CN106449099B - A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film - Google Patents
A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film Download PDFInfo
- Publication number
- CN106449099B CN106449099B CN201610980589.5A CN201610980589A CN106449099B CN 106449099 B CN106449099 B CN 106449099B CN 201610980589 A CN201610980589 A CN 201610980589A CN 106449099 B CN106449099 B CN 106449099B
- Authority
- CN
- China
- Prior art keywords
- photo
- anode film
- nano powder
- zno nano
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011858 nanopowder Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 22
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 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 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000001856 Ethyl cellulose Substances 0.000 claims description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims description 17
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- ZJLKZLGZJOXUSX-UHFFFAOYSA-N CO.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] Chemical compound CO.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] ZJLKZLGZJOXUSX-UHFFFAOYSA-N 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000012453 solvate Substances 0.000 claims description 2
- AJAVMTJTPWMHAE-UHFFFAOYSA-N 1h-imidazole;methanol Chemical compound OC.C1=CNC=N1 AJAVMTJTPWMHAE-UHFFFAOYSA-N 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 230000001788 irregular Effects 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000013019 agitation Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ZJYYHGLJYGJLLN-UHFFFAOYSA-N guanidinium thiocyanate Chemical compound SC#N.NC(N)=N ZJYYHGLJYGJLLN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a kind of preparation methods based on ZnO nano powder photo-anode film, and metal organic frame ZIF-8 is obtained ZnO nano powder after calcining, and then produce after ZnO slurry blade coating and ZnO photo-anode film is prepared in conductive glass surface.Photo-anode film made from above-mentioned preparation method is utilized in addition, also disclosing.The present invention have the characteristics that preparation process is simple, film thickness is controllable, powder diameter is adjustable, it is at low cost, can large area film, reaction condition is mild, and controllability and repeatability are strong, suitable for prepare the photo-anode film of large area, is conducive to promote and apply and industrialized realization.
Description
Technical field
The present invention relates to technical field of energy material more particularly to a kind of zno-based dye-sensitized solar cell anodes
The preparation method of film and its photo-anode film obtained.
Background technique
Dye-sensitized solar cells has many advantages, such as that cheap, environmental-friendly, production is simple, it has also become the third generation is too
The representative of positive energy battery.Dye-sensitized solar cells by dye sensitization photo-anode film, to three part groups of electrode and electrolyte
At wherein photo-anode film is the core component in battery.
Currently, photo-anode film is mainly nanocrystalline TiO2Film.Since ZnO has and TiO2Similar forbidden bandwidth and electricity
Sub- compatibility, and the electron diffusion coefficient of ZnO is better than TiO2, therefore ZnO is as the photo-anode film material one for contaminating quick battery
Directly placed high hopes by people.Further, since the growth of ZnO crystal has anisotropy and the method for synthesis ZnO crystal a variety of
Multiplicity, therefore relative to TiO2For, ZnO is easier to synthesize the nanostructure of a variety of different-shapes, such as threadiness, sheet,
It is rodlike etc..And ZnO nano powder can adsorb more dyestuffs because it possesses big specific surface area and preferable light scattering property,
The absorptivity of light can be increased simultaneously, therefore its incident photon-to-electron conversion efficiency is higher based on the battery of ZnO nano powder photo-anode film.So
And the prior art is based on the preparation of ZnO nano powder and contaminates quick battery light anode film, in the prevalence of complex process, at high cost, controllable
Property and the problems such as poor repeatability, it is difficult to prepare the photo-anode film of large area, promote and apply difficult.Therefore, it is new to be badly in need of research and development
The preparation method of the ZnO nano powder photo-anode film of type, in favor of promoting and applying and industrialized realization.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of systems based on ZnO nano powder photo-anode film
Preparation Method obtains ZnO nano powder by calcining metal organic frame ZIF-8, and then produces ZnO slurry and scratched in leading
Photo-anode film is prepared in electric substrate surface, to obtain big face with simple process, controllability and repeated strong preparation method
Long-pending photo-anode film, in favor of promoting and applying and industrialized realization.Another object of the present invention is to provide utilize above-mentioned system
Photo-anode film made from Preparation Method.
The purpose of the present invention is achieved by the following technical programs:
A kind of preparation method based on ZnO nano powder photo-anode film provided by the invention, comprising the following steps:
(1) metal organic frame ZIF-8 is calcined and obtains ZnO nano powder；
(2) the ZnO nano powder is dispersed in the mixed solution being made of ethyl cellulose, terpinol and alcohol solvent
In, the rotary evaporation after vibrating and is ultrasonic obtains ZnO slurry；
(3) the ZnO slurry be coated in conductive substrates surface, calcined after heating, obtain be attached in conductive substrates,
The photo-anode film being made of ZnO nano powder.
Further, calcination temperature is 450~750 DEG C in step (1) of the present invention；The partial size of the ZnO nano powder
For 30~100nm.
Further, ethyl cellulose is 10cp ethyl cellulose and 46cp ethyl cellulose in step (2) of the present invention
Element；The 10cp ethyl cellulose, the mass-volume concentration of 46cp ethyl cellulose, terpinol in alcohol solvent are respectively
0.1~0.5g/cm3；ZnO nano powder mass percent concentration shared in mixed solution is 1~10wt%.It is described
The time vibrated in step (2) is 5~10min；The time of ultrasound is 20~40min；Oscillation and ultrasound cycle-index be 3~
5 times；The temperature of the rotary evaporation is 70~80 DEG C, and the time is 25~60min.
Further, in step (3) of the present invention ZnO slurry be coated in conductive substrates surface with a thickness of 7~35 μ
m；Heating temperature is 80~120 DEG C；Calcination temperature is 350~450 DEG C.
In above scheme, the preparation of metal organic frame ZIF-8 of the present invention are as follows: by zinc nitrate hexahydrate and 2- methyl miaow
Azoles is dissolved separately in methanol solvate and stirs evenly, and respectively obtains zinc nitrate hexahydrate methanol solution and 2-methylimidazole methanol is molten
Liquid；Then the zinc nitrate hexahydrate methanol solution is poured into 2-methylimidazole methanol solution, is carried out after being stirred to react at room temperature
Centrifugation, washing, drying, obtain metal organic frame ZIF-8.
Further, in zinc nitrate hexahydrate methanol solution of the present invention zinc nitrate hexahydrate molar concentration be 9~
30mM, the molar concentration of 2-methylimidazole is 72~240mM in 2-methylimidazole methanol solution.The time of the reaction be 1~
3h；Drying temperature is 50~70 DEG C.
Another object of the present invention is achieved by the following technical programs:
Using photo-anode film made from above-mentioned preparation method, the photo-anode film with a thickness of 7~35 μm, the ZnO receives
The partial size of rice flour is 30~100nm.
The invention has the following advantages:
(1) present invention have preparation process is simple, film thickness is controllable, powder diameter is adjustable, it is at low cost, can the spies such as large area film
Point, controllability and repeatability are strong, suitable for preparing the photo-anode film of large area, are conducive to promote and apply and industrialized realization.
(2) present invention obtains metal organic frame ZIF-8 using zinc nitrate hexahydrate and 2-methylimidazole as raw material at room temperature,
Reaction condition is mild, and the ZnO nano powder obtained after calcining is used for the preparation of dye-sensitized solar cell anode film, gained
The photo-anode film large specific surface area arrived, photoelectric conversion efficiency with higher.
Detailed description of the invention
Below in conjunction with embodiment and attached drawing, the present invention is described in further detail:
Fig. 1 is the field emission scanning electron microscope surface picture of ZnO photo-anode film obtained by the embodiment of the present invention one；
Fig. 2 is the field emission scanning electron microscope cross-section photographs of ZnO photo-anode film obtained by the embodiment of the present invention one；
Fig. 3 is the photoelectric current-for the dye-sensitized solar cells that ZnO photo-anode film is assembled into made from the embodiment of the present invention
Voltage curve.
Specific embodiment
A kind of preparation method based on ZnO nano powder photo-anode film of the embodiment of the present invention, using the fin oxide condutire of fluorine doped
Glass (FTO) or indium tin oxide-coated glass (ITO) are used as conductive substrates.
Embodiment one:
A kind of preparation method of the photo-anode film based on ZnO nano powder of the present embodiment, its step are as follows:
(1) metal organic frame ZIF-8 is calcined and obtains ZnO nano powder
The preparation of (1-1) metal organic frame ZIF-8: 2.93g zinc nitrate hexahydrate and 6.49g 2-methylimidazole point are weighed
It is not placed in two beakers, is separately added into 200mL methanol, magnetic agitation dissolution, obtaining zinc nitrate hexahydrate molar concentration is
The zinc nitrate hexahydrate methanol solution of 9.85mM, the 2-methylimidazole methanol solution that 2-methylimidazole molar concentration is 79.05mM；So
Zinc nitrate hexahydrate methanol solution is poured into rapidly in 2-methylimidazole methanol solution afterwards, magnetic agitation is reacted at room temperature
1h, after reaction, centrifugal treating simultaneously wash 3 times with methanol, dry at 50 °C, obtain metal organic frame ZIF-8；
(1-2) metal organic frame ZIF-8 is milled after in 500 DEG C of temperature lower calcinations, heating rate is 8 DEG C/min, is protected
The warm time is 5h, obtains ZnO nano powder；
(2) preparation of ZnO slurry
2.8g ethyl cellulose (46cp), 2.2g ethyl cellulose (10cp) and 3g terpinol are completely dissolved in 10mL
Mixed solution is formed in ethyl alcohol；It weighs 1g ZnO nano powder and pours into above-mentioned mixed solution, vibrate ultrasound after 5min
20min, repeats to make ZnO nano powder be uniformly dispersed in mixed solution the process 4 times；Then rotary evaporation at a temperature of 75 DEG C
ZnO slurry is obtained after 30min；
(3) preparation of ZnO photo-anode film
The ZnO slurry for scratching 4 layers of tape thickness using scraper method heats in 120 DEG C of heating plates to FTO substrate surface
It is put into electric furnace and calcines after 5min, first rise to 350 DEG C with the heating rate of 8 DEG C/min, keep the temperature after 1h with the heating of 8 DEG C/min
Rate rises to 450 DEG C, keeps the temperature Temperature fall after 30min, obtains the light for being attached in conductive substrates, being made of ZnO nano powder
Anode film.
As shown in Figure 1, the particle size of the present embodiment ZnO nano powder is 50nm.As shown in Fig. 2, the present embodiment light anode
Film with a thickness of 30 μm, film thickness can increase with the increase of the adhesive tape number of plies；And photo-anode film is made of ZnO nano powder.
Embodiment two:
A kind of preparation method of the photo-anode film based on ZnO nano powder of the present embodiment, its step are as follows:
(1) metal organic frame ZIF-8 is calcined and obtains ZnO nano powder
The preparation of (1-1) metal organic frame ZIF-8: 5.86g zinc nitrate hexahydrate and 12.98g 2-methylimidazole point are weighed
It is not placed in two beakers, is separately added into 200mL methanol, magnetic agitation dissolution, obtaining zinc nitrate hexahydrate molar concentration is
The zinc nitrate hexahydrate methanol solution of 19.70mM, the 2- methylimidazole methanol that 2-methylimidazole molar concentration is 158.10mM are molten
Liquid；Then zinc nitrate hexahydrate methanol solution is poured into rapidly in 2-methylimidazole methanol solution, at room temperature magnetic agitation
It reacts 1h, after reaction, centrifugal treating and washs 3 times, drying at a temperature of 60 DEG C with methanol, obtain metal organic frame
ZIF-8；
(1-2) metal organic frame ZIF-8 is milled after in 550 DEG C of temperature lower calcinations, heating rate is 8 DEG C/min, is protected
The warm time is 5h, obtains ZnO nano powder；
(2) preparation of ZnO slurry
2.8g ethyl cellulose (46cp), 2.2g ethyl cellulose (10cp) and 3.5g terpinol are completely dissolved in 10mL
Mixed solution is formed in alcohol solvent；It weighs 1.2g ZnO nano powder and pours into above-mentioned mixed solution, surpass after vibrating 5min
Sound 20min, repeats to make ZnO nano powder be uniformly dispersed in mixed solution the process 4 times；Then rotary evaporation at a temperature of 70 DEG C
ZnO slurry is obtained after 50min；
(3) preparation of ZnO photo-anode film
The ZnO slurry for scratching 4 layers of tape thickness using scraper method heats in 100 DEG C of heating plates to FTO substrate surface
It is put into electric furnace and calcines after 5min, first rise to 350 DEG C with the heating rate of 8 DEG C/min, keep the temperature after 1h with the heating of 8 DEG C/min
Rate rises to 450 DEG C, keeps the temperature Temperature fall after 30min, obtains the light for being attached in conductive substrates, being made of ZnO nano powder
Anode film.
Embodiment three:
A kind of preparation method of the photo-anode film based on ZnO nano powder of the present embodiment, its step are as follows:
(1) metal organic frame ZIF-8 is calcined and obtains ZnO nano powder
The preparation of (1-1) metal organic frame ZIF-8: 8.80g zinc nitrate hexahydrate and 12.98g 2-methylimidazole point are weighed
It is not placed in two beakers, is separately added into 200mL methanol, magnetic agitation dissolution, obtaining zinc nitrate hexahydrate molar concentration is
The zinc nitrate hexahydrate methanol solution of 29.58mM, the 2- methylimidazole methanol that 2-methylimidazole molar concentration is 237.15mM are molten
Liquid；Then zinc nitrate hexahydrate methanol solution is poured into rapidly in 2-methylimidazole methanol solution, at room temperature magnetic agitation
It reacts 1h, after reaction, centrifugal treating and washs 3 times, drying at a temperature of 70 DEG C with methanol, obtain metal organic frame
ZIF-8；
(1-2) metal organic frame ZIF-8 is milled after in 600 DEG C of temperature lower calcinations, heating rate is 8 DEG C/min, is protected
The warm time is 5h, obtains ZnO nano powder；
(2) preparation of ZnO slurry
2.8g ethyl cellulose (46cp), 2.2g ethyl cellulose (10cp) and 4g terpinol are completely dissolved in 10mL
Mixed solution is formed in alcohol solvent；It weighs 1.5g ZnO nano powder and pours into above-mentioned mixed solution, surpass after vibrating 5min
Sound 20min, repeats to make ZnO nano powder be uniformly dispersed in mixed solution the process 4 times；Then rotary evaporation at a temperature of 80 DEG C
ZnO slurry is obtained after 25min；
(3) preparation of ZnO photo-anode film
The ZnO slurry for scratching 4 layers of tape thickness using scraper method heats in 80 DEG C of heating plates to FTO substrate surface
It is put into electric furnace and calcines after 5min, first rise to 350 DEG C with the heating rate of 8 DEG C/min, keep the temperature after 1h with the heating of 8 DEG C/min
Rate rises to 450 DEG C, keeps the temperature Temperature fall after 30min, obtains the light for being attached in conductive substrates, being made of ZnO nano powder
Anode film.
Using photo-anode film obtained by the embodiment of the present invention, dye-sensitized solar cells is made in accordance with the following methods:
The ZnO photo-anode film that will be cooled to room temperature after calcining, the room temperature immersion 2h in 0.05mM N719 dyestuff take out light
Anode film rinses the N719 dyestuff on surface with dehydrated alcohol, and photo-anode film and the pyrolysis of N719 dyestuff then will have been adsorbed after drying
The FTO of platinum forms open sandwich structure battery to electrode.In photo-anode film and to electrolyte is added dropwise between electrode, it is electrolysed
The group of liquid become 0.6M 1- butyl -3- methylimidazole salt compounded of iodine, 0.06M LiI, 0.03M I2,0.5M 4- tert .-butylpyridine and
The acetonitrile solution of 0.1M guanidinium isothiocyanate.The J-V curve obtained after test is as shown in Figure 3, and the photoelectricity of battery is obtained after calculating
Transfer efficiency is 2.85%, shows that the ZnO photo-anode film of preparation of the embodiment of the present invention is suitable for dye-sensitized solar cells.
Claims (6)
1. a kind of preparation method based on ZnO nano powder photo-anode film, it is characterised in that the following steps are included:
(1) metal organic frame ZIF-8 obtains to partial size is 30~100nm, pattern is in 450~750 DEG C of temperature lower calcinations
Irregular spherical ZnO nano powder；Wherein, the metal organic frame ZIF-8's the preparation method is as follows:
Zinc nitrate hexahydrate and 2-methylimidazole are dissolved separately in methanol solvate and stirred evenly, zinc nitrate hexahydrate is respectively obtained
The 2- first that the molar concentration of zinc nitrate hexahydrate methanol solution and 2-methylimidazole that molar concentration is 9~30mM is 72~240mM
Base imidazolemethanol solution；Then the zinc nitrate hexahydrate methanol solution is poured into 2-methylimidazole methanol solution, is stirred at room temperature
It mixes and is centrifuged after 1~3h of reaction, washs, dry, obtain metal organic frame ZIF-8；
(2) the ZnO nano powder is dispersed in the mixed solution being made of ethyl cellulose, terpinol and alcohol solvent,
Wherein the ethyl cellulose is 10cp ethyl cellulose and 46cp ethyl cellulose, the 10cp ethyl cellulose, 46cp second
The mass-volume concentration of base cellulose, terpinol in alcohol solvent is respectively 0.1~0.5g/cm3, the ZnO nano powder exists
Shared mass percent concentration is 1~10wt% in mixed solution；Then the rotary evaporation after vibrating and is ultrasonic obtains ZnO slurry
Material；
(3) the ZnO slurry be coated in conductive substrates surface, calcined after heating, obtain be attached in conductive substrates, by
The photo-anode film that the ZnO nano powder that partial size is 30~100nm forms, photoelectric conversion efficiency 2.85%.
2. the preparation method according to claim 1 based on ZnO nano powder photo-anode film, it is characterised in that: the step
(2) time vibrated in is 5~10min；The time of ultrasound is 20~40min；The cycle-index of oscillation and ultrasound is 3~5 times；
The temperature of the rotary evaporation is 70~80 DEG C, and the time is 25~60min.
3. the preparation method according to claim 1 based on ZnO nano powder photo-anode film, it is characterised in that: the step
(3) ZnO slurry is coated in conductive substrates surface with a thickness of 7~35 μm in；Heating temperature is 80~120 DEG C；Calcination temperature is
350~450 DEG C.
4. the preparation method according to claim 1 based on ZnO nano powder photo-anode film, it is characterised in that: the metal
In the preparation method of organic frame ZIF-8, drying temperature is 50~70 DEG C.
5. utilizing photo-anode film made from the preparation method based on ZnO nano powder photo-anode film described in one of claim 1-4.
6. according to claim 5 be based on ZnO nano powder photo-anode film, it is characterised in that: the thickness of the photo-anode film
It is 7~35 μm, the partial size of the ZnO nano powder is 30~100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610980589.5A CN106449099B (en) | 2016-11-08 | 2016-11-08 | A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610980589.5A CN106449099B (en) | 2016-11-08 | 2016-11-08 | A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106449099A CN106449099A (en) | 2017-02-22 |
| CN106449099B true CN106449099B (en) | 2019-05-14 |
Family
ID=58207909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610980589.5A Expired - Fee Related CN106449099B (en) | 2016-11-08 | 2016-11-08 | A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106449099B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109243829B (en) * | 2018-09-19 | 2021-04-13 | 东莞理工学院 | Dye-sensitized cell electrode, preparation method thereof and application of MIL-47 material |
| CN111185150A (en) * | 2020-01-18 | 2020-05-22 | 温州大学 | Preparation method for preparing ZnO crystal based on ZIF-8 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9214288B2 (en) * | 2013-09-05 | 2015-12-15 | National Cheng Kung University | Flexible photo-anode of dye-sensitized solar cell and manufacturing method thereof |
| CN103854865B (en) * | 2014-03-21 | 2016-08-17 | 武汉理工大学 | ZnO/TiO for light anode material2composite and preparation method thereof |
| CN104021942B (en) * | 2014-06-12 | 2016-10-05 | 福州大学 | A kind of method improving Zinc oxide-base DSSC photoelectric properties |
-
2016
- 2016-11-08 CN CN201610980589.5A patent/CN106449099B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106449099A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107068872B (en) | It is a kind of to prepare perovskite Cs3Bi2I9The method of hull cell | |
| CN104393103B (en) | A kind of Cu2ZnSnS4The preparation method of semiconductive thin film and application thereof | |
| CN104241447B (en) | Method for preparing copper, zinc, tin and sulfur film material | |
| CN102153138B (en) | Graded titanium dioxide microspheres consisting of nano rods and nano granules | |
| CN104021942B (en) | A kind of method improving Zinc oxide-base DSSC photoelectric properties | |
| CN102723208B (en) | Preparation method of composite nanowire array with one-dimensional ZnO(zinc oxide)-TiO2(titanium dioxide) core-shell structure | |
| CN105498773A (en) | Preparation method for doped iron oxide nanorod catalyst | |
| CN109841740A (en) | A kind of preparation method of the perovskite solar cell based on nickel oxide hole transmission layer | |
| WO2016026339A1 (en) | Synthesis method for tio2 nanocrystal | |
| CN104377036B (en) | Method for preparing AgInS2 quantum dot sensitized TiO2 photoelectrode with In2S3 used as buffer layer | |
| CN104810480A (en) | Preparation method for thin titanium dioxide layer of perovskite cell | |
| CN108281550B (en) | Based on the titania-doped perovskite solar battery and preparation method thereof of magnesium | |
| CN104952626B (en) | It is a kind of nanocrystalline to electrode and preparation method thereof | |
| CN105810832A (en) | Perovskite solar cell optimized based on oxide with excellent conductivity | |
| CN104952627A (en) | Quantum dot sensitized solar battery and preparation method thereof | |
| CN106449099B (en) | A kind of preparation method and photo-anode film based on ZnO nano powder photo-anode film | |
| CN106629830B (en) | A kind of zinc titanate nano-material and its application in perovskite solar cell | |
| CN105244168B (en) | The preparation method of a kind of ZnO nano sheet thin film with multilevel hierarchy and prepared thin film thereof | |
| CN103258647B (en) | The preparation method of dye-sensitized cell titanium dioxide photo anode and application thereof | |
| CN105244171B (en) | A kind of fabricated in situ ZnO nano piece photo-anode film and preparation method thereof | |
| CN108878657A (en) | A kind of preparation method of high-efficient carbon based perovskite solar battery | |
| CN102005303B (en) | Method for preparing SiO2-modified ZnO nano-porous thin film composite electrode | |
| CN104393069B (en) | Titanium dioxide nanocrystal particle, manufacturing method thereof, and applications to solar cell | |
| CN107946079B (en) | Preparation of flexible full-printing quantum dot sensitized solar cell | |
| CN107946077A (en) | Preparation method for quantum dot sensitized solar cell nanometer club shaped structure light anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190514 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |