CN102583506A - Preparation method and use of porous micro/nano grading structure ZnO spheres - Google Patents
Preparation method and use of porous micro/nano grading structure ZnO spheres Download PDFInfo
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- CN102583506A CN102583506A CN2012100538015A CN201210053801A CN102583506A CN 102583506 A CN102583506 A CN 102583506A CN 2012100538015 A CN2012100538015 A CN 2012100538015A CN 201210053801 A CN201210053801 A CN 201210053801A CN 102583506 A CN102583506 A CN 102583506A
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Abstract
The invention relates to a preparation method of porous micro/nano grading structure ZnO spheres. The preparation method comprises the following steps: 1, adding zinc nitrate hexahydrate and urea to water according to a molar ratio of 1:3-1:6, and uniformly dispersing them; 2, putting the obtained solution into an autoclave, and reacting for 1-6h at 100-180DEG C; 3, allowing the obtained product to stand to room temperature, and sequentially washing, drying and filtering the product to obtain a precipitate; and 4, calcining the precipitate for 30-60min at 300-500DEG C to obtain the porous micro/nano grading structure ZnO spheres. The morphologies of the prepared porous micro/nano grading structure ZnO spheres are spheres assembled by nanoscale porous ZnO sheets, and the structure is benefit for the electrolyte transmission and the light scattering, so the photoelectric conversion efficiency of DSSC (dye sensitized solar cell) is improved.
Description
Technical field
The present invention relates to a kind of porous little/receive hierarchy the ZnO ball the preparation method and as the application of dye-sensitized cell (DSSC) optoelectronic pole, belong to new material technology field.
Background technology
Along with energy dilemma and problem of environmental pollution are more and more serious; Various circles of society are to the sustainable development pay attention to day by day of energy consumption; Especially caused national governments to concern and favor cleaning, renewable energy source, novel energy becomes international academic community and various countries are studied, the emphasis of exploitation.Sun power has the incomparable advantage of other energy as a kind of renewable energy source, and is inexhaustible, nexhaustible, safe, pollution-free, do not receive the restriction of geographical conditions etc., makes one of its main direction that becomes the new forms of energy development
In recent years, people have been developed a kind of solar cell of novelty---dye sensitization solar battery (DSSC).Its preparation technology is simple, the starting material source is abundant, with low cost, has higher market outlook and popularizes value, is described as third generation solar cell.Therefore, dye sensitization solar battery also is considered to become the leading of following solar cell.Dye sensitization solar battery belongs to photoelectrochemical cell, and its structure mainly can be divided into 3 parts: negative pole (working electrode), ionogen and counter electrode.On conductive substrates, prepare one deck nano-crystal oxide semiconductor film, and then dye molecule is adsorbed in the semiconductor film, so just constitute negative pole (cathode), i.e. working electrode.Anodal (anode) generally is the conductive glass of deposition platinum.Ionogen and comprises redox couple between positive pole and negative pole, the most frequently used redox couple is I
3-/ I
-Working electrode and counter electrode are assembled into after battery injects ionogen, draw lead from electrode and receive load and produce voltage and current.
But this battery also is faced with the lower problem of photoelectric transformation efficiency at present, and its major cause is: the nanocrystalline ionogen that is unfavorable for of (1) atresia transmits in film.(2) scattering power of film a little less than, cause photon and combination of dyes efficient relatively poor.Therefore, in the preparation of dye-sensitized solar cells, need: the structure that (1) is synthesizing porous helps the transmission of ionogen in film; (2) synthetic special microstructure strengthens the scattering of light ability.
In sum, developing the little/hierarchical Z nO ball of receiving with vesicular structure has great importance to the electricity conversion that improves dye-sensitized solar cells.
Summary of the invention
The object of the present invention is to provide a kind of preparation porous little/receive hierarchical Z nO ball method; The present invention also aims to provide a kind of porous little/receive the purposes of hierarchical Z nO ball; Prepared product helps the transmission of ionogen in film with its unique pattern; Scattering of light has improved the optoelectronic transformation efficiency of DSSC.
That the present invention proposes a kind of preparation porous is little/receive hierarchical Z nO ball method, and be that solvent reacts under 120 ℃ lesser temps with water, cardinal principle is following:
5Zn
2?+?+2CO(NH
2)
2?+?6OH
-+?4H
2O?=?Zn
5(OH)
6(CO
3)
2+?4NH
4 ?+
Zn
5(OH)
6(CO
3)
2=?ZnO?+?4H
2O?+?CO
2↑
Technical scheme of the present invention is: the preparation porous is little/receive hierarchical Z nO ball method, and at first zinc nitrate hexahydrate, urea are added in the entry, be uniformly dispersed; Put into autoclave 100 ~ 180 ℃ of reactions down, wherein, zinc nitrate hexahydrate: the mol ratio of urea is 1:3 ~ 1:6, and the reaction times is 1 ~ 6 hour; Be placed into room temperature then, washing successively, drying is filtered to obtain deposition;
The gained deposition is through calcining (in retort furnace, calcining).300 ~ 500 ℃ of down calcinings 30 ~ 60 minutes, obtain porous little/receive the ZnO ball of hierarchy; As preferred version, said zinc nitrate hexahydrate: the mol ratio of urea is 1:3, and the said reaction times is 2-4h, and calcining temperature is 500 ℃, and calcination time is 30 minutes.
Especially put into autoclave and react 3h down at 115 ~ 125 ℃.
Porous is little/receive the application of ZnO ball of hierarchy; It is characterized in that with the porous of preparation little/receive hierarchical Z nO ball as the DSSC optoelectronic pole: under the room temperature condition; With absolute ethyl alcohol and 0.1g porous little/the hierarchical Z nO ball of receiving is ground to pulpous state in mortar; The ZnO of pulpous state is transferred in the beaker of a 50ml, stirred ultrasonic 10 minutes 10 minutes; After adding the TKK 021 of anhydrous Terpineol 350s of 2 grams and 4g, stir, ultrasonic respectively 10 minutes; 38 ℃ of condition underspins steam to the agglutination thing; Clean the adulterated White tin oxide FTO of fluorine conductive glass, use spread coating that made jelly is applied to FTO and process the film that thickness is 100 μ m; 125 ℃ of air dryings 2 hours, 450 ℃ of annealing 15 minutes down, 500 ℃ of following sintering 15 minutes, film immerses N719 ethanol electrolyte solution and soaks after 2-5 hour, processes the DSSC optoelectronic pole.
The invention has the beneficial effects as follows: to be solvent with water react being low to moderate under 120 ℃ the lesser temps this method, reduced the protection of production cost and enabling environment.Porous of the present invention is little/receive the purposes of hierarchical Z nO ball: and behind (1) glue it is applied on the conductive glass (FTO), bubble is gone in the dyestuff behind the certain hour, makes the optoelectronic pole of dye sensitization solar battery, and higher electricity conversion is arranged.Compare the present invention with traditional synthesis method and have following obvious advantage: the water that (1) this building-up process has only been used cheapness and toxicological harmless is not only protected environment as solvent, and is easy to recycle, and cost reduces significantly.(2) this process only relates to dissolving, filtration, and conventional unit operation such as stirring, and common laboratory all can be operated, and also is easy to realize suitability for industrialized production.(3) the prepared porous of the present invention little/receive hierarchical Z nO ball, be that nano level porous flake ZnO is assembled into sphere, this structure is more conducive to the transmission of electrolytic solution, scattering of light, thus improved the photoelectric transformation efficiency of DSSC.Has big application potential in photoelectricity conversion field.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1.
Fig. 2 is the sem photograph of the embodiment of the invention 1 product.
Fig. 3 is the transmission electron microscope picture of the embodiment of the invention 1 product.
Fig. 4 is the SEM figure of the embodiment of the invention 2 products.
Fig. 5 is the SEM figure of the embodiment of the invention 3 products.
Fig. 6 is the XRD figure of product among the present invention.
Fig. 7 is the SEM figure of Comparative Examples 1 product of the present invention.
Fig. 8 is the SEM figure of Comparative Examples 2 products of the present invention.
Fig. 9 is the SEM figure of Comparative Examples 3 products of the present invention.
Figure 10 is the SEM figure of Comparative Examples 4 products of the present invention.
Figure 11 be porous little/receive hierarchical Z nO ball IPCE and wavelength relationship graphic representation during as the DSSC optoelectronic pole.
Figure 12 be porous little/receive hierarchical Z nO ball I-V graph of relation during as the DSSC optoelectronic pole.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
(1) 0.4mol zinc nitrate hexahydrate, 1.2mol urea are added in the 30ml water, adopt magnetic agitation 0.5 ~ 1h, obtain colorless clear liquid;
(2) colorless clear liquid is poured in the 50ml teflon-lined stainless steel autoclave, be warming up to 120 ° of C, reaction 3h has reacted the back furnace cooling;
(3) with the reaction product spinning, obtain pressed powder, then use distilled water wash, dry 6 ~ 24h under 60 ° of C then puts into 500 ° of C of retort furnace calcining after 30 minutes down, and the porous that obtains white is little/receive hierarchical Z nO ball.
Adopt X ray optical diffraction (XRD), sem (SEM) and transmission electron microscope (TEM) that product is analyzed.
Fig. 1 is the XRD figure of embodiment 1 product, and the result shows that present embodiment 1 product is ZnO, has no impurity.
Fig. 2 is the SEM figure of embodiment 1 product, from figure, can know that the ZnO ball is assembled by porous ZnO sheet among the embodiment 1.The diameter of ZnO ball is 4 ~ 5 μ m, and size evenly.
Fig. 3 is the TEM figure of embodiment 1 product, and as can be seen from the figure, the diameter in the hole on the ZnO sheet is approximately 30 ~ 50nm.
Step and instance 1 are basic identical, and difference is: zinc nitrate hexahydrate: the mol ratio of urea is 1:6.
Product that makes and embodiment 1 basically identical, its sem photograph is as shown in Figure 4, but the ZnO sheet is comparatively sparse.
Step and instance 1 are basic identical, and difference is: the reaction times is 6 hours.
Product that makes and embodiment 1 basically identical, its sem photograph is as shown in Figure 5, but the diameter of ZnO ball is big slightly than instance 1, and size is not too even.
Comparative Examples 1
Step and instance 1 are basic identical, and difference is: the reaction times is 1 hour.
The XRD spectra of product is seen Fig. 6 (a), and this product is ZnO.
Fig. 7 is the ESEM picture of product, and the ZnO sheet of forming the ZnO ball is comparatively sparse, and the size of ball is not too even.
Comparative Examples 2
Step and instance 1 are basic identical, and difference is: temperature of reaction is 100 ℃.The XRD figure of product is seen Fig. 6 (b), and its composition is ZnO.
The ESEM picture of this product is as shown in Figure 8, and its pattern is the nanometer flower that nanometer sheet is assembled into, and the length of nanometer sheet is 8 ~ 10 μ m, and wide is 4 ~ 5 μ m.
Comparative Examples 3
Step and instance 1 are basic identical, and difference is: temperature of reaction is 180 ℃.The XRD figure of product is seen Fig. 6 (c), and its composition is ZnO.
The ESEM picture of this product is as shown in Figure 9, and its pattern is a porous nano-sheet.
Comparative Examples 4
Step and instance 1 are basic identical, and difference is: in retort furnace, do not calcine.
The XRD figure of product is seen Fig. 6 (d), and its composition is Zn
5(OH)
6(CO
3)
2
The ESEM picture of this product is shown in figure 10, and the product pattern is the ball that the nanometer sheet of atresia is formed.
Application examples
Porous with embodiment 1 preparation is little/receive hierarchical Z nO ball as the DSSC optoelectronic pole, survey its electricity conversion, be specially: under the room temperature condition, with absolute ethyl alcohol and 0.1g porous little/the hierarchical Z nO ball of receiving is ground to no big reunion in mortar till.The ZnO of pulpous state is transferred in the beaker of a 50ml, stirred ultrasonic 10 minutes 10 minutes.After adding the TKK 021 of anhydrous Terpineol 350s of 2 grams and 4g, stir, ultrasonic respectively 10 minutes.38 ℃ of condition underspins steam to the agglutination thing.
Use washing composition successively, dilute hydrochloric acid solution, Pottasium Hydroxide, ethanolic soln and deionized water clean the adulterated White tin oxide of fluorine (FTO) conductive glass (15 Ω/sq) in the ultrasonic cleaning machine.Use the blade coating technology that made jelly is applied to FTO and process the film that thickness is 100 μ m.125 ℃ of air dryings 2 hours, 450 ℃ of annealing 15 minutes down, 500 ℃ of following sintering 15 minutes.When temperature was reduced to 80 ℃, film immersed N719 ethanol electrolyte solution.Soak after 4 hours, test.The I-V relation that obtains is shown in figure 12.The result shows, porous is little/receive hierarchical Z nO ball as the DSSC optoelectronic pole, and have higher electricity conversion.
Claims (8)
- Porous little/receive the preparation method of ZnO ball of hierarchy, it is characterized in that step is following: zinc nitrate hexahydrate, urea are added in the entry, be uniformly dispersed; Put into autoclave 100 ~ 180 ℃ of reactions down, wherein, zinc nitrate hexahydrate: the mol ratio of urea is 1:3 ~ 1:6, and the reaction times is 1 ~ 6 hour; Be placed into room temperature then, washing successively, drying is filtered to obtain deposition; Gained deposition is through calcining, 300 ~ 500 ℃ of calcinings 30 ~ 60 minutes down, obtain porous little/receive the ZnO ball of hierarchy.
- 2. porous according to claim 1 is little/receive the preparation method of ZnO ball of hierarchy, and it is characterized in that said zinc nitrate hexahydrate: the mol ratio of urea is 1:3.
- 3. porous according to claim 1 and 2 is little/receive the preparation method of ZnO ball of hierarchy, it is characterized in that putting into autoclave at 115 ~ 125 ℃ of reaction 3h down.
- 4. porous according to claim 1 and 2 is little/receive the preparation method of ZnO ball of hierarchy, it is characterized in that under said 500 ℃ that calcining is 30 minutes in retort furnace.
- By claim 1 or 2 or 3 or 4 described porous little/receive the preparation method of ZnO ball of hierarchy, it is characterized in that: after adding zinc nitrate hexahydrate, urea in the entry, magnetic agitation 0.5 ~ 1h is to be uniformly dispersed.
- By claim 1 or 2 or 3 or 4 described porous little/receive the preparation method of ZnO ball of hierarchy, it is characterized in that: after the spinning, adopt water that product is washed.
- By claim 1 or 2 or 3 or 4 described porous little/receive the preparation method of ZnO ball of hierarchy, it is characterized in that: adopt oven drying, drying temperature is 60 ℃, and the time is 8 ~ 24h.
- By claim 1 or 2 or 3 or 4 described porous little/receive the application of ZnO ball of hierarchy; It is characterized in that with the porous of preparation little/receive hierarchical Z nO ball as the DSSC optoelectronic pole: under the room temperature condition; With absolute ethyl alcohol and 0.1g porous little/the hierarchical Z nO ball of receiving is ground to pulpous state in mortar; The ZnO of pulpous state is transferred in the beaker of a 50ml, stirred ultrasonic 10 minutes 10 minutes; After adding the TKK 021 of anhydrous Terpineol 350s of 2 grams and 4g, stir, ultrasonic respectively 10 minutes; 38 ℃ of condition underspins steam to the agglutination thing; Clean the adulterated White tin oxide FTO of fluorine conductive glass, use spread coating that made jelly is applied to FTO and process the film that thickness is 100 μ m; 125 ℃ of air dryings 2 hours, 450 ℃ of annealing 15 minutes down, 500 ℃ of following sintering 15 minutes, film immerses N719 ethanol electrolyte solution and soaks after 2-5 hour, processes the DSSC optoelectronic pole.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983009A (en) * | 2012-11-06 | 2013-03-20 | 南京大学昆山创新研究院 | Flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet and preparation of flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet |
| CN104986793A (en) * | 2015-06-26 | 2015-10-21 | 西安理工大学 | Preparation method for ZnO nanomaterial with hierarchical porous structure |
| CN107434257A (en) * | 2017-07-20 | 2017-12-05 | 韩胜强 | Method for synthesizing nano-metal-oxide and products thereof and application |
| CN109521061A (en) * | 2017-09-20 | 2019-03-26 | 全球能源互联网研究院 | A kind of CO gas sensor and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723436A (en) * | 2009-12-31 | 2010-06-09 | 厦门大学 | Self-assembly zinc oxide hollow sphere and preparation method thereof |
-
2012
- 2012-03-02 CN CN2012100538015A patent/CN102583506A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723436A (en) * | 2009-12-31 | 2010-06-09 | 厦门大学 | Self-assembly zinc oxide hollow sphere and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983009A (en) * | 2012-11-06 | 2013-03-20 | 南京大学昆山创新研究院 | Flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet and preparation of flexible photo-anode of dye-sensitized solar cell based on zinc oxide nano-sheet |
| CN104986793A (en) * | 2015-06-26 | 2015-10-21 | 西安理工大学 | Preparation method for ZnO nanomaterial with hierarchical porous structure |
| CN107434257A (en) * | 2017-07-20 | 2017-12-05 | 韩胜强 | Method for synthesizing nano-metal-oxide and products thereof and application |
| CN109521061A (en) * | 2017-09-20 | 2019-03-26 | 全球能源互联网研究院 | A kind of CO gas sensor and preparation method |
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Application publication date: 20120718 |