CN105244171B - A kind of fabricated in situ ZnO nano piece photo-anode film and preparation method thereof - Google Patents
A kind of fabricated in situ ZnO nano piece photo-anode film and preparation method thereof Download PDFInfo
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- CN105244171B CN105244171B CN201510700819.3A CN201510700819A CN105244171B CN 105244171 B CN105244171 B CN 105244171B CN 201510700819 A CN201510700819 A CN 201510700819A CN 105244171 B CN105244171 B CN 105244171B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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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- 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
Abstract
The invention discloses a kind of fabricated in situ ZnO nano piece photo-anode films and preparation method thereof, by using the zinc nitrate hexahydrate and hexamethylenetetramine aqueous solution of high concentration, and by extending the hydrothermal synthesis reaction time, there is the ZnO nano piece dye-sensitized solar cell anode film of multilevel hierarchy using hydrothermal synthesis method fabricated in situ.ZnO nano piece film prepared by the present invention has following features：Prepared two-dimentional ZnO nano piece shortens the transmission path of light induced electron；There is prepared ZnO nano piece film micropore, micropore to be conducive to diffusion of the electrolyte in nanometer sheet film；Prepared ZnO nano piece film has a large amount of mesoporous, mesoporous specific surface areas for increasing ZnO nano piece film, is conducive to increase Dye Adsorption amount, to increase the short circuit current of battery.It is high that the obtained photo-anode film of the present invention is assembled into dye-sensitized solar cells electricity conversion.The present invention also has many advantages, such as that reaction temperature is low, technical process is simple, equipment is simple and at low cost.
Description
Technical field
The present invention relates to technical field of solar batteries, especially a kind of fabricated in situ ZnO nano piece photo-anode film and its
Preparation method.
Background technology
Currently, research and most widely used solar cell be mainly silicon systems solar cell, but due to its is of high cost,
Complex process, energy consumption be big, the problems such as can cause environmental pollution in production process, to limit its extensive use.1991,Deng reporting dye-sensitized solar cells (Dye Sensitized of the photoelectric conversion efficiency up to 7.9% for the first time
Solar Cell, abbreviation DSSC), start the uncharted field of solar cell research and development.DSSC by light anode, to electricity
Several parts such as pole, dye sensitizing agent, conductive substrates, electrolyte are constituted, and wherein light anode is the core component of DSSC.Nano-ZnO
Material is a kind of important DSSC light anode materials, currently obtains and answers general research.There are many ZnO of different-shape to apply
In DSSC, such as ZnO nanorod, multilevel hierarchy ZnO microsphere, ZnO nano grain, ZnO nano-wire and ZnO composite constructions.Tool
There is the ZnO nano piece of multilevel hierarchy to increase dyestuff suction due to larger specific surface area and good pore channel, being conducive to
Attached amount, the diffusion of electrolyte and electronics transmission, therefore be conducive to the raising of efficiency of dye-sensitized solar battery.
Preparing ZnO nano piece photo-anode film main method has electrochemical deposition method and chemical bath deposition method at present, wherein electricity
The film that chemical deposition obtains is relatively thin.Chemical bath deposition method mainly using two water zinc acetates/methanol, zinc nitrate hexahydrate/
Urea is starting reaction system, both reaction systems can prepare the porous ZnO nanometer sheet of vertical conduction substrate.Six water nitric acid
Zinc/hexamethylenetetramine water solution system is widely used in the growth of ZnO nanorod, because ZnO is polar crystal, liquid phase method
When synthesizing ZnO, growth unit [Zn (OH)4]2-It is easy to assemble on positive polarity face, pushes ZnO crystal quick along c-axis direction
Growth so that ZnO crystal easily present it is rodlike.But the specific surface area of ZnO nanorod light anode is smaller, adsorbs amount of dye
It is low, to limit the photoelectric conversion rate of ZnO nanorod DSSC.
Invention content
The invention aims to solve the deficiency of prior art problem, a kind of fabricated in situ ZnO nano piece light sun is provided
Pole film and preparation method thereof, using zinc nitrate hexahydrate/hexamethylenetetramine aqueous solution of high concentration, and by extending hydrothermal synthesis
Reaction time makes the ZnO sticks of growth be redissolved then synthesis ZnO nano piece.
In order to achieve the above objectives, the present invention is implemented according to following technical scheme：
A kind of fabricated in situ ZnO nano piece photo-anode film, including FTO electro-conductive glass further include being located at FTO electro-conductive glass
The ZnO nano lamella formed that is staggeredly stacked by ZnO nano piece on conductive layer, it is interlaced between the ZnO nano piece, stack
Form micropore.
Further, the ZnO nano piece is made of ZnO nano particle, a diameter of 20~25nm of ZnO particle, described
It is furnished between the ZnO nano particle of ZnO nano on piece mesoporous.
A kind of preparation method of fabricated in situ ZnO nano piece photo-anode film, includes the following steps：
1) preparation of growth-promoting media：Zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in 25 DEG C of deionized water, and will
Solution stirs evenly to get growth-promoting media, and zinc nitrate hexahydrate is identical with the concentration of hexamethylenetetramine in aqueous solution in growth-promoting media；
2) preparation of ZnO nano piece film：The conducting surface of the FTO electro-conductive glass cleaned up is downwardly inclined and is positioned over hydro-thermal
In reaction kettle, the growth-promoting media prepared is moved into hydrothermal reaction kettle, and the liquid level of growth-promoting media is higher than FTO electro-conductive glass highests
Point；Hydrothermal reaction kettle is placed on and has been heated to carry out 72~144h of hydro-thermal reaction in 90~120 DEG C of baking oven, after reaction will
Reaction kettle takes out, and takes out the growth in situ FTO electro-conductive glass of film, with deionized water flushing membrane surface, to remove
Responseless growth-promoting media, then dries film, then the film after drying is calcined, and ZnO nano piece light anode is obtained after calcining
Film.
As present invention further optimization scheme, it is 100~120 DEG C that temperature, which is dried, in film in the step 2).
As present invention further optimization scheme, it is 250~450 DEG C that film, which is carried out calcination temperature, in the step 2).
As present invention further optimization scheme, heating rate is 8 DEG C/min when calcining in the step 2).
It as present invention further optimization scheme, is kept the temperature after being calcined film in the step 2), when heat preservation
Between be 30~120min
Compared with prior art, the invention has the advantages that：
(1) zinc nitrate hexahydrate and hexamethylenetetramine is used only as reaction raw materials in the present invention, is synthesized using low-temperature hydrothermal
Method, reaction temperature is low, technical process is simple, equipment is simple, at low cost；
(2) photo-anode film produced by the present invention is this by being formed by film with the unordered stacking of multilevel hierarchy ZnO nano piece
ZnO nano piece film exists simultaneously two kinds of pore structures：One is interlaced between nanometer sheet and nanometer sheet, stacking formation micro-
Hole；Another kind is to be clouded in mesoporous in nanometer sheet, and micropore is conducive to diffusion of the electrolyte in nanometer sheet film；It is mesoporous to increase
The specific surface area of ZnO nano piece film is conducive to increase Dye Adsorption amount, to increase the short circuit current of battery.ZnO of the present invention receives
Rice this structure of piece film is as the advantage of DSSC working electrodes：A. relative to the light sun being made of completely ZnO nano particle
Pole, in ZnO meso-porous nano chip architectures, light induced electron can directly be transmitted along two-dimensional nano piece, improve the collection of light induced electron
Efficiency；B. the densely covered mesoporous specific surface area for substantially increasing nanometer sheet, to increase Dye Adsorption amount and photogenerated current；
C. micron-sized gap is penetrated into convenient for electrolyte between nanometer sheet.Therefore, the ZnO nano piece of double pores system of the present invention is conducive to
The absorption of dyestuff, the infiltration of electrolyte and electronics light anode/dyestuff/electrolyte interface transmission, to obtain higher light
Photoelectric transformation efficiency.
Description of the drawings
Fig. 1 is the structural schematic diagram of the ZnO nano piece film of the present invention；
Fig. 2 is the vertical view of the ZnO nano piece film of the present invention；
Fig. 3 is the cross-section diagram of the field emission scanning electron microscope (FESEM) of ZnO nano piece film of the present invention；
Fig. 4 is the exterior view of the field emission scanning electron microscope (FESEM) of ZnO nano piece film of the present invention；
Fig. 5 is that the present invention is assembled into the I-V curve tested after battery.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, in the illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment one
A kind of preparation process of ZnO nano piece dye-sensitized solar cell anode film of the present embodiment is as follows：
(1) preparation of growth-promoting media
The deionized water that 140ml is measured with graduated cylinder is poured into beaker, sequentially adds 8.32g into beaker under magnetic stirring
Zinc nitrate hexahydrate and 3.92g hexamethylenetetramines, are stirred at 25 DEG C, and solution is stirred evenly up to growth-promoting media；Six water nitric acid
The concentration of zinc and hexamethylenetetramine in aqueous solution is 0.2M；
(2) preparation of multistage ZnO nano piece film
The electro-conductive glass conducting surface cleaned up is tilted down and is put into the hydrothermal reaction kettle that volume is 200ml, then
140ml growth-promoting medias are poured into hydrothermal reaction kettle, the volume filling rate of hydrothermal reaction kettle is 70%, then puts hydrothermal reaction kettle
Enter to be heated to carry out hydro-thermal reaction in 90 DEG C of baking oven.The hydro-thermal reaction time is 144h.After hydro-thermal reaction, by reaction kettle
It takes out, waits for that temperature of reaction kettle is down to 25 DEG C of room temperature, take the film out, film is rinsed with deionized water.Film is dried at 120 DEG C
It is dry, it is then calcined in Muffle furnace, calcination temperature is 350 DEG C, soaking time 30min, and calcining heating rate is 8 DEG C/min；
To obtain ZnO nano piece photo-anode film.
Embodiment two
A kind of preparation process of ZnO nano piece dye-sensitized solar cell anode film of the present embodiment is as follows：
(1) preparation of growth-promoting media
The deionized water that 140ml is measured with graduated cylinder is poured into beaker, sequentially adds 8.32g into beaker under magnetic stirring
Zinc nitrate hexahydrate and 3.92g hexamethylenetetramines, are stirred at 25 DEG C, and solution is stirred evenly up to growth-promoting media；Six water nitric acid
The concentration of zinc and hexamethylenetetramine in aqueous solution is 0.2M；
(2) preparation of multistage ZnO nano piece film
The electro-conductive glass conducting surface cleaned up is tilted down and is put into the hydrothermal reaction kettle that volume is 200ml, then
140ml growth-promoting medias are poured into hydrothermal reaction kettle, the volume filling rate of hydrothermal reaction kettle is 70%, then puts hydrothermal reaction kettle
Enter to be heated to carry out hydro-thermal reaction in 90 DEG C of baking oven.The hydro-thermal reaction time is 72h.After hydro-thermal reaction, by reaction kettle
It takes out, waits for that temperature of reaction kettle is down to 25 DEG C of room temperature, there is the electro-conductive glass of film to take out growth, film is rinsed with deionized water.It will
Film is dried at 120 DEG C, is then calcined in Muffle furnace, and calcination temperature is 350 DEG C, soaking time 30min, calcining heating
Rate is 8 DEG C/min；To obtain ZnO nano piece photo-anode film.
Embodiment three
A kind of preparation process of ZnO nano piece dye-sensitized solar cell anode film of the present embodiment is as follows：
(1) preparation of growth-promoting media
The deionized water that 140ml is measured with graduated cylinder is poured into beaker, sequentially adds 8.32g into beaker under magnetic stirring
Zinc nitrate hexahydrate and 3.92g hexamethylenetetramines stir at a temperature of 25 DEG C, and solution is stirred evenly up to growth-promoting media；Six water
The concentration of zinc nitrate and hexamethylenetetramine in aqueous solution is 0.2M；
(2) preparation of multistage ZnO nano piece film
The electro-conductive glass conducting surface cleaned up is tilted down and is put into the hydrothermal reaction kettle that volume is 200ml, then
140ml growth-promoting medias are poured into hydrothermal reaction kettle, the volume filling rate of hydrothermal reaction kettle is 70%, then puts hydrothermal reaction kettle
Enter to be heated to carry out hydro-thermal reaction in 120 DEG C of baking oven.The hydro-thermal reaction time is 72h.After hydro-thermal reaction, by reaction kettle
It takes out, waits for that temperature of reaction kettle is down to 25 DEG C of room temperature, there is the electro-conductive glass of film to take out growth, film is rinsed with deionized water.It will
Film is dried at 120 DEG C, is then calcined in Muffle furnace, and calcination temperature is 250 DEG C, soaking time 30min, calcining heating
Rate is 8 DEG C/min；To obtain ZnO nano piece photo-anode film.
Example IV
A kind of preparation process of ZnO nano piece dye-sensitized solar cell anode film of the present embodiment is as follows：
(1) preparation of growth-promoting media
The deionized water that 140ml is measured with graduated cylinder is poured into beaker, is sequentially added under magnetic stirring into beaker
16.65g zinc nitrate hexahydrates and 7.85g hexamethylenetetramines, are stirred at 25 DEG C, and solution is stirred evenly up to growth-promoting media；Six
The concentration of water zinc nitrate and hexamethylenetetramine in aqueous solution is 0.4M；
(2) preparation of multistage ZnO nano piece film
The electro-conductive glass conducting surface cleaned up is tilted down and is put into the hydrothermal reaction kettle that volume is 200ml, then
140ml growth-promoting medias are poured into hydrothermal reaction kettle, the volume filling rate of hydrothermal reaction kettle is 70%, then puts hydrothermal reaction kettle
Enter to be heated to carry out hydro-thermal reaction in 90 DEG C of baking oven.The hydro-thermal reaction time is 144h.After hydro-thermal reaction, by reaction kettle
It takes out, waits for that temperature of reaction kettle is down to 25 DEG C of room temperature, there is the electro-conductive glass of film to take out growth, film is rinsed with deionized water.It will
Film is dried at 120 DEG C, is then calcined in Muffle furnace, and calcination temperature is 350 DEG C, soaking time 30min, calcining heating
Rate is 8 DEG C/min；To obtain ZnO nano piece photo-anode film.
Referring to the photo-anode film obtained by Fig. 1, Fig. 2, Fig. 3 and Fig. 4 embodiment of the present invention by further including being located at FTO conduction glass
The ZnO nano lamella 2 formed that is staggeredly stacked by ZnO nano piece on the conductive layer of glass 1, is mutually handed between the ZnO nano piece
Wrong, stacking forms micropore 3.ZnO nano piece is made of ZnO nano particle 4, and the diameter of ZnO particle 4 is 20~25nm, ZnO
It is furnished with mesoporous 5 between ZnO nano particle 4 in nanometer sheet.
Photo-anode film prepared by the present invention is since there are micropores and mesoporous in structure, while electronics passes between two-dimensional nano piece
Defeated fast compound few feature, so the performance of battery is as shown in figure 5, the dye sensitization sun is made in the ZnO photo-anode film of the present invention
Can battery the specific steps are：The ZnO photo-anode film of postcooling to 80 DEG C will be calcined, in 0.05mM N719 dyestuffs at room temperature
2h is impregnated, the N719 dyestuffs that photo-anode film rinses surface with absolute ethyl alcohol is taken out, N719 dyestuffs then will have been adsorbed after drying
The FTO of photo-anode film and pyrolysis platinum forms electrode on open sandwich structure battery.It is dripped in light anode and between electrode
Liquid electrolyte, the group of liquid electrolyte is added to become 0.6M 1- butyl -3- methylimidazoles salt compounded of iodine, 0.06M LiI, 0.03M I2、
The acetonitrile solution of 0.5M 4- tert .-butylpyridines and 0.1M guanidinium isothiocyanates.
Technical scheme of the present invention is not limited to the limitation of above-mentioned specific embodiment, every to do according to the technique and scheme of the present invention
The technology deformation gone out, each falls within protection scope of the present invention.
Claims (1)
1. a kind of preparation method of fabricated in situ ZnO nano piece photo-anode film, which is characterized in that include the following steps：
1) preparation of growth-promoting media：Zinc nitrate hexahydrate and hexamethylenetetramine are dissolved in 25 DEG C of deionized water, and by solution
It stirs evenly to get growth-promoting media, zinc nitrate hexahydrate is identical with the concentration of hexamethylenetetramine in aqueous solution in growth-promoting media；
2) preparation of ZnO nano piece film：The conducting surface of the FTO electro-conductive glass cleaned up is downwardly inclined and is positioned over hydro-thermal reaction
In kettle, the growth-promoting media prepared is moved into hydrothermal reaction kettle, and the liquid level of growth-promoting media is higher than FTO electro-conductive glass peaks；
Hydrothermal reaction kettle is placed on and has been heated to carry out 72~144h of hydro-thermal reaction in 90~120 DEG C of baking oven, it after reaction will be anti-
It answers kettle to take out, and takes out the growth in situ FTO electro-conductive glass of film, with deionized water flushing membrane surface, do not have to remove
The growth-promoting media for having reaction, then dries film, and drying temperature is 100~120 DEG C, then the film after drying is calcined, liter when calcining
Warm rate is 8 DEG C/min, and calcination temperature is 250~450 DEG C, is kept the temperature after calcining, and soaking time is 30~120min, heat preservation
Terminate to obtain ZnO nano piece photo-anode film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106381513A (en) * | 2016-08-31 | 2017-02-08 | 昆明理工大学 | Preparation method and application of multi-stage nanosheet zinc oxide |
| CN109872877B (en) * | 2019-02-28 | 2021-04-13 | 江苏赛清科技有限公司 | ZnO photo-anode of dye-sensitized solar cell and preparation method thereof |
| CN109879607A (en) * | 2019-03-28 | 2019-06-14 | 中国民航大学 | The preparation method of the modified hydrophobic automatically cleaning film of ZnO/ZnS nano-chip arrays |
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Non-Patent Citations (2)
| Title |
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| A Facile Template-free Route to Synthesize Porous ZnO Nanosheets with High Surface Area;Hu X et.al.;<Journal of Alloys and Compounds>;20131231;373-376 * |
| 垂直导电衬底的ZnO纳米片的制备及其染料敏化太阳电池的性能;王艳香 等;《人工晶体学报》;20151015;第44卷(第10期);第2828-2846页 * |
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