limited, but for example, a method of melt kneading with a Banbury mixer, a single screw extruder, a twin screw extruder, a method of solution mixing by stirring (solution blend), and the like. Can be mentioned. Among these, the method of solution mixing is preferable. In addition, in order to allow the metal salt to exist in a balanced distribution in the epoxy resin in the process of solution mixing, it is preferable to appropriately share dispersion mixing and distribution mixing. To this end, a method of preparing a master batch by dissolving a metal salt in a small amount of epoxy resin in advance and injecting it during mixing is preferable.
- the epoxy resin used in the present invention can be used in the form of a liquid or solid phase at the beginning of use, and these can be used by mixing two or more kinds as necessary.
- a solvent is not used in the process of forming an electrolyte coating layer
- solution coating is possible on a counter electrode on which a titanium dioxide layer is formed using a liquid epoxy resin, and when the solvent is dried, After dissolving the solid epoxy resin in a solvent, it is possible to form a solid electrolyte coating layer by increasing the drying temperature above the boiling point of the solvent in the process of coating on the counter electrode.
- the polymer electrolyte for dye-sensitized solar cells according to the present invention has a viscosity capable of solution coating, preferably 10 cps (centi poise) to 8,000 cps, more preferably 50 cps to 3,000 cps and more preferably 100 cps to 500 cps. Is good.
- the viscosity is 10 cps or less, it is difficult to secure a space with the counter electrode when forming the electrolyte layer on the working electrode on which the oxide semiconductor layer is formed.
- the viscosity reaches 8,000 cps, the electrolyte is formed by nano-sized pores of the oxide semiconductor layer. This is because the layer becomes difficult to penetrate.
- Solid dye-sensitized solar cells exhibit lower energy conversion efficiencies than liquid dye-sensitized solar cells, mainly due to the low conductivity of solid electrolytes and incomplete contact of electrolytes and electrodes. This creates a high rate of electron recombination between the photoelectrode and the solid electrolyte, which greatly affects the overall efficiency. If the polymer electrolyte does not penetrate well into the pores of the nano-sized semiconductor oxide layer, the transfer efficiency of electrons emitted from the dye decreases, which not only directly reduces energy conversion efficiency but also shows practical solar cell manufacturing limitations. .
- the penetration of the electrolyte into the semiconductor oxide layer is improved, thereby increasing the current generation of the working electrode and consequently the low electrode of the solid electrolyte.
- the problem of contact is solved.
- the epoxy resin has an inherent property as an adhesive, it exhibits adhesive strength during bonding between the working electrode and the counter electrode in the module manufacturing process of the battery, thereby providing durability and providing a conventional liquid electrolyte.
- the epoxy resin has an inherent property as an adhesive, it exhibits adhesive strength during bonding between the working electrode and the counter electrode in the module manufacturing process of the battery, thereby providing durability and providing a conventional liquid electrolyte.
- a module encapsulation process that is essential to use is not necessary, when manufacturing a large-area solar cell, it will bring a significant improvement in productivity.
- the polymer electrolyte for dye-sensitized solar cells according to the present invention can be formed by various methods.
- the polymer electrolyte blend is coated on a substrate on which a semiconductor oxide layer is formed by a known roll knife coater, gravure coater, die coater, reverse coater, or the like, followed by drying.
- a polymer electrolyte layer is formed, and a counter electrode is laminated on the polymer electrolyte layer by a roll lamination method, or the polymer electrolyte layer is coated on a counter electrode by a known method and dried, followed by lamination to a working electrode to apply heat.
- a method of infiltrating the polymer electrolyte into the semiconductor oxide layer is possible.
- a polymer electrolyte solution may be simply prepared and then coated by spin coating on each electrode.
- the polymer electrolyte of the present invention when forming an electrolyte layer on a large-area glass substrate, the polymer electrolyte of the present invention is required to undergo a process of injecting and sealing a liquid electrolyte for a long time in a conventional manner.
- solution coating as well as hot melt bonding is possible, and when a flexible substrate such as a polymer film is used as an electrode material, a continuous process is possible, thereby enabling mass production of a large area dye-sensitized solar cell.
- epoxy resin used in the present invention can be used without particular limitation as long as it is cured to exhibit an adhesive action.
- epoxy resins having a molecular weight of preferably 500 to 8000, more preferably 500 to 3000 can be used.
- bifunctional epoxy resins such as bisphenol A (bisphenol A) type epoxy resins and bisphenol F type epoxy resins, furnaces such as phenol novolac epoxy resins and cresol novolac epoxy resins A ballac type epoxy resin etc. can be used.
- a polyfunctional epoxy resin, a heterocyclic containing epoxy resin, etc. can also be used.
- the polymer electrolyte for dye-sensitized solar cells according to the present invention is characterized by using an imidazole-based curing accelerator for the curing initiation reaction of the thermosetting epoxy resin.
- the imidazole-based curing accelerator initiates the curing reaction of the epoxy resin, implements an amorphous cure structure, and simultaneously forms a cationic bond point after the reaction with the epoxy resin, thereby dissociating metal salts.
- ionic transfer ionic transfer
- the solid polymer electrolyte of the present invention is characterized by using an imidazole-based curing accelerator to form a branched structure.
- the polymer electrolyte forms a branch structure through polyetherification of nitrogen atoms attached to the side chains of the epoxy resin and the imidazole series curing agent (Kinetics study of imidazole-cured epoxy-phenol resins, Yi). -Cheng Chen et al,: Polymer Chemistry, Vol 37, Issue 16, Pg3233-3242).
- an amorphous cured structure of the epoxy resin can be obtained by ion polymerization, and the obtained epoxy cured structure enables the movement of metal cations and anions by the presence of free branched volume inside. .
- Curing accelerators used in the polymer electrolyte for dye-sensitized solar cells according to the present invention can be used limited to imidazole.
- imidazole For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-benzyl-4-methylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1- ( 2-cyanoethyl) 2-phenyl-4, 5-di- (cyanoethoxymethyl) Imidazole etc. are mentioned, These can also use together 1 type (s) or 2 or more types.
- imidazole series is, for example, Shikoku Kasei Co., Ltd., under the trade names of 2,4EMIZ, 2B4MIZ, 2-EI, 2-PI, 2-PDHMI, 2E4MZ, 2PZ-CN, 2PZ-CNS. It is commercially available.
- the content of the imidazole-based curing accelerator is preferably from 0.1 to 20% by weight per 100 parts by weight of the epoxy resin, when less than 0.1 by weight of the epoxy resin is hardly made hard to form a branch structure and exceeds 20 weight In this case, the curing of the epoxy resin proceeds so rapidly that the change over time during the preparation of the electrolyte is not preferable.
- an amine curing agent having a primary or secondary amine group may be used, but in this case, the final curing structure forms a linear chain. Because of this, there is a disadvantage in that the crystallization is finally increased. Therefore, it is most preferable to use the imidazole type which can cross-link ion polymerization.
- the polyelectrolyte is usually composed of an alkali-based metal salt having a low lattice energy that is based on a polymer including a polar group and provides an oxidation / reduction pair.
- the cation of the metal salt and the polar group such as oxygen or nitrogen of the polymer form a coordination bond through Lewis acid-base interaction to form an oxidation / reduction pair such as I- or I3-.
- the resulting oxidation / reduction pair generates or consumes the required electrons through oxidation / reduction reactions.
- the electrons are transported by the movement of ions in the polymer electrolyte and the movement of ions in the polymer electrolyte is known to occur in the amorphous region due to the segmental movement of the polymer chain.
- concentration of the charge carriers also has a big impact.
- the Mitate Group said that in order to improve the energy conversion efficiency of quasi solid state DSSCs, the polymer network must be structured through chemical bonds and contain a large amount of liquid electrolyte. It is suggested. Through crosslinking in the polymer network, reactive molecules are connected by chemical bonds and form a 3-D network structure.
- the epoxy resin is used to form a branched polymer network in the solid phase
- the imidazole-based curing accelerator is used as a crosslinking point to increase the movement of anions by oxidation / reduction pairs such as I- and I3-.
- the redox derivative used in the solid polymer electrolyte of the present invention is a material capable of providing a redox pair as lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), lithium bromide (BrI), brominated Halogenated metal salts such as sodium and potassium bromide; And imidazolium salt, pyrridinium salt, quaternary ammonium salt, pyrolidium salt, pyrazolidium salt, isothiazolidinium salt, isoxazolidinium salt Iodides of heterocyclic nitrogen-containing compounds such as (isooxazolidinium) salts can be used.
- organic solvent acetonitrile, 3-methoxypropionitrile, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate carbonate, ethyl methyl carbonate, tetrahydrofuran or gama-butyrolacton, and the like.
- the content of the metal salt is preferably 1 to 200 weight per 100 parts by weight of the thermosetting epoxy resin, and when the content of the metal salt is less than 1 weight, the ion conductivity is almost expressed. If it is not more than 200 weight, it is most preferable to set the above range because the aggregation phenomenon of the metal salt is severe and the preparation of the electrolyte is impossible.
- a method of manufacturing a dye-sensitized solar cell using the polymer electrolyte for dye-sensitized solar cells according to the present invention is a method for manufacturing a solar cell using the above-described polymer electrolyte for dye-sensitized solar cells. It is used as an adhesive between the electrode and the counter electrode and is characterized in that the form of the final junction maintains the solid phase.
- the bonding between the electrode substrates may be hot melt bonding, or the bonding between the electrode substrates may be continuous roll coating or continuous roll hot melt bonding using a flexible substrate.
- a FTO glass substrate was prepared, and a coating composition containing titanium dioxide (TiO 2 ) was coated on the transparent conductive oxide layer of the substrate by a doctor blade method, and thermally treated at 520 ° C. for 40 minutes to form a nanoscale metal oxide layer. Contact and filling were performed to form a nano oxide layer about 7 ⁇ m thick. The thickness was adjusted using 3M Magic Tape as a spacer. Subsequently, the same coating composition was applied to the top of the nano oxide layer by the same method, and heat-treated at 40 ° C. for 40 minutes to form a nano oxide layer having a thickness of about 15 ⁇ m. After preparing a dye solution with S-Nix 719 dye with ethanol, the substrate on which the nano-oxide layer was formed was dipped for 48 hours and dried to adsorb a dye to the nano-sized metal oxide. Prepared.
- TiO 2 titanium dioxide
- Sample 1 was prepared in the same manner as in Sample 1 except that 10 weight of lithium iodide was used.
- Sample 1 was prepared in the same manner as in Sample 1 except that 30 weight of lithium iodide was used.
- Sample 1 was prepared in the same manner as in Sample 1 except that 50 weight of lithium iodide was used.
- the prepared polymer electrolyte solution was coated on the prepared working electrode by Mayer bar coating, and then dried at 80 ° C. for 5 minutes to remove the solvent, thereby obtaining a polymer electrolyte layer having a thickness of about 50 ⁇ m. Subsequently, the counter electrode was laminated, and then pressed under a condition of 130 ° C. 0.01 Mpa in a hot press to prepare a dye-sensitized solar cell without a separate sealing process.
- Example 1 In Example 1 (3) except that 100 weight of bisphenol A liquid epoxy resin (DOTGAsei Co., Ltd., YD128) was used instead of cresol novolac epoxy resin in the preparation of the polymer electrolyte in the same manner as in Example 1 It was.
- DOTGAsei Co., Ltd., YD1228 100 weight of bisphenol A liquid epoxy resin (DOTGAsei Co., Ltd., YD128) was used instead of cresol novolac epoxy resin in the preparation of the polymer electrolyte in the same manner as in Example 1 It was.
- Example 1 (3) in the preparation of the polymer electrolyte 100 weight of polyethylene oxide (Sigma Aldrich, PEO) was used instead of the cresol novolac epoxy resin and the curing accelerator was excluded, and the solvent was acetonitrile (Sigma Aldrich, acetonitrile).
- the dilution ratio was divided into 5 parts by weight and 30 parts by weight of solid solution, and then 5 parts by weight of the solution was applied first, followed by waiting for 2 hours, followed by application of 30 parts by weight to complete the formation of the electrolyte layer. It carried out in the same way.
- An impedence analyzer was used to evaluate the ion conductivity of the polymer electrolyte prepared in Examples and Comparative Examples, and the ion conductivity value was measured by the following equation.
- R is the resistance
- r is the ion conductivity
- l is the distance between electrodes
- A is the measurement cross-sectional area of the sample.
- the photovoltaic characteristics were observed by measuring the photovoltage and the photocurrent as follows, and the current density (Isc) obtained through the above was opened. Voltage (Voc), and filling factor Xenon lamp (Oriel) was used as the light source, and the solar condition (AM 1.5) of the xenon lamp was calibrated using a standard solar cell.
- Equation 2 "P” represents 100 mW / cm 2 (1 sun).
- the polymer electrolytes of Examples 1 to 2 according to the present invention showed high ionic conductivity at room temperature, and a dye comprising a coating layer formed from the polymer electrolyte of Examples 1 to 2 according to the present invention.
- the sensitized solar cell was compared with the dye-sensitized solar cell of Comparative Example 1 including a coating layer formed from a polymer electrolyte containing polyethylene oxide, which is a conventional polymer component, and it was confirmed that the current density and voltage were increased and the light conversion efficiency was improved.
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Abstract
Description
Claims (8)
- 염료감응태양전지용 고분자전해질에 있어서,열경화형 에폭시수지, 이미다졸계 경화촉진제 및 금속염을 포함하는 것을 특징으로 하는, 염료감응태양전지용 고분자전해질.
- 제1항에 있어서,상기 에폭시수지는 2 내지 8관능기를 가지고, 분자량이 500 내지 8000인 것을 특징으로 하는, 염료감응태양전지용 고분자전해질.
- 제1항에 있어서,상기 이미다졸계 경화촉진제의 함량은 상기 에폭시수지 100중량부 당 0.1중량 내지 20중량인 것을 특징으로 하는, 염료감응태양전지용 고분자전해질.
- 제1항에 있어서,상기 금속염의 함량은 상기 열경화형 에폭시수지 100중량부 당 1중량 내지 200중량인 것을 특징으로 하는, 염료감응태양전지용 고분자전해질.
- 제1항에 있어서,상기 염료감응태양전지용 고분자전해질의 점도는 10cp(centi poise) 내지 8,000cp 인 것을 특징으로 하는, 염료감응태양전지용 고분자전해질.
- 제1항 내지 제5항 중 어느 한 항에 따른 염료감응태양전지용 고분자전해질을 사용하되, 상기 염료감응태양전지용 고분자전해질을 작동전극과 상대전극간의 접착물로 이용하고 최종적인 접합의 형태가 고체상을 유지하는 것을 특징으로 하는, 염료감응태양전지용 고분자전해질을 이용한 염료감응태양전지의 제조방법.
- 제6항에 있어서,상기 전극기판간의 접합은 핫멜트 접합인 것을 특징으로 하는, 염료감응태양전지용 고분자전해질을 이용한 염료감응태양전지의 제조방법.
- 제6항에 있어서,상기 전극기판간의 접합은 플렉시블기판을 이용하여 연속적인 롤 코팅 또는 연속적인 롤 핫멜트 접합인 것을 특징으로 하는, 염료감응태양전지용 고분자전해질을 이용한 염료감응태양전지의 제조방법.
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EP10840218.1A EP2385559B1 (en) | 2010-03-19 | 2010-03-22 | Polymer electrolyte for dye-sensitized solar cells and a fabrication method of dye-sensitized solar cells using the polymer electrolyte |
US13/254,241 US8263428B2 (en) | 2010-03-19 | 2010-03-22 | Polymer electrolytes for dye-sensitized solar cells and method for manufacturing modules of dye-sensitized solar cells using the same |
CN201080009780.6A CN102334195B (zh) | 2010-03-19 | 2010-03-22 | 染料敏化太阳能电池用聚合物电解质和使用其制造染料敏化太阳能电池模块的方法 |
JP2012505804A JP5445987B2 (ja) | 2010-03-19 | 2010-03-22 | 色素増感太陽電池用高分子電解質及びこれを利用した色素増感太陽電池の製造方法 |
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WO2023191270A1 (ko) * | 2022-03-31 | 2023-10-05 | 주식회사 엘지에너지솔루션 | 가교 시간이 단축된 겔 폴리머 전해질 조성물, 이를 포함하는 이차전지 및 상기 이차전지의 제조방법 |
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US20120160295A1 (en) * | 2010-06-25 | 2012-06-28 | International Business Machines Corporation | Solar cell classification method |
KR101381873B1 (ko) * | 2012-04-13 | 2014-04-14 | 한국과학기술연구원 | 고분자 젤 전해질 조성물, 이의 제조방법 및 이를 포함하는 염료감응 태양전지 |
KR101574516B1 (ko) * | 2014-03-17 | 2015-12-07 | 주식회사 상보 | 플랙서블 염료감응 태양전지 제조방법 및 장치 |
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KR102229457B1 (ko) * | 2017-09-21 | 2021-03-18 | 주식회사 엘지화학 | 고분자 전해질 및 이의 제조방법 |
JP2019117889A (ja) * | 2017-12-27 | 2019-07-18 | 太陽誘電株式会社 | 色素増感太陽電池 |
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Also Published As
Publication number | Publication date |
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US8263428B2 (en) | 2012-09-11 |
CN102334195A (zh) | 2012-01-25 |
EP2385559B1 (en) | 2016-03-16 |
KR20110105449A (ko) | 2011-09-27 |
CN102334195B (zh) | 2014-06-18 |
JP5445987B2 (ja) | 2014-03-19 |
EP2385559A4 (en) | 2013-02-13 |
EP2385559A1 (en) | 2011-11-09 |
US20120009715A1 (en) | 2012-01-12 |
JP2012514847A (ja) | 2012-06-28 |
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