CN102568849B - Carbon counter electrode for dye-sensitized solar cell and preparation method for carbon counter electrode - Google Patents
Carbon counter electrode for dye-sensitized solar cell and preparation method for carbon counter electrode Download PDFInfo
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- CN102568849B CN102568849B CN201110453533.1A CN201110453533A CN102568849B CN 102568849 B CN102568849 B CN 102568849B CN 201110453533 A CN201110453533 A CN 201110453533A CN 102568849 B CN102568849 B CN 102568849B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000003763 carbonization Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000003610 charcoal Substances 0.000 claims description 88
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229920001568 phenolic resin Polymers 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 241000209094 Oryza Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000002817 coal dust Substances 0.000 claims description 4
- 239000011280 coal tar Substances 0.000 claims description 4
- 239000002482 conductive additive Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000002931 mesocarbon microbead Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229920006260 polyaryletherketone Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000004643 cyanate ester Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 241000143437 Aciculosporium take Species 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
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- 238000012545 processing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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Classifications
-
- 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
- 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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- Hybrid Cells (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a carbon counter electrode for a dye-sensitized solar cell and a preparation method for the carbon counter electrode, and belongs to the field of carbon materials. The carbon counter electrode consists of a carbon substrate and a carbon catalytically-active layer compounded on the surface of the carbon substrate. The preparation method comprises the following steps of: forming and carbonizing the carbon substrate, and compounding and carbonizing the carbon catalytically-active layer on the carbon substrate. Because the precursor polymer solution of the carbon catalytically-active layer has a pore seepage effect in the coating compounding process, the polymer solution is firmly attached to the carbon substrate, and an integrated structure is formed by high-temperature carbonization. The prepared carbon counter electrode has high catalytic activity and good electric conductivity, the series resistance and the interface charge exchange resistance of a cell element are reduced, and the short-circuit current density (Jsc), the filling factor (ff) and the photoelectric conversion efficiency (eta) of the dye-sensitized solar cell are improved.
Description
Technical field
The present invention relates to a kind of charcoal for DSSC to electrode and preparation method thereof, belong to field of charcoal material.
Background technology
From 1991, the Michael of Lausanne, SUI Gao Deng engineering institute
nanocrystalline porous film is introduced DSSC (Dye-sensitized Solar Cells by the research group of professor leader, be called for short DSSC) in, the photoelectric conversion efficiency of this battery is had increased significantly (Nature, Vol.353,737,1991) one of novel solar battery of being hopeful most to be applied, is become gradually.Compared to silica-based solar cell, DSSC battery with its cheap cost, simple technique and relatively high photoelectric conversion efficiency and cause global extensive concern and started rapidly research boom.
DSSC is mainly divided into three parts: be adsorbed with the semiconductive thin film light anode of dyestuff, to electrode and be filled in therebetween containing oxidation-reduction pair (I
3 -/ I
-) electrolyte.That the electronics flowed into by external circuit is passed to I fast to the effect of electrode
3 -, and catalysis I
3 -be reduced to I
-.When comparatively large to electrode resistance, but when catalytic activity is fine, will cause electronics can not the transmission of quick nondestructive consumption in whole process, battery can not obtain good efficiency; Otherwise, very little to electrode resistance, but when catalytic activity is not good, the electronics be delivered to electrode can be made not to be reduced fast, and whole battery can not realize maximal efficiency.Therefore as the important component part of battery, good conductivity should be had to have good electrochemical catalysis active again to electrode, also want resistance to chemical attack simultaneously, and there is certain mechanical strength.
Traditional to electrode, its substrate is electro-conductive glass (Transparent Conducting Oxide is called for short TCO), and play a part to collect and transmission positive and negative electrode electronics, catalytic active layer is generally Pt.Although DSSC is with low cost relative to silicon solar cell, the electro-conductive glass as base material and the Pt price as catalyst still very expensive, the square resistance that simultaneously electro-conductive glass is larger also have impact on the efficiency of battery.In order to reduce the cost of DSSC further and raise the efficiency, sight turns to other new material to substitute electro-conductive glass or catalyst Pt by many researchers.But in current research, still electro-conductive glass is adopted to the substrate majority of electrode, the substitution material of Pt catalytic active layer mainly comprises two classes: conducting polymer materials and the various Carbon Materials with catalytic activity, the former catalytic activity is general lower, and conducting polymer PEDOT (poly (3,4-ethylenedioxythiophene)) its price with high catalytic activity is still higher.Carbon Materials becomes the focus of research because having good conductivity and catalytic activity, mechanical strength and the feature such as thermal stability and resistance to chemical attack.But under study for action, still conventional method is adopted to prepare charcoal to electrode, namely apply one deck Pd/carbon catalyst prepare C/ITO or C/FTO to electrode at indium tin oxide (indium tin oxide is called for short ITO) or FTO (fluorine tin oxide) conductive substrates.Adopt Carbon Materials to make and be its wide material sources to the great advantage of electrode, price is lower, and substrate adopts expensive electro-conductive glass and the charcoal that makes useless obviously reduces the manufacturing cost of electrode, fundamentally solves the difficult problem that DSSC holds at high price.In addition, the adhesive force between the charcoal catalytic active layer of coating and base conductive glass is poor, in use there is catalyst obscission, reduces the photoelectric efficiency of DSSC.
Summary of the invention
The object of the invention is to: for the problem that current DSSC manufacturing cost is high, provide a kind of cheap, substrate and catalytic active layer to be Carbon Materials and the charcoal with the integral structure of high adhesion force to electrode and preparation method thereof.
The technical scheme that the present invention deals with problems is: a kind of charcoal for DSSC is to electrode, be made up of charcoal substrate and compound charcoal catalytic active layer in its surface, described charcoal catalytic active layer is compounded in the porous layer of charcoal that the suprabasil one deck of charcoal formed through high temperature carbonization by polymer.
Charcoal is adopt the method for coating to be compounded in charcoal substrate by polymer to electrode, hole occurs in coating procedure and oozes effect, make polymer solution be firmly attached to carbon matrix, after high temperature carbonization, form integral structure.
The pore passage structure of described hole layer of charcoal is orderly pore passage structure or unordered pore passage structure, and aperture is 1 ~ 10nm, and porosity is 10 ~ 40%, and specific area is 600 ~ 1200m
2/ g, thickness is 1 ~ 10 μm.
Described charcoal base material is rupture strength is 2 ~ 10MPa, and resistivity is the tabular Carbon Materials of 0.01 ~ 10 Ω/, and thickness is 0.1 ~ 2mm.
Another object of the present invention is to provide above-mentioned arbitrary charcoal for DSSC to the preparation method of electrode, its concrete technology step is as follows:
A. take according to following mass percent: charcoal micro-nano ground rice: 50 ~ 98%, conductive additive: 1 ~ 40%, binding agent: 1 ~ 10%, after Homogeneous phase mixing, adopt and cold pressing or the mode of hot pressing, make tabular carbon slab at the pressure of 20 ~ 60MPa;
B., under inert atmosphere protection, carbon slab is made charcoal substrate through high temperature carbonization, and carbonization condition is: carbonization temperature 850 ~ 1000 DEG C, heating rate 3 ~ 10 DEG C/min, constant temperature time 1 ~ 4h, shielding gas flow amount 1 ~ 10L/min;
C. after surface finish polishing being carried out in obtained charcoal substrate, adopt rotary coating, blade coating, polymer solution is compounded in charcoal substrate by the mode of spraying or silk screen printing, wherein polymer accounts for 10 ~ 20% of polymer solution quality, drying 15 ~ 24 hours at 30 ~ 100 DEG C, high temperature carbonization makes integrated charcoal catalytic active layer in an inert atmosphere; Carbonization condition is: carbonization temperature 700 ~ 850 DEG C, heating rate 1 ~ 5 DEG C/min, constant temperature time 1 ~ 2h, shielding gas flow amount 0.5 ~ 5L/min;
D. the number of times by repeating step c controls the thickness of catalytic activity layer of charcoal between 1 ~ 10 μm, obtains charcoal to electrode.
Carrying out primary coating and carbonizing the thickness processing the charcoal catalytic active layer produced is 1 ~ 3 μm, and can control charcoal catalytic activity layer thickness through repeating step c, thickness is preferably 1 ~ 10 μm.
In the above-mentioned course of reaction of the present invention, charcoal micro-nano ground rice is preferably coal dust, activated carbon powder, plant base powdered carbon, resin-based powdered carbon, MCMB or graphite powder, and for ensureing fully carrying out of reaction, the granularity of charcoal micro-nano ground rice is preferably 0.1 ~ 10 μm.
Wherein, plant base powdered carbon refers to plant to be the carbide that raw material obtains through high temperature carbonization; Resin-based powdered carbon refers to fluoropolymer resin to be the carbide that raw material obtains through high temperature carbonization; MCMB refers to mesophase pitch microbeads to be the carbide that raw material obtains through high temperature carbonization.
In the above-mentioned course of reaction of the present invention, described polymer solution refers to the solution that dissolution of polymer is formed in a solvent.Polymer is preferably poly furfuryl alcohol, phenolic resins, mesoporous polyimides, mesoporous phenolic resin, mesoporous PAEK, benzoxazine colophony, polyethersulfone ketone or cyanate ester resin; Solvent is preferably the one in DMA (DMAc), 1-METHYLPYRROLIDONE (NMP), acetone, ethanol.
Wherein, mesoporous polyimides, mesoporous phenolic resin, mesoporous PAEK refer to and add template if organic-block co-polymer or pore creating material are as additives such as polyethylene glycol in polymer synthesis process, obtain polymeric articles after heat of solidification process, these additives such as template or pore creating material can be separated out and be formed some apertures is the hole of 20 ~ 50nm and mesoporous.These polymer are referred to as mesoporous polymer as above-mentioned polymer.
Conductive additive is preferably a kind of of conductive black, electrically conductive graphite, Graphene, carbon nano-tube or Carbon fibe or their mixture;
Binding agent is preferably cellulose, coal tar asphalt or phenolic resins.Cellulose is methylcellulose, carboxymethyl cellulose or ethyl cellulose more preferably.
The invention has the beneficial effects as follows:
1) charcoal prepared by the present invention is the integrated tactic pattern of substrate and catalytic active layer to electrode, has good conductivity and electrochemical catalysis is active, and electrolyte resistance corrosive power is strong.Therefore, it is possible to series resistance in reduction cell device and interface charge exchange resistance, improve the short-circuit current density (Jsc) of DSSC, fill factor, curve factor (ff) and photoelectric conversion efficiency.
2) the charcoal substrate prepared of the present invention is compared with electro-conductive glass substrate, has less square resistance, can the electronics that flows into of quicker, loss-free collection external circuit; In area battery manufacturing process capable of reducing using or avoid use metal and stream lead-in wire, simplify preparation technology.
3) charcoal prepared of the present invention is to electrode low cost of manufacture, cheap, replace carrying Pt electro-conductive glass to electrode, on the basis keeping the higher electricity conversion of DSSC and stability, significantly can reduce the manufacturing cost of DSSC, be suitable for the manufacture of area battery, the density of charcoal to electrode is less simultaneously, the weight of energy battery component can be effectively reduced, realize the lighting of solar cell, reduce cost of transportation.Be conducive to promoting the commercialization of DSSC and applying.
Accompanying drawing explanation
Accompanying drawing 4 width of the present invention,
Fig. 1 be in embodiment 6 charcoal to the structural representation of electrode for DSSC;
Fig. 2 be in embodiment 1 charcoal to the photoelectric current-photovoltage curve of the DSSC of electrode assembling;
Fig. 3 be in embodiment 1 charcoal to the scanning electron microscopic picture on electrode integral structure surface;
Fig. 4 be in embodiment 1 charcoal to the scanning electron microscopic picture of electrode integral structure section.
Accompanying drawing is described as follows: 1, nanocrystalline TiO
2film, 2, light anode, 3, I
3 -/ I
-electrolyte, 4, to electrode, 5, charcoal catalytic active layer, 6, charcoal substrate, 7, tin ash (FTO) conductive film of doped with fluorine, 8, electro-conductive glass, 9, sunlight.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
What in the present invention, square resistance test adopted is four point probe resistance meter (RST-9, China).Adopt electrochemical workstation to carry out photovoltaic performance test (Keithley 2601, USA), that adopt in test process is AM1.5 analog light source (the 100mW cm of standard
-2, Solar Light Co., INC., USA).That scanning electron microscope analysis adopts is FEIHitachi S-4800 (USA).What specific area and pore analysis adopted is nitrogen adsorption desorption tester (Antosorb-1, Quantachrome, USA).
Embodiment 1
Take the coal dust that 4g granularity is 10 μm, add 1g electrically conductive graphite and 0.2g carboxymethyl cellulose, after Homogeneous phase mixing, hydraulic press cold moudling under the pressure of 50MPa is used to prepare carbon slab, then under nitrogen atmosphere through 900 DEG C of charings, prepare charcoal substrate, thickness is about 2.0mm, resistance 134m Ω/.Be the DMAc solution of the mesoporous phenolic resin of 14% by mass percent be polymer solution, be compounded in charcoal substrate by the method for rotary coating, 80 DEG C of heat dryings 24 hours in an oven, charcoal substrate forms polymer foil, puts into retort thin polymer film under argon shield and there is the pure charcoal of integration of catalytic activity layer of charcoal to electrode through 750 DEG C of charing formation; Catalytic activity layer of charcoal is without ordered meso-porous structure, and thickness is about 8 μm, and aperture is about 5.5nm, and specific area is 875m
2g
-1, prepare charcoal to electrode simultaneously, and carry out cell package test under AM1.5 illumination simulation, its parameters is open circuit voltage Voc=0.80V, short-circuit current density Jsc=13.24mAcm
-2, fill factor, curve factor ff=0.74, efficiency eta=7.84%.
Embodiment 2
Take the coal dust that 4g granularity is 5 μm, add 1.5g conductive black and 0.2g carboxymethyl cellulose, after Homogeneous phase mixing, hydraulic press cold moudling under the pressure of 30MPa is used to prepare carbon slab, then under nitrogen atmosphere through 950 DEG C of charings, prepare charcoal substrate, thickness is about 1mm, resistance 0.2 Ω/.Simultaneously respectively service quality percentage be 12% mesoporous polyimides, mesoporous phenolic resin, mesoporous PAEK, benzoxazine colophony, polyethersulfone ketone and cyanate ester resin DMAc solution as polymer solution, be compounded in the charcoal substrate of surface finish polishing by the method for spin-coating, in an oven according to ramped heating schedule to 60 DEG C of dryings 24 hours, substrate is formed polyalcohol stephanoporate thin layer, puts into retort and there is the integrated charcoal of catalytic activity layer of charcoal to electrode through 800 DEG C of high temperature carbonizations formation under argon shield; Prepared charcoal simultaneously and under AM1.5 illumination simulation, cell package test carried out to electrode, their structural parameters and photoelectric properties as shown in table 1.
In table 1 embodiment 2, charcoal is to the structural parameters of electrode and photoelectric properties
Embodiment 3
Take the plant base powdered carbon that 4g granularity is 3 μm, add 1.0g Carbon fibe and 0.5g phenolic resins, after Homogeneous phase mixing, use hydraulic press cold moudling under the pressure of 25MPa to prepare carbon slab, 1000 DEG C of charings, prepare charcoal substrate under nitrogen atmosphere, thickness is about 1.2mm, resistance 679m Ω/.Be polymer solution with the mesoporous polyimides DMAc solution that mass percent is 10%, be compounded in charcoal substrate by the method for spraying, 60 DEG C of heat dryings 20 hours in an oven, substrate forms polymer foil, puts into retort thin polymer film under argon shield and there is the pure charcoal of integration of catalytic activity layer of charcoal to electrode through 750 DEG C of charing formation; Catalytic activity layer of charcoal is unordered micro-meso-hole structure, and thickness is 1 μm, and aperture is about 5nm, and specific area is 720m
2g
-1, prepare charcoal to electrode simultaneously, and carry out cell package test under AM1.5 illumination simulation, its parameters is open circuit voltage Voc=0.78V, short-circuit current density Jsc=10.84mAcm
-2, fill factor, curve factor ff=0.73, efficiency eta=6.31%.
Embodiment 4
Take the MCMB that 4g granularity is 1 μm, add 0.4g carbon nanotube and 0.5g coal tar asphalt, after Homogeneous phase mixing, use that hydraulic press is hot-forming under the pressure of 35MPa prepares carbon slab, then under nitrogen atmosphere through 950 DEG C of charings, prepare charcoal substrate, thickness is about 2.0mm, resistance 145m Ω/.Be polymer solution with the mesoporous phenolic resin ethanolic solution that mass percent is 15%, be coated in charcoal substrate by the method for silk screen printing, 90 DEG C of heat dryings 18 hours in an oven, substrate forms polymer foil, put into retort polymer foil under argon shield and carbonize formation catalytic activity layer of charcoal through 750 DEG C, repeat 1 above-mentioned blade coating-drying-carbonization process, the thickness finally obtaining catalytic activity layer of charcoal is that the integrated charcoal of 5 μm is to electrode; Catalytic activity layer of charcoal is ordered mesopore structure, and aperture is about 4nm, and specific area is 580m
2g
-1, porosity 38%.Prepare charcoal to electrode simultaneously, and carry out cell package test under AM1.5 illumination simulation, its parameters is open circuit voltage Voc=0.78V, short-circuit current density Jsc=11.02mAcm
-2, fill factor, curve factor ff=0.75, efficiency eta=6.45%.
Embodiment 5
Take the resin-based powdered carbon that 4g granularity is 0.8 μm, add 0.2g Graphene and 0.5g phenolic resins, after Homogeneous phase mixing, use that hydraulic press is hot-forming under the pressure of 45MPa prepares carbon slab, then under nitrogen atmosphere through 900 DEG C of charings, prepare charcoal substrate, thickness is 2mm, resistance 129m Ω/.Be polymer solution with the polyethersulfone ketone nmp solution of mass percent 10%, be compounded in charcoal substrate by the method for spraying, 70 DEG C of heat dryings 15 hours in an oven, substrate forms polymer foil, puts into retort thin polymer film under argon shield and there is the pure charcoal of integration of catalytic activity layer of charcoal to electrode through 800 DEG C of charing formation; Catalytic activity layer of charcoal is without ordered meso-porous structure, and thickness is 3 μm, and aperture is about 2nm, and specific area is 650m
2g
-1, prepare charcoal to electrode simultaneously, and carry out cell package test under AM1.5 illumination simulation, its parameters is open circuit voltage Voc=0.80V, short-circuit current density Jsc=11.57mAcm
-2, fill factor, curve factor ff=0.74, efficiency eta=6.84%.
Embodiment 6
Take the activated carbon powder that 4g granularity is 10 μm, add 2.5g electrically conductive graphite and 0.5g coal tar asphalt, after Homogeneous phase mixing, use that hydraulic press is hot-forming under the pressure of 35MPa prepares carbon slab, then under nitrogen atmosphere through 900 DEG C of charings, prepare charcoal substrate A, thickness is 1.5mm, resistance 169m Ω/.Be polymer solution with the poly furfuryl alcohol acetone soln that mass percent is 15%, be coated on the charcoal substrate A of surface finish polishing by the method for blade coating, 80 DEG C of heat dryings 20 hours in an oven, substrate forms polymer foil, put into retort thin polymer film under argon shield and carbonize formation catalytic activity layer of charcoal through 700 DEG C, repeat 3 above-mentioned blade coating-drying-carbonization process, the thickness finally obtaining catalytic activity layer of charcoal is that the integrated charcoal of 9.2 μm is to electrode; Catalytic activity layer of charcoal B be unordered microcellular structure, aperture is about 1.3nm, and specific area is 642mwg
-1, porosity is 34%, prepares charcoal to electrode simultaneously, and carry out cell package test under AM1.5 illumination simulation, and its parameters is open circuit voltage Voc=0.78V, short-circuit current density Jsc=9.91mAcm
-2, fill factor, curve factor ff=0.74, efficiency eta=5.71%.
Claims (5)
1. for the charcoal of DSSC to a preparation method for electrode, it is characterized in that: described preparation method comprises following processing step:
A. take according to following mass percent: charcoal micro-nano ground rice: 50 ~ 98%, conductive additive: 1 ~ 40%, binding agent: 1 ~ 10%, after Homogeneous phase mixing, adopt and cold pressing or the mode of hot pressing, make tabular carbon slab at the pressure of 20 ~ 60MPa;
B., under inert atmosphere protection, carbon slab is made charcoal substrate through high temperature carbonization, and carbonization condition is: carbonization temperature 850 ~ 1000 DEG C, heating rate 3 ~ 10 DEG C/min, constant temperature time 1 ~ 4h, shielding gas flow amount 1 ~ 10L/min;
C. after surface finish polishing being carried out in obtained charcoal substrate, adopt rotary coating, blade coating, polymer solution is compounded in charcoal substrate by the mode of spraying or silk screen printing, wherein polymer accounts for 10 ~ 20% of polymer solution quality, drying 15 ~ 24 hours at 30 ~ 100 DEG C, high temperature carbonization makes integrated charcoal catalytic active layer in an inert atmosphere; Carbonization condition is: carbonization temperature 700 ~ 850 DEG C, heating rate 1 ~ 5 DEG C/min, constant temperature time 1 ~ 2h, shielding gas flow amount 0.5 ~ 5L/min;
D. the number of times by repeating step c controls the thickness of charcoal catalytic active layer between 1 ~ 10 μm, obtains charcoal to electrode.
2. method according to claim 1, is characterized in that: described polymer is poly furfuryl alcohol, phenolic resins, mesoporous polyimides, mesoporous phenolic resin, mesoporous PAEK, benzoxazine colophony, polyethersulfone ketone or cyanate ester resin.
3. method according to claim 1, is characterized in that: described charcoal micro-nano ground rice is coal dust, activated carbon powder, plant base powdered carbon, resin-based powdered carbon, MCMB or graphite powder, and the granularity of described charcoal micro-nano ground rice is 0.1 ~ 10 μm.
4. method according to claim 1, is characterized in that: described conductive additive is a kind of in conductive black, electrically conductive graphite, Graphene, carbon nano-tube or Carbon fibe or their mixture.
5. method according to claim 1, is characterized in that: described binding agent is cellulose, coal tar asphalt or phenolic resins.
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| CN101170137A (en) * | 2007-11-21 | 2008-04-30 | 清华大学 | Medium hole carbon pole of dye sensitized solar battery and its making method |
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