CN107393722B - A kind of preparation method of graphene-zinc oxide nano tube array dye-sensitized solar cell anode - Google Patents
A kind of preparation method of graphene-zinc oxide nano tube array dye-sensitized solar cell anode Download PDFInfo
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- CN107393722B CN107393722B CN201710626843.6A CN201710626843A CN107393722B CN 107393722 B CN107393722 B CN 107393722B CN 201710626843 A CN201710626843 A CN 201710626843A CN 107393722 B CN107393722 B CN 107393722B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 105
- 239000002071 nanotube Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 28
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 28
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims abstract description 28
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 28
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 19
- 239000000975 dye Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004070 electrodeposition Methods 0.000 claims description 13
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- -1 graphite alkene Chemical class 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 2
- 238000003958 fumigation Methods 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 230000005611 electricity Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 229960001296 zinc oxide Drugs 0.000 description 70
- 239000000243 solution Substances 0.000 description 15
- 238000006884 silylation reaction Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920005573 silicon-containing polymer Polymers 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to area of solar cell, disclose a kind of preparation method of graphene-zinc oxide nano tube array dye-sensitized solar cell anode, the present invention first prepares zinc oxide nano tube array, again with the reaction of the hydroxyl on aminopropyl trimethoxysilane and zinc oxide nano tube array surface, form compound, the graphene oxide of carboxylated is introduced again, so that the carboxyl on graphene is reacted with the amino in aminopropyl trimethoxysilane.Combine graphene in the form of chemical bond with ZnO; this combination is more stronger than simple physical action; the mobility that the presence of chemical bond substantially increases electronics is also to be more easier to carry out using PDMS stripping nano pipe in next step; it is wrapped in even compact the graphene on backing material surface simultaneously; the protective effect of backing material can be given full play to; the chemical stability of composite material is greatly increased, to extend the stability of dye-sensitized cell.
Description
Technical field
The present invention relates to area of solar cell more particularly to a kind of graphene-zinc oxide nano tube array dye sensitizations
The preparation method of solar battery light anode.
Background technique
Dye-sensitized solar cells is because its is at low cost, and preparation method is simple, and photoelectric conversion efficiency is relatively
Height becomes one of the important technology of energy alleviating energy crisis.Typically DSSC (dye-sensitized solar cells) device is usually
A kind of sandwich structure, metal-oxide semiconductor (MOS) such as titanium dioxide (TiO2), zinc oxide (ZnO), tungstic acid (WO3) load
It is used as working electrode on electro-conductive glass, adsorb dyestuff and transmits electronics；Platinum (Pt) film is used as to electrode；Electrolyte solution expands
It dissipates between electrodes, makes the Electronic reproduction in dyestuff.Since the dye-sensitized solar cells of Michael invention since 1991,
Concern of the DSSC by researcher.
Dye-sensitized solar cells is mostly by TiO2As light anode, and ZnO because with TiO2Similar performance, and possess system
The important of research dye-sensitized solar cells is had become for the advantages that simple, environmental protection and economy, pattern is changeable, and electron mobility is high
Material.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of graphene-zinc oxide nano tube array dye sensitizations
The preparation method of solar battery light anode.The zinc oxide nano tube array surface that the present invention is prepared by the way of electro-deposition
There are a large amount of hydroxyl, it is amino-NH that aminopropyl trimethoxysilane, which is a kind of one end,2, the other end is that silylation is silane coupled
Agent, silylation are reacted with the hydroxyl on zinc oxide nano tube array surface first, form aminopropyl trimethoxysilane-zinc oxide nano
The compound of mitron array, then the graphene oxide of carboxylated is introduced, so that carboxyl and aminopropyl trimethoxy on graphene
Amino reaction on base silane.The presence of aminopropyl trimethoxysilane combines graphene in the form of chemical bond with ZnO,
This combination is more stronger than simple physical action, the presence of chemical bond substantially increase electronics mobility be also under
One step is more easier to carry out using PDMS stripping nano pipe, at the same even compact be wrapped in the graphene on backing material surface,
The protective effect that backing material can be given full play to, greatly increases the chemical stability of composite material, to extend dyestuff
The stability of sensitized cells.
The specific technical proposal of the invention is: a kind of graphene-zinc oxide nano tube array dye-sensitized solar cells
The preparation method of light anode, comprising the following steps:
Step 1: electrochemical deposition method prepares nanometic zinc oxide rod array: using two electrode systems, zinc nitrate solution is made
It is placed in heated at constant temperature in water-bath for electrolyte, the electro-conductive glass that the zinc foil cut and left and right ends post insulating tape is distinguished
Anode and cathode as electro-deposition accesses circuit, after deposition, electro-conductive glass is taken out, with deionized water cleaning, drying.
The left and right ends of electro-conductive glass are to facilitate for reserved space and coat PDMS in step 5 close to insulating tape.
Step 2: the nanometic zinc oxide rod array that step 1 is obtained immerses in KOH solution, and constant temperature is anti-under water bath condition
It answers, obtains zinc oxide nano tube array.
The middle section for being added to dissolution zinc oxide nano rod of KOH solution, dissolves preferentially from the core of nanometer rods
Start, the side of nanometer rods is left, so as to form tubular structure.
Step 3: coupling agent modification zinc oxide nano-tube array: fumigating zinc oxide nano tube array with vapor,
Zinc oxide nano tube array is transferred in the acetone soln of aminopropyl trimethoxysilane after natural drying, is stood；Use ethyl alcohol
Rinse solidifies in drying box.
Step 4: zinc oxide nano tube array/graphene oxide composite material preparation: by electro-conductive glass/zinc-oxide nano
Pipe array is immersed in GO-COOH dispersion liquid, water-bath, is dried to obtain zinc oxide nano tube array/graphene oxide film.
Step 5: zinc-oxide nano the preparation of zinc oxide nano tube array/redox graphene composite material: will be covered with
Pipe array/graphene oxide film electro-conductive glass is placed under hydrazine steam, and 60-70 DEG C, reduction is overnight.
Step 6: electro-conductive glass/zinc oxide nano tube array/graphene being placed in spin coater, spin coating PDMS, be put in true
Vacuum drying in empty drying box, removes bubble, after its solidification, by zinc oxide nano tube array/redox graphene/PDMS
Film is removed from electro-conductive glass.
PDMS makees substrate, not only assigns solar cell flexible, maintains the zinc oxide nano mitron stripped down
Original regularity is conducive to the transmitting of electronics, improves the efficiency of dye-sensitized solar cells.
Step 7, at room temperature in zinc oxide nano tube array/redox graphene/PDMS film surface coated dye,
Obtain photo-anode film flexible.
There are a large amount of hydroxyl, ammonia third on the zinc oxide nano tube array surface that the present invention is prepared by the way of electro-deposition
It is amino-NH that base trimethoxy silane, which is a kind of one end,2, the other end is silylation silane coupling agent, and silylation is first and oxidation
The hydroxyl on zinc nano-tube array surface reacts, and forms aminopropyl trimethoxysilane-zinc oxide nano tube array compound, then
The graphene oxide of carboxylated is introduced, so that the carboxyl on graphene is reacted with the amino in aminopropyl trimethoxysilane.
The presence of aminopropyl trimethoxysilane combines graphene in the form of chemical bond with ZnO, and this combination is than simple
Physical action want stronger, the presence of chemical bond substantially increase electronics mobility be also in next step using PDMS removing receive
Mitron is more easier to carry out, at the same even compact be wrapped in the graphene on backing material surface, fid can be given full play to
The protective effect of material, greatly increases the chemical stability of composite material, to extend the stability of dye-sensitized cell.
Preferably, the concentration of GO-COOH dispersion liquid is 0.15-0.25wt%, soaking time 1.5- in step 4
2.5h, bath temperature are 65-75 DEG C.
The carboxyl of graphene oxide can form amido bond in conjunction with the amino of aminopropyl trimethoxysilane.Graphene with
The combination of ZnO chemical bond is more stronger than simple physical action, and the presence of chemical bond substantially increases the migration of electronics
Rate is also to be more easier to carry out using PDMS stripping nano pipe in next step.
Preferably, the concentration of zinc nitrate solution is 0.005M in step 1；Bath temperature is 70-80 DEG C；The conduction
Glass is ITO or FTO electro-conductive glass；Circuital current is 0.7-0.9mA, sedimentation time 3.5-4.5h.
Preferably, the concentration of KOH solution is 0.15-0.2M in step 2；Bath temperature is 70-90 DEG C, the reaction time
For 1.5-2h.
Preferably, fumigation time is 20-40 min in step 3；The body of aminopropyl trimethoxysilane and acetone soln
For product than being 1:9, time of repose is 4-5 h；Solidification temperature is 100-110 DEG C, and curing time is 30-40 min.
Preferably, the PDMS includes the PDMS prepolymer and curing agent that mass ratio is 9-11:1 in step 5, it will be pre-
15-25min, vacuum drying time 8-12min are stirred after polymers and curing agent mixture；Spin coating rate is 550-650rpm,
Solidification temperature is 65-75 DEG C, curing time 1.5-2.5h.
Preferably, the dyestuff is one of N719, N3, Z907, porphyrin in step 6.
Preferably, dyestuff coating method are as follows: the dye solution for preparing 2-3mol/L drips dye solution in zinc oxide nano
Mitron array/graphene surface, it is primary every 7.5-8.5h drop, after placing 20-28h, surface is rinsed with deionized water, it is naturally dry
It is dry, obtain solar energy anode film flexible.
Preferably, the solvent of dye solution is chloroform, n,N-Dimethylformamide, dimethyl sulfoxide or chloroform
One kind.
It is compared with the prior art, the beneficial effects of the present invention are:
1, the present invention is prepared for one-dimensional nano-array zinc oxide by electrochemical method, with the consistent spatial orientation of height
Good specific surface area so that the absorption of dyestuff and the quick transmitting of electronics.
2, there are a large amount of hydroxyl, aminopropyls three on the zinc oxide nano tube array surface prepared by the way of electro-deposition
It is amino-NH that methoxy silane, which is a kind of one end,2, the other end is silylation silane coupling agent, and silylation is first and zinc oxide nano
The hydroxyl of mitron array surface reacts, and forms aminopropyl trimethoxysilane-zinc oxide nano tube array compound, then by carboxylic
The graphene oxide of base introduces, so that the carboxyl on graphene is reacted with the amino in aminopropyl trimethoxysilane.Ammonia third
The presence of base trimethoxy silane combines graphene in the form of chemical bond with ZnO, and this combination is than simple object
Reason effect wants stronger, and the mobility that the presence of chemical bond substantially increases electronics is also in next step using PDMS stripping nano pipe
Be more easier to carry out, at the same even compact be wrapped in the graphene on backing material surface, backing material can be given full play to
Protective effect, greatly increases the chemical stability of composite material, to extend the stability of dye-sensitized cell.
3, PDMS is made substrate by the present invention, is not only assigned solar cell flexible, is also made the zinc oxide nano stripped down
Mitron maintains original regularity, is conducive to the transmitting of electronics, improves the efficiency of dye-sensitized solar cells.
Specific embodiment
The present invention will be further described with reference to the examples below.
Embodiment 1
1) electrochemical deposition method prepares nanometic zinc oxide rod array
Using two electrode systems, the zinc nitrate solution of 0.005M is placed on 70 DEG C of constant temperature in water-bath as electrolyte and is added
Heat, using the zinc foil cut and left and right ends close to insulating tape clean electro-conductive glass as the anode of electro-deposition and yin
Circuit is accessed in pole.Control circuit electric current is 0.9mA, time 4h.After deposition, electro-conductive glass is taken out, uses deionized water
Cleaning, drying.By the nanometic zinc oxide rod array after obtained drying, prepared 0.2M KOH solution is immersed, in water-bath item
The lower 90 DEG C of isothermal reaction 2h of part, can be obtained zinc oxide nano tube array.
2) coupling agent modification zinc oxide nano-tube array
Stifling 30 min are carried out to zinc oxide nano tube array with vapor, by zinc oxide nano mitron battle array after natural drying
Column jump (V:V=1:9) into the acetone soln of aminopropyl trimethoxysilane stands 4h.With ethyl alcohol rinse, in drying box
100 DEG C of solidification 30min.
3) zinc oxide nano tube array/graphene oxide composite material preparation: by electro-conductive glass/zinc oxide nano mitron battle array
Column are immersed in 0.2wt% GO-COOH dispersion liquid, 70 DEG C of water-baths, are impregnated 2h, are dried to obtain zinc oxide nano tube array/oxidation
Graphene film.
4) zinc oxide nano mitron battle array will zinc oxide nano tube array/redox graphene composite material preparation: be covered with
Column/graphene oxide film electro-conductive glass is placed under hydrazine steam, and 65 DEG C, reduction is overnight.
5) electro-conductive glass/zinc oxide nano tube array/graphene is placed in spin coater, prepolymer and curing agent is mixed
20min, spin coating PDMS(dimethyl silicone polymer 10: curing agent 1 are stirred after object).It is placed on 10min in vacuum drying oven, removes degassing
Bubble.Spin coating rate is 600rpm, and solidification temperature is 70 DEG C, curing time 2h.By zinc oxide nano tube array/graphite after cooling
Alkene/PDMS film is removed from electro-conductive glass.
6) zinc oxide nano tube array/graphene/PDMS film painting is covered with 3mol/L tetracarboxylic corproporphyrin at room temperature
Chloroform soln, it is primary every 8h drop, after placing for 24 hours, rinse surface with deionized water, spontaneously dry, obtain flexible
Solar energy anode film.
Embodiment 2
1) electrochemical deposition method prepares nanometic zinc oxide rod array
Using two electrode systems, the zinc nitrate solution of 0.005M is placed on 70 DEG C of constant temperature in water-bath as electrolyte and is added
Heat, using the zinc foil cut and left and right ends close to insulating tape clean electro-conductive glass as the anode of electro-deposition and yin
Circuit is accessed in pole.Control circuit electric current is 0.9mA, time 4h.After deposition, FTO electro-conductive glass is taken out, deionization is used
Water cleaning, drying.By the nanometic zinc oxide rod array after obtained drying, prepared 0.2M KOH solution is immersed, in water-bath
Under the conditions of 90 DEG C of isothermal reaction 2h, zinc oxide nano tube array can be obtained.
2) coupling agent modification zinc oxide nano-tube array
Stifling 30 min are carried out to zinc oxide nano tube array with vapor, by zinc oxide nano mitron battle array after natural drying
Column jump (V:V=1:9) into the acetone soln of aminopropyl trimethoxysilane stands 4h.With ethyl alcohol rinse, in drying box
100 DEG C of solidification 30min.
3) zinc oxide nano tube array/graphene oxide composite material preparation: by electro-conductive glass/zinc oxide nano mitron battle array
Column are immersed in 0.2wt% GO-COOH dispersion liquid, 70 DEG C of water-baths, are impregnated 2h, are dried to obtain zinc oxide nano tube array/oxidation
Graphene film.
4) zinc oxide nano mitron battle array will zinc oxide nano tube array/redox graphene composite material preparation: be covered with
Column/graphene oxide film electro-conductive glass is placed under hydrazine steam, and 65 DEG C, reduction is overnight.
5) electro-conductive glass/zinc oxide nano tube array/graphene is placed in spin coater, prepolymer and curing agent is mixed
20min, spin coating PDMS(dimethyl silicone polymer 10: curing agent 1 are stirred after object).It is placed on 10min in vacuum drying oven, is removed
Bubble.Spin coating rate is 600rpm, and solidification temperature is 70 DEG C, curing time 2h.By zinc oxide nano tube array/stone after cooling
Black alkene/PDMS film is removed from electro-conductive glass.
6) zinc oxide nano tube array/graphene/PDMS film is applied to the N, N- bis- for being covered with 3mol/L N719 at room temperature
Methylformamide solution, it is primary every 8h drop, after placing for 24 hours, surface is rinsed with deionized water, spontaneously dries, obtains flexible
Solar energy anode film.
Embodiment 3
1) electrochemical deposition method prepares nanometic zinc oxide rod array
Using two electrode systems, the zinc nitrate solution of 0.005M is placed on 70 DEG C of constant temperature in water-bath as electrolyte and is added
Heat, using the zinc foil cut and left and right ends close to insulating tape clean electro-conductive glass as the anode of electro-deposition and yin
Circuit is accessed in pole.Control circuit electric current is 0.9mA, time 4h.After deposition, ITO electro-conductive glass is taken out, deionization is used
Water cleaning, drying.By the nanometic zinc oxide rod array after obtained drying, prepared 0.2M KOH solution is immersed, in water-bath
Under the conditions of 90 DEG C of isothermal reaction 2h, zinc oxide nano tube array can be obtained.
2) coupling agent modification zinc oxide nano-tube array
Stifling 30 min are carried out to zinc oxide nano tube array with vapor, by zinc oxide nano mitron battle array after natural drying
Column jump (V:V=1:9) into the acetone soln of aminopropyl trimethoxysilane stands 4h.With ethyl alcohol rinse, in drying box
100 DEG C of solidification 30min.
3) zinc oxide nano tube array/graphene oxide composite material preparation: by electro-conductive glass/zinc oxide nano mitron battle array
Column are immersed in 0.2wt% GO-COOH dispersion liquid, 70 DEG C of water-baths, are impregnated 2h, are dried to obtain zinc oxide nano tube array/oxidation
Graphene film.
4) zinc oxide nano mitron battle array will zinc oxide nano tube array/redox graphene composite material preparation: be covered with
Column/graphene oxide film electro-conductive glass is placed under hydrazine steam, and 65 DEG C, reduction is overnight.
5) electro-conductive glass/zinc oxide nano tube array/graphene is placed in spin coater, prepolymer and curing agent is mixed
20min, spin coating PDMS(dimethyl silicone polymer 10: curing agent 1 are stirred after object).It is placed on 10min in vacuum drying oven, is removed
Bubble.Spin coating rate is 600rpm, and solidification temperature is 70 DEG C, curing time 2h.By zinc oxide nano tube array/stone after cooling
Black alkene/PDMS film is removed from electro-conductive glass.
6) chloroform for zinc oxide nano tube array/graphene/PDMS film painting being covered with 3mol/L Z907 at room temperature is molten
Liquid, it is primary every 8h drop, after placing for 24 hours, surface is rinsed with deionized water, spontaneously dries, obtains solar energy anode flexible
Film.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (9)
1. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode preparation method, feature exist
In the following steps are included:
Step 1: electrochemical deposition method prepares nanometic zinc oxide rod array: two electrode systems is used, using zinc nitrate solution as electricity
Solution liquid is placed in heated at constant temperature in water-bath, using the zinc foil cut and left and right ends post the electro-conductive glass of insulating tape as
The anode and cathode of electro-deposition accesses circuit, after deposition, electro-conductive glass is taken out, with deionized water cleaning, drying；
Step 2: the nanometic zinc oxide rod array that step 1 is obtained immerses in KOH solution, and the isothermal reaction under water bath condition obtains
To zinc oxide nano tube array；
Step 3: coupling agent modification zinc oxide nano-tube array: fumigating zinc oxide nano tube array with vapor, natural
Zinc oxide nano tube array is transferred in the acetone soln of aminopropyl trimethoxysilane after drying, is stood；With ethyl alcohol rinse,
Solidify in drying box；
Step 4: the preparation of zinc oxide nano tube array/graphene oxide film: electro-conductive glass/zinc oxide nano tube array being soaked
For bubble in GO-COOH dispersion liquid, water-bath is dried to obtain zinc oxide nano tube array/graphene oxide film；
Step 5: zinc oxide nano tube array/oxygen the preparation of zinc oxide nano tube array/oxidation graphene film: will be covered with
The electro-conductive glass of graphite alkene film is placed under hydrazine steam, and 60-70 DEG C, reduction is overnight；
Step 6: will be placed in spin coater, revolve with zinc oxide nano tube array/oxidation graphene film electro-conductive glass
PDMS is applied, vacuum drying in vacuum oven is put in, removes bubble, after its solidification, by zinc oxide nano tube array/oxygen reduction
Graphite alkene/PDMS film is removed from electro-conductive glass；
Step 7, it is obtained at room temperature in zinc oxide nano tube array/redox graphene/PDMS film surface coated dye
Graphene flexible-zinc oxide nano tube array dye-sensitized solar cell anode.
2. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as described in claim 1
Preparation method, which is characterized in that in step 4, the concentration of GO-COOH dispersion liquid is 0.15-0.25wt%, soaking time 1.5-
2.5h, bath temperature are 65-75 DEG C.
3. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as described in claim 1
Preparation method, which is characterized in that in step 1, the concentration of zinc nitrate solution is 0.005M；Bath temperature is 70-80 DEG C；It is described to lead
Electric glass is ITO or FTO electro-conductive glass；Circuital current is 0.7-0.9mA, sedimentation time 3.5-4.5h.
4. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as described in claim 1
Preparation method, which is characterized in that in step 2, the concentration of KOH solution is 0.15-0.2M；Bath temperature is 70-90 DEG C, when reaction
Between be 1.5-2h.
5. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as described in claim 1
Preparation method, which is characterized in that in step 3, fumigation time 20-40min；The volume of aminopropyl trimethoxysilane and acetone
Than being 1: 9, time of repose 4-5h；Solidification temperature is 100-110 DEG C, curing time 30-40min.
6. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as described in claim 1
Preparation method, which is characterized in that in step 6, the PDMS includes the PDMS prepolymer and curing agent that mass ratio is 9-11: 1, will
15-25min, vacuum drying time 8-12min are stirred after prepolymer and curing agent mixing；Spin coating rate is 550-650rpm,
Solidification temperature is 65-75 DEG C, curing time 1.5-2.5h.
7. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as described in claim 1
Preparation method, which is characterized in that in step 7, the dyestuff is one of N719, N3, Z907, porphyrin.
8. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as claimed in claim 7
Preparation method, which is characterized in that dyestuff coating method are as follows: the dye solution for preparing 2-3mol/L drips dye solution in oxidation
Zinc nano-tube array/redox graphene/PDMS film surface, it is primary every 7.5-8.5h drop, after placing 20-28h, spend
Ionized water rinses surface, spontaneously dries, obtains graphene flexible-zinc oxide nano tube array dye-sensitized solar cells light
Anode.
9. a kind of graphene-zinc oxide nano tube array dye-sensitized solar cell anode as claimed in claim 8
Preparation method, which is characterized in that the solvent of dye solution is the one of n,N-Dimethylformamide, dimethyl sulfoxide or chloroform
Kind.
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