CN100570902C - The flexible carbon of dye sensitization nanocrystalline thin-film solar cell high pore space is to electrode and preparation method - Google Patents
The flexible carbon of dye sensitization nanocrystalline thin-film solar cell high pore space is to electrode and preparation method Download PDFInfo
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- CN100570902C CN100570902C CNB2007101334508A CN200710133450A CN100570902C CN 100570902 C CN100570902 C CN 100570902C CN B2007101334508 A CNB2007101334508 A CN B2007101334508A CN 200710133450 A CN200710133450 A CN 200710133450A CN 100570902 C CN100570902 C CN 100570902C
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 title claims abstract description 13
- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 9
- 230000008313 sensitization Effects 0.000 title claims abstract description 9
- 239000010409 thin film Substances 0.000 title claims abstract description 9
- 239000010408 film Substances 0.000 claims abstract description 55
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 37
- 239000004917 carbon fiber Substances 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009792 diffusion process Methods 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000005087 graphitization Methods 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000004020 conductor Substances 0.000 claims abstract description 8
- 239000002159 nanocrystal Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000011302 mesophase pitch Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910003594 H2PtCl6.6H2O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The high pore space flexible carbon of dye sensitization nano-crystal thin-film solar cell is to electrode, and described high pore space flexible carbon comprises that to electrode one has the carbon-fiber film of three-dimensional porous diffusion micro-structural and the composite membrane that one deck polytetrafluoroethylene film is formed by one deck; It is the semiconductor work electrode that film is provided with the titanium dioxide semiconductor porous membrane.The preparation method of electrode is, to the carbon-fiber film graphitization with support the nanometer platinum black and handle, with this composite membrane be dye-sensitized solar cells to electrode, form dye-sensitized solar cells with conductor oxidate work electrode based on rigid basement; Or form full flexible dye-sensitized solar cell with conductor oxidate work electrode based on flexible substrates; And to the carbon-fiber film graphitization with support the nanometer platinum black and handle, handle the composite membrane that back and one deck polytetrafluoroethylene film are formed; With this composite membrane be dye-sensitized solar cells to electrode.
Description
Technical field
The invention belongs to technical field of nano material, and a kind of electrode of solar cell, especially a kind of dye sensitization nano-film solar cell high pore space flexible carbon also belongs to technical field of new energies to electrode and preparation method.
Background technology
Energy problem is related to the sustainable development in the whole world, becomes the key factor of restriction social development.With at present on market in the highest flight the expensive production cost of silicon solar cell and the preparation technology of complexity compare, the most attracting characteristics of dye-sensitized solar cells (Dye-sensitized Solar Cell is called for short DSSC) are its cheap raw material and relative simple manufacture craft, and stable performance, decay are lacked, and have long-range application prospect.
1991
Nanoporous TiO with high-specific surface area
2Film is applied on the dye-sensitized solar cells, and photoelectric conversion efficiency arrives 7.1%.Nanocrystalline TiO
2Perforated membrane is than level and smooth TiO
2Membrane area has increased nearly thousand times, makes only just can reach enough light absorption with the dyestuff monolayer.The laboratory photoelectric conversion efficiency of this dye-sensitized nano film solar battery is called by industry near business-like amorphous silicon solar cell
Battery becomes the important new direction that develops a kind of low price, efficient solar battery.
1993,
Reported once more that Deng the people photoelectric conversion efficiency reaches 10% dye-sensitized solar cells, by 1997, its photoelectric conversion efficiency reached 10%～11%.The black dye of development in 1997 has widened 100nm than the absorption spectrum ranges of N3 dyestuff to infrared region.1998,
Adopt the alternative electrolytical all-solid-state dye-sensitized solar cell of liquid of SOLID ORGANIC hole mobile material to succeed in developing Deng the people, its monochromatic light conversion efficiency reaches 33%, thereby has caused global concern.2004, use composite polymeric electrolyte such as Korea S Jong Hak Kim were made all-solid-state dye-sensitized solar cell, and its photoelectric conversion efficiency also reaches 4.5%.But photoelectric conversion efficiency is lower, the encapsulation of large tracts of landization, liquid electrolyte and long-time stability are technical problem underlying of dye-sensitized solar cells.
The structure of dye-sensitized cell is, there are the following problems, because the actual process of objective reality is made the stress deformation that the sum of errors high-temperature process is brought, there is flatness error in electro-conductive glass, cause with electro-conductive glass adhere to work electrode that conductor oxidate makes with make with attached catalyst on the electro-conductive glass (as Pt) there is big gap in electrode stack back, the electrolyte skewness, the redox reaction speed that electronics injects electrolyte descends rapidly, so that battery efficiency descends.In the battery of large tracts of land (more than the 10cm X10cm), this problem is more outstanding.
The liquid electrolyte dye-sensitized cell exists the too high battery that causes of electrolyte vapour pressure and damages problem, and promptly high temperature is down owing to the thermal expansion of solution, encapsulating material and the porous TiO that contraction causes
2The problems such as evaporation of the peeling off of film, electrolyte leakage and solvent.
With the electro-conductive glass be substrate to electrode, catalyst Pt adheres on the assorted smooth glass surface, three-dimensional porous relatively diffusion micro-structural, its catalysis area is limited, is restricting the lifting of battery efficiency.
In addition, work electrode and all adopt electro-conductive glass (FTO, ITO) to do substrate to electrode, the cost height, and cell thickness is the thickness of twice electro-conductive glass at least, is unfavorable for the lighting that battery is installed and used.
Summary of the invention
The present invention seeks to: the high pore space flexible carbon that a kind of dye sensitization nano-crystal thin-film solar cell is provided is to electrode and preparation method thereof, a kind of three-dimensional porous diffusion micro-structural is proposed, improve electrolyte in catalytic reduction reaction speed, and be that a kind of high pore space flexible carbon of flexible dye-sensitized nano-crystal thin-film solar cell is to electrode electrode.
Technical scheme of the present invention is: the high pore space flexible carbon of dye sensitization nano-crystal thin-film solar cell is to electrode and preparation method thereof, and high pore space flexible carbon comprises that to electrode one has the carbon-fiber film of three-dimensional porous diffusion micro-structural and the composite membrane that one deck polytetrafluoroethylene film is formed by one deck; It is the semiconductor work electrode that film is provided with the titanium dioxide semiconductor porous membrane.The preparation method comprises the carbon-fiber film graphitization and supports the processing of nanometer platinum black, with this composite membrane be dye-sensitized solar cells to electrode, form dye-sensitized solar cells with conductor oxidate work electrode, or form full flexible dye-sensitized solar cell with conductor oxidate work electrode based on flexible substrates based on rigid basement.Among the preparation method, comprise the carbon-fiber film graphitization and support the nanometer platinum black and handle, handle the composite membrane that back and one deck polytetrafluoroethylene film are formed; With this composite membrane be dye-sensitized solar cells to electrode, and with form dye-sensitized solar cells based on the conductor oxidate work electrode of rigid basement, or form full flexible dye-sensitized solar cell with conductor oxidate work electrode based on flexible substrates;
To the carbon-fiber film graphitization with support nanometer platinum black processing method and be: with the carbon fiber paper body paper through dipping, mould, carbonization, graphitization, prepare three-dimensional porous diffusion micro-structural. after the carbon fiber body paper being immersed the ethanol solution of dissolving mesophase pitch and phenolic resins, at the baking oven heating, drying; Putting on the vulcanizing press under pressure and 300-600 ℃ of temperature hot pressing or mould then is shaped; Goods after the mould are put into carbide furnace, are warming up to more than 1000 ℃ under inert gas shielding and are incubated 10-60min; Obtain the carbon fiber of three-dimensional porous diffusion micro-structural; Its graphitization temperature is at 1000-2500 ℃, and the thickness after its mould is 1 μ m-1700 μ m.
Carbon-fiber film catalysis and Pt/C catalyst modification to above-mentioned three-dimensional porous diffusion micro-structural: earlier the HCl with 1～3mol/L cleaned carbon-fiber film 6-48 hour, filter, with hot second distillation water washing to filtrate pH=5～6,110 ℃ under drying 12 hours; With mass fraction is that 15% hydrogen peroxide oxidation was handled 24 hours, be washed to filtrate with second distillation again and be neutral, in 110 ℃ dry 12 hours down; To the carbon-fiber film catalyst Pt/C modification of three-dimensional porous diffusion micro-structural, the content of its Pt is 1x10 then
-6-1mol/cm
3
Use pressure sintering that carbon-fiber film formation hot pressing film, the rigidity work electrode of polytetrafluoroethylene film and three-dimensional porous diffusion micro-structural are compressed on half complete flexible dye-sensitized battery of hot pressing film periphery sealing, the temperature range of compacting is 65 ℃-375 ℃, pressure is 0.1-5MPa, and the time is 0.1s-600s.
The invention has the beneficial effects as follows: when being used for the liquid electrolyte dye-sensitized solar cells, its three-dimensional porous micro-structural is dynamically stored liquid electrolyte, has solved under the high temperature by the thermal expansion of solution, contraction and the encapsulating material and the porous TiO that cause
2The problems such as evaporation of the peeling off of film, electrolyte leakage and solvent.Substitute to carry the platinum electro-conductive glass to electrode with the present invention, then make expensive electro-conductive glass substrate use amount reduce half, reduced the manufacturing cost of dye-sensitized cell, the thickness of battery also reduced near half.The present invention also can with flexible TiO
2Work electrode cooperates, and is used for full flexible dye-sensitized solar cell.Flexible electrode has overcome work electrode that the flatness error of large tracts of land electro-conductive glass substrate brings and electrode has been contacted problem of non-uniform, is suitable for the manufacturing of area battery.
Description of drawings
Fig. 1 is the microphoto of the carbon-fiber film of the three-dimensional porous diffusion micro-structural of the present invention
Fig. 2 is the dye sensitization nano-crystal thin-film solar cell i-v curve schematic diagram of high pore space flexible carbon of the present invention to electrode
Fig. 3 is a solar battery structure schematic diagram of the present invention
Electro-conductive glass substrate 1, oxide semiconductor film electrode 2, electrolyte 3, three-dimensional porous diffusion micro-structural carbon-fiber film 4, polytetrafluoroethylene film 5.
Embodiment
With the carbon fiber paper body paper through dipping, mould, carbonization, graphitization, prepare three-dimensional porous diffusion micro-structural. after the carbon fiber body paper being immersed the ethanol solution of a certain amount of mesophase pitch and phenolic resins, at the baking oven heating, drying.Put on the vulcanizing press hot forming under pressure and 300-600 ℃ of temperature then.Goods after the mould are put into carbide furnace, are warming up to more than 1000 ℃ under inert gas shielding and are incubated 10-60min, and take out the cooling back, puts into 2000 ℃ of Medium frequency induction graphitizing furnaces, processing time 10-60min.
2. to carbon-fiber film catalysis, the Pt modification of three-dimensional porous diffusion micro-structural.The Fundamentals that influence the Pt/ catalytic activity are particle size and function of surface groups thereof of catalyst, comprise the microstructure size of preliminary treatment, Preparation of catalysts method, carbon-fiber film of carbon carbon-fiber film and performance, to processing method of catalyst etc.
The processing of carbon-fiber film:
Earlier the HCl with 1～3mol/L cleaned carbon-fiber film 6-48 hour, filter, with hot second distillation water washing to filtrate pH=5～6,110 ℃ under drying 12 hours; With mass fraction is that 15% hydrogen peroxide oxidation was handled 24 hours, be washed to filtrate with second distillation again and be neutral, in 110 ℃ down dry 12 hours standby.
(1) Pt/C Preparation of catalysts
Directly reduction chloroplatinic acid legal system 10%Pt/C adds the 2.5ml isopropyl alcohol to improve its wettability with the treated carbon black of 100mg, adds in the 5ml redistilled water to be made into suspension-turbid liquid, and ultrasonic stirring 15min makes and mixes.Add the H2PtCl6.6H2O solution that contains Pt 25mg, ultrasonic agitation 30min is warmed up to 80 ℃, keeps 2h, with 1mol/LNa2CO3 the pH of solution is transferred to neutrality, do the reducing agent reduction with sodium formate, 80 ℃ are continued to stir 45min, are cooled to room temperature, suction filtration, washing to filtrate does not have chloride ion, will be deposited in 80 ℃ of vacuumize 12h, and 800 ℃ of heat treatment 30min get final product in the argon gas that flows then.
(2) the inorganic colloid legal system is equipped with the Pt/C catalyst
(i) at first to the H of 10mL 0.0125mol/L
2PtC
6Add 0.3g solid NaHSO in the solution
3, reaction generates intermediate H
3Pt (SO
3)
2OH; 5.0～5.3, the back slowly adds 10% hydrogen peroxide 1.5mL with the pH of 0.075mol/L NaOH solution regulation system, and reaction generates PtO
2Colloid (in the process that adds hydrogen peroxide, needs the Ph value with NaOH solution regulation system all the time, makes it remain on 5.0～5.3.) 95mg carbon black and 5mL isopropyl alcohol are joined PtO
2In the colloidal solution, ultrasonic concussion 30min fully mixes it, adds excessive 6% reducing agent formaldehyde under continuous stirring, makes PtO
2Fully be reduced into Pt, the reduction reaction time is 3h, with hot deionized water repeatedly wash remove chloride ion after, in 80 degree vacuumize 6h, the 600 degree argon gas heating 30min. down that flows
(ii) at first to the H of 10mL 0.0125mol/L
2PtCl
6Add 0.3g solid NaHSO in the solution
3, reaction generates intermediate H
3Pt (SO
3)
2OH; 5.0～5.3, the back slowly adds 10% hydrogen peroxide 1.5mL with the pH of 0.1mol/LNaOH+0.1mol/L sodium acetate mixed solution regulation system, and reaction generates PtO
2Colloid (in the process that adds hydrogen peroxide, needs the Ph value with 0.1mol/L NaOH+0.1mol/L sodium acetate mixed solution regulation system all the time, makes it remain on 5.0～5.3.) 95mg carbon black and 5mL isopropyl alcohol are joined PtO
2In the colloidal solution, ultrasonic concussion 30min fully mixes it, adds excessive 6% reducing agent formaldehyde under continuous stirring, makes PtO
2Fully be reduced into Pt, the reduction reaction time is 3h, with hot deionized water repeatedly wash remove chloride ion after, in 80 ℃ of vacuumize 6h, the 600 degree argon gas heating 30min. down that flows
3. semiconductor work electrode and three-dimensional porous diffusion micro-structural flexibility are to the preparation of electrode
Use screen process press to print the titanium dioxide semiconductor porous membrane and be the semiconductor work electrode, step is as follows:
Use sol-gel to prepare titania gel and make dense film, volume metatitanic acid fourth fat: hydrochloric acid: (increase is in proper order :-hydrochloric acid-ethanol-metatitanic acid in ethanol=17: 1: 33 (33%: 1.96%: 64.7%) mixing, solution occurs transparent)--stir (ultrasonic), leave standstill 10 hours-lifted 450 ℃ of-60 degree oven dryings 15 minutes-Muffle furnaces 10 minutes, A glue;
12g (0.2mol) (1.7518) acetate is added drop-wise under stirring at room in 58.6g (0.2mol) (8.554) isopropyl titanate, after above-mentioned solution stirs 15min (0), pour into as early as possible in 290ml (42.3236) water, want strong agitation (700rpm) when toppling over, white depositions can appear in this moment at once, stirs to make hydrolysis (1 hour) fully in 1 hour.Add 65% nitric acid, colloidal solution is divided into two kinds of (B:5.4ml by adding different amounts; C:4ml) mixed liquor is heated to 78 ℃ from room temperature, heating time 40min, after insulation 75min makes into the glue cooling, add entry volume is transferred to 370ml, and place 250 ℃ of 570ml autoclaves heating 12h to add 2.4ml 65% nitric acid the solution, and put into the ultrasonic dispersion of 200W, ultrasonic per second 15 subpulses are concentrated into gained colloidal sol and contain TiO by Rotary Evaporators
218% by centrifugal removal nitric acid, cleans three times with ethanol, obtains the TiO of ethanol
2Colloidal solution contains TiO
240%, water 4%TiO
2Ethanol colloidal sol and terpineol (claiming terpinol again), be dissolved in the ethyl cellulose mixing Rotary Evaporators of ethanol and remove the second alcohol and water, prescription A contains the TiO of 16.2%20nm
2With 4.5% ethyl cellulose, contain the TiO of 28.6%400nm among the prescription B
2With 7.2% ethyl cellulose.The solvent of B, C all is a terpineol.At first czochralski method prepares dense film, uses silk screen printing one deck 20nmTiO again
2(prescription B), silk screen printing one deck TiO again
2(prescription C) is warming up to 500 ℃ of calcinings gradually under oxygen atmosphere.
Send out by following hot pressing and to make up one and have the carbon-fiber film of three-dimensional porous diffusion micro-structural and the composite membrane that one deck polytetrafluoroethylene film is formed by one deck.
Seascape is got over energy development Co., Ltd precise flat Plate hot press in the use, is dye-sensitized solar cells to electrode by the preparation of following parameter and method with the flexible carbon-fiber film of three-dimensional porous diffusion micro-structural.
Embodiment 1: use 175c, and 3MPa, 3 minutes, the carbon-fiber film+work electrode of polytetrafluoroethylene film+hot pressing film+three-dimensional porous diffusion micro-structural, the periphery sealing is complete.
Embodiment 2: use 175c, and 1MPa, 2 minutes, the carbon-fiber film+work electrode of polytetrafluoroethylene film+hot pressing film+three-dimensional porous diffusion micro-structural, the periphery sealing is complete.
Embodiment 3: use 175c, and 0.8MPa, 2 minutes, the carbon-fiber film+work electrode of polytetrafluoroethylene film+hot pressing film+three-dimensional porous diffusion micro-structural, the periphery sealing is more complete.
Wherein, oil cylinder piston diameter=8cm, by the convert relation of kgf of whole compressing tablet of pressure gauge: (8*8)/pressure of 4*3.14* meter reading (MPa) x 10=(meter reading * 502.4) kgf=whole compressing tablet;
Pressure/the quilt of whole compressing tablet is pressed the kgf on the lifting surface area=unit are of sample.If the kgf on the known unit area, then meter reading is required to be:
Meter reading=(being pressed the kgf on the lifting surface area * unit are of sample)/502.4, unit is MPa.
Claims (2)
1, the high pore space flexible carbon of dye sensitization nano-crystal thin-film solar cell is to electrode, it is characterized in that described high pore space flexible carbon comprises that to electrode one has the carbon-fiber film of three-dimensional porous diffusion micro-structural and the composite membrane that one deck polytetrafluoroethylene film is formed by one deck; It is the semiconductor work electrode that film is provided with the titanium dioxide semiconductor porous membrane.
2, the high pore space flexible carbon of dye sensitization nano-crystal thin-film solar cell is characterized in that comprising to the carbon-fiber film graphitization and supports nanometer platinum carbon and handle electrode preparation method, handles the composite membrane that back and one deck polytetrafluoroethylene film are formed; With this composite membrane be dye-sensitized solar cells to electrode, form full flexible dye-sensitized solar cell with conductor oxidate work electrode based on flexible substrates;
To carbon-fiber film graphitization processing method be: the carbon fiber paper body paper through dipping, mould, carbonization, graphitization, is prepared three-dimensional porous diffusion micro-structural; After the carbon fiber body paper being immersed the ethanol solution of dissolving mesophase pitch and phenolic resins, at the baking oven heating, drying; Putting on the vulcanizing press under pressure and 300-600 ℃ of temperature hot pressing or mould then is shaped; Goods after the mould are put into carbide furnace, are warming up to more than 1000 ℃ under inert gas shielding and are incubated 10-60min; Obtain the carbon fiber of three-dimensional porous diffusion micro-structural; Its graphitization temperature is at 1000-2500 ℃, and the thickness after its mould is 1 μ m-1700 μ m;
The method of the carbon-fiber film of described three-dimensional porous diffusion micro-structural being carried out the Pt/C catalyst modification is: earlier with the HCl cleaning carbon-fiber film of 1～3mol/L 6-48 hour, filter, to filtrate pH=5～6, drying is 12 hours under 110 ℃ with hot second distillation water washing; With mass fraction is that 15% hydrogen peroxide oxidation was handled 24 hours, be washed to filtrate with second distillation again and be neutral, in 110 ℃ dry 12 hours down; To the carbon-fiber film catalyst Pt/C modification of three-dimensional porous diffusion micro-structural, the content of its Pt is 1x10 then
-6-1mol/cm
3
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| CN102082032B (en) * | 2010-09-27 | 2012-06-20 | 清华大学 | Paper dye sensitization solar battery photo-anode and preparation method thereof |
| CN102543466B (en) * | 2011-12-28 | 2013-11-20 | 大连理工大学 | Counter electrode material for dye sensitization solar battery and preparation method and application thereof |
| CN102832049A (en) * | 2012-08-03 | 2012-12-19 | 复旦大学 | Method of preparing conductive carbon fiber/platinum nanometer material and application of conductive carbon fiber/platinum nanometer material |
| CN102903527A (en) * | 2012-09-28 | 2013-01-30 | 彩虹集团公司 | Preparation method of dye-sensitized solar cell photo-anode paste |
| CN103265085B (en) * | 2013-06-04 | 2015-02-11 | 西安凯立化工有限公司 | Method for preparing platinum dioxide by adopting liquid phase process |
| CN111969073A (en) * | 2020-08-13 | 2020-11-20 | 苏州萨弗瑞能源科技有限公司 | Semi-flexible solar module and manufacturing method thereof |
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Non-Patent Citations (4)
| Title |
|---|
| Charge transfer resisitance of spray deposited andcompressed counter electrodes for dye-sensitizednanoparticle solar cells on plastic substrates. Janne Halme, Minna Toivola et al.Solar Energy Materials & Solar Cells,Vol.90 No.7-8. 2006 |
| Effects of the incorporation of carbon powder intonanostructured TiO2 film for dye sensitized solar cell. Soon Hyung Kang, Jae-Yup Kim et al.Journal of Photochemistry and Photobiology A,Vol.186 No.2-3. 2007 |
| 碳纤维微电极制作与电化学行为的研究. 赵叔晞，胡器浩.中国科学技术大学学报，第17卷第2期. 1987 |
| 碳纤维微电极制作与电化学行为的研究. 赵叔晞，胡器浩.中国科学技术大学学报，第17卷第2期. 1987 * |
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