CN110444403B - Dye-sensitized solar cell and full-3D printing preparation method thereof - Google Patents
Dye-sensitized solar cell and full-3D printing preparation method thereof Download PDFInfo
- Publication number
- CN110444403B CN110444403B CN201910712876.1A CN201910712876A CN110444403B CN 110444403 B CN110444403 B CN 110444403B CN 201910712876 A CN201910712876 A CN 201910712876A CN 110444403 B CN110444403 B CN 110444403B
- Authority
- CN
- China
- Prior art keywords
- printing
- dye
- solar cell
- sensitized solar
- full
- 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.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
Abstract
The invention relates to a dye-sensitized solar cell and a full 3D printing preparation method thereof, wherein the full 3D printing preparation method comprises the following steps: s1, printing the photo-anode slurry on a first transparent conductive substrate by a 3D printing method, and sintering and sensitizing to obtain a photo-anode; s2, printing the electrolyte on the photo-anode by adopting a 3D printing method to obtain an electrolyte layer; s3, printing the counter electrode slurry on a second transparent conductive substrate by adopting a 3D printing method, and sintering to obtain a counter electrode; and S4, attaching the electrolyte layer and the counter electrode, and packaging to obtain the dye-sensitized solar cell. According to the invention, the photo-anode is prepared by 3D printing, the pattern and the area of the photo-anode can be flexibly changed, and the quasi-solid electrolyte is printed on the surface of the sensitized photo-anode by 3D printing, so that the problem of packaging the modular dye solar cell is solved.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a dye-sensitized solar cell and a full-3D printing preparation method thereof.
Background
Dye Sensitized Solar Cells (DSSCs) provide a clean way of harnessing solar energy compared to conventional solar cells. The dye-sensitized solar cell takes nano titanium dioxide, dye, electrolyte and other materials as main raw materials, simulates natural photosynthesis of plants in the nature, and converts light energy into electric energy. The dye-sensitized solar cell is of a classic sandwich structure consisting of a photo-anode, an electrolyte containing a redox couple and a counter electrode.
The photoanode plays multiple roles of adsorbing dye molecules, electron acceptors, electron transportation and the like in the DSSCs, and the surface performance and the internal electrical performance of the photoanode directly influence the photoelectric conversion efficiency of the DSSCs. At present, methods such as a blade coating method, a screen printing method, a spin coating method and the like are mostly adopted to prepare the DSSCs photoanode, and the methods have the defects of complex process and need to be coated for many times; poor film quality, uneven large-area photo-anode film, inability to prepare patterned photo-anodes, and the like. These problems still make the photoelectric conversion efficiency of DSSCs low, and the cumbersome preparation process hinders their commercial development. Therefore, the conventional method for preparing the DSSCs photoanode cannot meet the requirement of further preparing the DSSCs in a large area and in a patterned manner.
In typical DSSCs, the electrolyte is a key component required for charge transport between the photoanode and the counter electrode. On one hand, the dye in an oxidation state is reduced and regenerated as an electron donor, and on the other hand, the dye serves as an electron acceptor on a counter electrode and is reduced by electrons of an external circuit, so that the internal circulation of the battery is completed. Both the photovoltaic performance and the long-term stability of DSSCs depend to a large extent on the electrolyte. Conventional liquid electrolytes consist of iodide/triiodide (I)-/I3 -) The redox electrode is composed of volatile organic solvent (such as acetonitrile, ethylene carbonate and the like) and other additives, and a high-efficiency battery can be produced. However, due to the characteristics of the organic solvent, the DSSCs based on the organic solvent electrolyte have the problems of volatile solvent, complex sealing process and the like. Furthermore, by iodine (I) in the electrolyte2) And I-Electrolyte I produced by the reaction between3 -The ions are corrosive and partially absorbing in the visible. Thus, the above-mentioned problems result in the impairment of the long-term stability and efficiency of DSSCs. Meanwhile, the common quasi-solid electrolyte generally has the problem of difficult packaging, and the quasi-solid electrolyte can not cover the surface of the photo-anode in a common mode, so that the application of preparing a large-area modular dye-sensitized solar cell is limited.
Disclosure of Invention
The invention mainly aims to provide a dye-sensitized solar cell and a full 3D printing preparation method thereof, aiming at solving the technical problems that a photo-anode is prepared through 3D printing, the pattern and the area of the photo-anode can be flexibly changed, and quasi-solid electrolyte is printed on the surface of the sensitized photo-anode through 3D printing, so that the problem of packaging of a modular dye-sensitized solar cell is solved, and the method is more practical.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a full-3D printing preparation method of a dye-sensitized solar cell, which comprises the following steps: s1, printing the photo-anode slurry on a first transparent conductive substrate by a 3D printing method, and sintering and sensitizing to obtain a photo-anode;
s2, printing the electrolyte on the photo-anode by adopting a 3D printing method to obtain an electrolyte layer;
s3, printing the counter electrode slurry on a second transparent conductive substrate by adopting a 3D printing method, and sintering to obtain a counter electrode;
and S4, attaching the electrolyte layer and the counter electrode, and packaging to obtain the dye-sensitized solar cell.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the method for preparing the full 3D printing of the dye-sensitized solar cell comprises the following steps: adding ethyl cellulose into an ethanol solution, magnetically stirring until the ethyl cellulose is completely dissolved, adding oxide and terpineol, stirring until the oxide and the terpineol are dispersed, then adding absolute ethyl alcohol, carrying out ultrasonic mixing, and carrying out rotary evaporation to remove the solvent to obtain photoanode slurry;
the mass ratio of the ethyl cellulose to the oxide to the terpineol is 1: 2-5: 6-8.
Preferably, in the method for preparing the full-3D printing of the dye-sensitized solar cell, the oxide is titanium oxide, zinc oxide or tin oxide.
Preferably, of the aforementioned dye-sensitized solar cellThe all-3D printing preparation method comprises the following steps of: adding a polymer to a solution of LiI, I2Stirring the mixture in acetonitrile solution of 1-propyl-3-methylimidazole iodized salt, 4-tert-butylpyridine and guanidine thiocyanate overnight in the dark to obtain an electrolyte;
the LiI, I2The mol ratio of the 1-propyl-3-methylimidazolium iodide salt to the 4-tert-butylpyridine to the guanidine thiocyanate is 1: 0.4-0.6: 5-7: 4-6: 0.5-1.5.
Preferably, in the method for preparing the dye-sensitized solar cell by full 3D printing, the polymer is polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride, polyacrylonitrile, polyvinyl chloride or polymethyl methacrylate;
the addition amount of the polymer is 3-7 wt% of the mass of the acetonitrile solution.
Preferably, the method for preparing the full-3D printing of the dye-sensitized solar cell comprises the following steps: and adding chloroplatinic acid and ethyl cellulose ethanol solution into terpineol, ultrasonically mixing, and performing rotary evaporation to remove the solvent to obtain the counter electrode slurry.
Preferably, in the method for preparing the full-3D printing of the dye-sensitized solar cell, the volume ratio of the ethanol solution of chloroplatinic acid and ethyl cellulose to terpineol is 10: 4-5;
in the ethanol solution, the mass concentration of chloroplatinic acid is 3-7 g/L; the mass concentration of the ethyl cellulose is 0.1-0.15 g/L.
Preferably, the aforementioned full 3D printing preparation method of the dye-sensitized solar cell, wherein in the step S1, the step S2 and the step S3, the 3D printing method includes: setting a starting point, and performing 3D printing;
the speed of 3D printing is 15mm/s, 20mm/s, 25mm/s or 30 mm/s;
the line width of the 3D printing is 4mm, 5mm, 6mm, 7mm, 8mm or 10 mm;
the spacing of the 3D printing is 8mm, 10mm, 12mm or 14 mm.
Preferably, in the foregoing method for preparing a full 3D print of a dye-sensitized solar cell, in step S1, the sintering includes: sintering at 400-600 ℃ for 20-40 min; the sensitizing comprises: sensitizing for 20-28h in 0.1-1mmol/L N719 photosensitive dye ethanol solution;
in step S3, the sintering includes: sintering at 500 ℃ for 20-40min at 300-.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the dye-sensitized solar cell provided by the invention, the dye-sensitized solar cell is prepared by any one of the full-3D printing preparation methods.
By the technical scheme, the dye-sensitized solar cell and the full-3D printing preparation method thereof provided by the invention at least have the following advantages:
the dye-sensitized solar cell is prepared by a full 3D printing method, and the technical problem that the pattern and the area of the photo-anode cannot be flexibly changed in the conventional photo-anode prepared by silk-screen printing at present is solved; and meanwhile, the quasi-solid electrolyte is printed on the surface of the sensitized photoanode in a 3D printing mode, so that solvent evaporation is inhibited, electrolyte leakage is reduced, and the long-term stability of the DSSCs is improved.
According to the invention, the dye-sensitized solar cell is prepared by a full 3D printing method, so that the problem of packaging the modular dye solar cell is solved. Meanwhile, the 3D printing preparation process is simple, and the photo-anode materials with different areas and patterns can be prepared without tool limitation (for example, different silk-screen printing plates need to be replaced in silk-screen printing). This is of great significance in reducing manufacturing costs.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic view of the structure of a dye-sensitized solar cell according to the present invention;
fig. 2 is a photo-voltage-current graph of a full 3D printed dye-sensitized solar cell device.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description will be made on the specific implementation, structure, features and effects of the dye-sensitized solar cell and the full 3D printing preparation method thereof according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The full-3D printing preparation method of the dye-sensitized solar cell provided by one embodiment of the invention specifically comprises the following steps:
(1) pretreating a conductive substrate, soaking the cut transparent conductive substrate in absolute ethyl alcohol in advance, ultrasonically cleaning the transparent conductive substrate with acetone, ethyl alcohol and deionized water respectively before experiment, and blow-drying the transparent conductive substrate with nitrogen for later use;
in the embodiment of the invention, the conductive substrate is made of transparent conductive glass, and fluorine-doped tin oxide (FTO) is preferred.
(2) Preparing a photo-anode: weighing ethyl cellulose, adding an ethanol solution, magnetically stirring until the ethyl cellulose is completely dissolved, adding oxide and terpineol, stirring until the oxide and the terpineol are dispersed, then adding absolute ethyl alcohol, carrying out ultrasonic mixing, and carrying out rotary evaporation to remove the solvent, so as to obtain the photoanode slurry capable of being printed in 3D;
in this step, the oxide is preferably titanium oxide, zinc oxide, or tin oxide.
The mass ratio of the ethyl cellulose to the oxide to the terpineol is as follows: 1: 2-5: 6-8. Preferably, the mass ratio of the ethyl cellulose to the oxide to the terpineol is 1: 2: 7.
the dosage of the ethanol solution is not particularly limited in the embodiment of the invention, and the mass ratio of the ethyl cellulose to the ethanol solution is preferably 1:10, based on the fact that the ethyl cellulose can be completely dissolved; the amount of the absolute ethyl alcohol is also not particularly limited, and the absolute ethyl alcohol is added for the purpose of better dispersion of the oxide into the solution, and it is preferable to add the absolute ethyl alcohol in the same mass as the previous ethanol solution.
Printing a required pattern on a first transparent conductive substrate by using the photo-anode paste through a 3D printer produced by Tensun company, setting a starting point, selecting a printing needle head from a 25G, 27G, 30G, 32G or 34G 1/2-inch plastic steel screw dispensing needle head, selecting a syringe from 10cc or 30cc, the precision is 0.01mm, the speed is 15mm/s, 20mm/s, 25mm/s or 30mm/s, the printing line width is 4mm, 5mm, 6mm, 7mm, 8mm or 10mm, and the interval is 8mm, 10mm, 12mm or 14 mm; then sintering at 400-600 ℃ for 30-50min, and sensitizing in 0.1-1mmol/L N719 photosensitive dye ethanol solution for 20-28 h;
the parameters of the 3D printing in the step are not specifically limited and are selected according to actual needs.
In this step, the active ingredient of the photo-anode is a semiconductor oxide, and titanium oxide, zinc oxide, and tin oxide are usually selected. On one hand, the slurry is used as a supporting layer of the photosensitive dye, is bonded with the photosensitive dye through hydrogen bonds or ester groups, and is added with ethyl cellulose and terpineol, so that the slurry is suitable for 3D printing, and simultaneously can generate a porous structure after sintering to increase the surface area, thereby increasing the adsorption capacity of the photosensitive dye and improving the photoelectric conversion efficiency; on one hand, the photosensitive dye is used as an electron transmission layer to transmit the photo-generated electrons generated by the photosensitive dye to an external circuit.
(3) Preparing a quasi-solid electrolyte: weighing polymer, adding the polymer into dissolved LiI and I2Stirring the mixture in acetonitrile solution of 1-propyl-3-methylimidazole iodized salt, 4-tert-butylpyridine and guanidine thiocyanate overnight in the dark to obtain an electrolyte;
the LiI, I2The mol ratio of the 1-propyl-3-methylimidazolium iodide salt to the 4-tert-butylpyridine to the guanidine thiocyanate is 1: 0.4-0.6: 5-7: 4-6: 0.5-1.5.
Specifically, 0.5g of the polymer was added to 3ml of a solution containing 0.1mol/L of LiI and 0.05mol/L of I20.6 mol/L1-propyl-3-methylimidazolium iodide (PMII), 0.5 mol/L4-tert-butylpyridine (TBP) and 0.1mol/L guanidine thiocyanate (GuSCN) in acetonitrile.
In this step, the polymer is preferably polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), polyvinyl chloride (PVC), or polymethyl methacrylate (PMMA). The addition of the polymer enables the electrolyte to be converted from a liquid state to a quasi-solid state, so that the volatilization of an organic solvent is inhibited, and the stability of the dye-sensitized solar cell is improved. By adjusting the content of the polymer in the electrolyte, various physical and chemical properties of the electrolyte and photoelectrochemical parameters of an assembled battery are optimized.
The addition amount of the polymer is 3-7 wt% of the mass of the acetonitrile solution.
Printing a layer of quasi-solid electrolyte on the upper layer of a dye-bath photocathode by a 3D printer produced by Tensun company, setting a starting point, selecting an 1/2-inch plastic steel screw dispensing needle head of 25G, 27G, 30G, 32G and 34G as a printing needle head, selecting 10cc or 30cc as a needle cylinder, selecting the precision to be 0.01mm, the speed to be 15mm/s, 20mm/s, 25mm/s or 30mm/s, printing the line width to be 5mm, 6mm, 7mm, 8mm, 9mm or 10mm, and spacing to be 8mm, 10mm, 12mm or 14 mm;
the parameters of the 3D printing in the step are not specifically limited and are selected according to actual needs.
(4) Preparing a counter electrode: adding chloroplatinic acid and ethyl cellulose ethanol solution into terpineol, ultrasonically mixing, and performing rotary evaporation to remove the solvent to obtain counter electrode slurry;
as a preferred embodiment, the volume ratio of the ethanol solution of chloroplatinic acid and ethyl cellulose to the terpineol is 10: 4-5;
in the ethanol solution, the mass concentration of chloroplatinic acid is 3-7g/L, and more preferably 5 g/L; the mass concentration of the ethyl cellulose is 0.1-0.15g/L, more preferably 0.12 g/L.
Printing the counter electrode slurry on a second transparent conductive substrate by a 3D printer produced by Tensun company to prepare a counter electrode, setting a starting point, selecting a printing needle head from a 25G, 27G, 30G, 32G or 34G 1/2-inch plastic steel screw dispensing needle head, selecting a needle cylinder from 10cc and 30cc, wherein the precision is 0.01mm, the speed is 15mm/s, 20mm/s, 25mm/s or 30mm/s, the printing line width is 8mm, 9mm, 10mm, 11mm or 12mm, and the interval is 8mm, 10mm, 12mm or 14 mm; finally, sintering the mixture for 30-50min at the temperature of 300-500 ℃ to obtain a counter electrode;
the parameters of the 3D printing in the step are not specifically limited and are selected according to actual needs.
(5) And attaching the electrolyte layer and the counter electrode, and packaging to obtain the dye-sensitized solar cell.
In the step, the photo-anode is attached to the upper surface of the first transparent conductive substrate, the quasi-solid electrolyte is printed on the surface of the photo-anode through 3D, the counter electrode is printed on the second transparent conductive substrate, during lamination, the conductive surface of the counter electrode is tightly attached to the surface of the quasi-solid electrolyte, the gaps around the conductive surface of the counter electrode are filled with ultraviolet curing glue, and the packaged solar cell can be obtained after ultraviolet curing. All gaps in the structure need to be packaged to prevent air from entering and affecting the performance of the solar cell.
It is important to note that, in the preparation method of the present invention, each step is not fixed, and the setting of the steps is only for convenience and the following further limitation. If the steps of printing the photoanode and the electrolyte layer on the first transparent conductive substrate and the step of printing the counter electrode on the second transparent conductive substrate are performed separately before the electrolyte layer is attached to the counter electrode, the two steps are not in sequence, and neither step has a substantial influence on the result.
The dye-sensitized solar cell is prepared by a full 3D printing method, and the technical problem that the pattern and the area of the photo-anode cannot be flexibly changed in the conventional photo-anode prepared by silk-screen printing at present is solved; and meanwhile, the quasi-solid electrolyte is printed on the surface of the sensitized photoanode in a 3D printing mode, so that solvent evaporation is inhibited, electrolyte leakage is reduced, and the long-term stability of the DSSCs is improved. The preparation method of full-3D printing adopted by the invention solves the problem of packaging of the modular dye solar cell, and meanwhile, the preparation method of 3D printing is simple, and the photo-anode materials with different areas and patterns can be prepared without being limited by tools (for example, different silk-screen printing plates need to be replaced in silk-screen printing). This is of great significance in reducing manufacturing costs.
Another embodiment of the present invention provides a dye-sensitized solar cell, which is manufactured by the above full 3D printing preparation method.
As shown in fig. 1, the dye-sensitized solar cell includes a first transparent conductive substrate 1, a photo-anode 2, an electrolyte layer 3, a counter electrode 4, a second transparent conductive substrate 5, and an encapsulation layer 6 filled between the first transparent conductive substrate 1 and the second transparent conductive substrate 5 for encapsulating the photo-anode 2, the electrolyte layer 3, and the counter electrode 4.
The photo-anode 2 is attached to the first transparent conductive substrate 1, the quasi-solid electrolyte layer 3 is formed on the photo-anode 2 through 3D printing, the counter electrode 4 is attached to the second transparent conductive substrate 5, the conductive surface of the counter electrode 4 is tightly attached to the other surface, opposite to the second transparent conductive substrate 5, of the quasi-solid electrolyte layer 3, and the packaging layer 6 is filled in gaps generated by the photo-anode 2, the electrolyte layer 3, the counter electrode 4, the first transparent conductive substrate 1 and the second transparent conductive substrate 5.
The ultraviolet curing glue is filled in the gaps generated by the photo-anode, the electrolyte and the counter electrode and the two conductive substrates to form the packaging layer 6, so that the DSSCs can be well isolated from oxygen and water in the air, and the service life of the DSSCs is greatly prolonged.
The method comprises the steps of sequentially printing a photo-anode and a quasi-solid electrolyte on the surface of a first conductive substrate through a 3D printing technology, printing a counter electrode on the surface of a second conductive substrate, and then enabling printing surfaces of the two conductive substrates to be attached to form a laminated structure of the conductive substrate/the photo-anode/the quasi-solid electrolyte/the counter electrode/the conductive substrate. Due to the adoption of the 3D printing technology, the steps and the preparation time of the traditional process can be greatly saved, and the prepared DSSCs are close to the solar cells prepared by the traditional process in the aspect of photoelectric conversion performance. Meanwhile, due to the programmability of 3D printing, the shapes and sizes of the photo-anode, the electrolyte and the counter electrode can be changed at will.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
Example 1
A full-3D printing preparation method of a dye-sensitized solar cell specifically comprises the following steps:
1) conductive substrate pretreatment: soaking the cut FTO substrate in absolute ethyl alcohol in advance, ultrasonically cleaning the FTO substrate by using acetone, ethyl alcohol and deionized water respectively before experiment, and drying the FTO substrate by using nitrogen for later use;
2) preparing a semiconductor photo-anode: weighing 0.5g of ethyl cellulose, adding 5g of ethanol solution, magnetically stirring until the ethyl cellulose is completely dissolved, adding 1.0g of titanium oxide and 3.5g of terpineol, stirring until the titanium oxide and the terpineol are dispersed, then adding 5g of absolute ethanol, ultrasonically mixing for 30min, and removing the solvent by rotary evaporation to obtain semiconductor slurry capable of being printed in 3D;
printing the semiconductor slurry on an FTO substrate by a 3D printer produced by Tensun company to obtain a required pattern, selecting a 32G 1/2-inch plastic steel screw dispensing needle head as a printing needle head, selecting 10cc as a needle cylinder, selecting squares with the precision of 0.01mm and the speed of 20mm/s and the length of a printing line of 4mm, and spacing 10 mm. Then sintering at 500 ℃ for 30min, and sensitizing in 0.5mmol/L N719 photosensitive dye ethanol solution for 24 h;
3) preparing a quasi-solid electrolyte: 0.5g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) was weighed out and added to 3ml of a solution containing 0.1mol/L LiI, 0.05mol/L I20.6 mol/L1-propyl-3-methylimidazolium iodide (PMII), 0.5 mol/L4-tert-butylpyridine (TBP) and 0.1mol/L guanidine thiocyanate (GuSCN) in acetonitrile, and stirring overnight in the absence of light;
printing a layer of quasi-solid electrolyte on the dye-bath photocathode upper layer by a 3D printer produced by Tensun company, setting a starting point, selecting a 32G 1/2-inch plastic steel screw dispensing needle head for the printing needle head, selecting 10cc for the needle cylinder, having the precision of 0.01mm, the speed of 20mm/s, and printing 5mm squares with a line length and the interval of 10 mm;
4) preparing a counter electrode: adding 5g/L chloroplatinic acid and 0.12g/L ethyl cellulose ethanol solution into terpineol according to the volume ratio of 10: 3, mixing and ultrasonically mixing, and removing the solvent by rotary evaporation to obtain counter electrode slurry;
and preparing a counter electrode on the surface of the other FTO substrate by adopting the paste in a 3D printing mode, setting a starting point, selecting a 32G 1/2-inch plastic steel screw dispensing needle head as a printing needle head, selecting 10cc of a needle cylinder, wherein the precision is 0.01mm, the speed is 20mm/s, the length of the printing line is 8mm, and the interval is 10 mm. Finally, sintering the mixture for 30min at 400 ℃ to obtain a counter electrode;
5) packaging the dye-sensitized solar cell: and (3) tightly attaching the counter electrode to the surface of the quasi-solid electrolyte, filling ultraviolet curing glue into gaps around the counter electrode, and curing the ultraviolet rays to obtain the packaged solar cell.
Example 2
A full-3D printing preparation method of a dye-sensitized solar cell specifically comprises the following steps:
1) conductive substrate pretreatment: soaking the cut FTO substrate in absolute ethyl alcohol in advance, ultrasonically cleaning the FTO substrate by using acetone, ethyl alcohol and deionized water respectively before experiment, and drying the FTO substrate by using nitrogen for later use;
2) preparing a photo-anode: weighing 1g of ethyl cellulose, adding 10g of ethanol solution, magnetically stirring until the ethyl cellulose is completely dissolved, adding 5.0g of zinc oxide and 8g of terpineol, stirring until the zinc oxide and the terpineol are dispersed, then adding 10g of absolute ethanol, ultrasonically mixing for 40min, and removing the solvent by rotary evaporation to obtain the photoanode slurry capable of being printed in 3D;
printing the required pattern on the FTO substrate by the photo-anode slurry through a 3D printer produced by Tensun company, setting a starting point, selecting a printing needle head with 30G of 1/2-inch plastic steel screw dispensing needle head, selecting a needle cylinder with 30cc, the precision of 0.01mm, the speed of 25mm/s, the length of the printing wire being 5mm, and the interval being 12 mm. Then sintering at 600 ℃ for 400min, and sensitizing for 20h in 0.3mmol/L N719 photosensitive dye ethanol solution;
3) preparing a quasi-solid electrolyte: 0.6g of polyvinylidene fluoride (PVDF) was weighed out and added to 3ml of a solution containing 0.1mol/L LiI and 0.06mol/L I20.7 mol/L1-propyl-3-methylimidazolium iodide (PMII), 0.6 mol/L4-tert-butylpyridine (TBP) and 0.15mol/L guanidine thiocyanate (GuSCN) in acetonitrile, and stirring overnight in the absence of light;
printing a layer of quasi-solid electrolyte on the upper layer of a dye-bath photocathode by a 3D printer produced by Tensun corporation, setting a starting point, selecting a printing needle head from a 30G 1/2-inch plastic steel screw dispensing needle head, selecting a needle cylinder from 10cc, wherein the precision is 0.01mm, the speed is 25mm/s, the printing line width is 6mm, and the interval is 12 mm;
4) preparing a counter electrode: adding 7g/L chloroplatinic acid and 0.15g/L ethyl cellulose ethanol solution into terpineol according to the volume ratio of 5: 2, ultrasonically mixing, and rotationally evaporating to remove the solvent to obtain the counter electrode slurry.
Preparing a counter electrode on the surface of the other FTO substrate by the paste in a 3D printing mode, setting a starting point, selecting a 30G 1/2-inch plastic steel screw dispensing needle head for the printing needle head, selecting 30cc for the needle cylinder, wherein the precision is 0.01mm, the speed is 25mm/s, the printing line width is 9mm, and the interval is 12 mm; and finally, sintering at 450 ℃ for 25min to obtain the counter electrode.
5) Packaging the dye-sensitized solar cell: and (3) tightly attaching the counter electrode to the surface of the quasi-solid electrolyte, filling ultraviolet curing glue into gaps around the counter electrode, and curing the ultraviolet rays to obtain the packaged solar cell.
Comparative example 1
Compared with the example 1, the preparation method is different, and other parameters are the same as those of the example 1 except that the preparation method is different.
Comparative example 1 the conventional doctor blade method for preparing the photo-anode, the electrolyte layer, and the counter electrode has disadvantages of low preparation efficiency, complicated process, etc., which limits the commercial application of preparing the dye-sensitized solar cell. And embodiment 1 can prepare required functional layer by automation through 3D printing technology, greatly reduced the degree of difficulty of preparation, improved the efficiency of preparation.
As shown in the photo-voltage-current curve diagram of FIG. 2, the electrochemical workstation (AUT86832, Mrtrohm China Ltd.) is used to perform J-V characteristic curve analysis on DSSCs, the simulated light source is generated by a xenon high-brightness point light source parallel light source system (Beijing NBeT technologies Co., Ltd.), and the standard silicon solar cell (Beijing NBeT technologies Co., Ltd.) is used to adjust the light source, so that the light source is stabilized at 100mw/cm2。
Fig. 2 is a graph of photo-voltage-current of the dye-sensitized solar cell prepared by the full 3D printing method of example 1. From fig. 2, it can be seen that the short-circuit current density J of the dye-sensitized solar cell prepared by full 3D printingsc＝13.95mA/cm2Open circuit voltage Voc0.68V, 0.65 fill factor FF, photoelectric conversion efficiency Eff6.18%, close to the relevant parameters of the dye-sensitized solar cell prepared by the conventional doctor-blading method of comparative example 1, the photoelectric conversion efficiency of the dye-sensitized solar cell is similar. Compared with comparative example 1, the preparation process of example 1 is simpler and the preparation efficiency is higher.
Comparative example 2
A preparation method of a dye-sensitized solar cell specifically comprises the following steps:
1) conductive substrate pretreatment: soaking the cut FTO substrate in absolute ethyl alcohol in advance, ultrasonically cleaning the FTO substrate by using acetone, ethyl alcohol and deionized water respectively before experiment, and drying the FTO substrate by using nitrogen for later use;
2) preparing a photo-anode: weighing 1g of ethyl cellulose, adding 10g of ethanol solution, magnetically stirring until the ethyl cellulose is completely dissolved, adding 5.0g of zinc oxide and 8g of terpineol, stirring until the zinc oxide and the terpineol are dispersed, then adding 10g of absolute ethanol, ultrasonically mixing for 40min, and removing the solvent by rotary evaporation to obtain the photoanode slurry capable of being printed in 3D;
printing the required pattern on the FTO substrate by the photo-anode slurry through a 3D printer produced by Tensun company, setting a starting point, selecting a printing needle head with 30G of 1/2-inch plastic steel screw dispensing needle head, selecting a needle cylinder with 30cc, the precision of 0.01mm, the speed of 25mm/s, the length of the printing wire being 5mm, and the interval being 12 mm. Then sintering at 600 ℃ for 400min, and sensitizing for 20h in 0.3mmol/L N719 photosensitive dye ethanol solution;
3) preparing a liquid electrolyte: weighing 0.1mol/L LiI and 0.06mol/L I20.7 mol/L1-propyl-3-methylimidazolium iodide (PMII), 0.6 mol/L4-tert-butylpyridine (TBP) and 0.15mol/L guanidine thiocyanate (GuSCN) were added to acetonitrile, stirred overnight in the dark, and then allowed to stand in the dark for further use.
4) Preparing a counter electrode: firstly, drilling a small hole with the diameter of 1mm on the surface of the other conductive substrate; mixing an ethanol solution formed by mixing 7g/L chloroplatinic acid and 0.15g/L ethyl cellulose with terpineol according to the volume ratio of 5: 2, mixing by ultrasonic, and removing the solvent by rotary evaporation to obtain counter electrode slurry;
preparing a counter electrode by the paste in a 3D printing mode, setting a starting point, selecting a 30G 1/2-inch plastic steel screw dispensing needle head as a printing needle head, selecting 30cc of a needle cylinder, wherein the precision is 0.01mm, the speed is 25mm/s, the printing line width is 9mm, and the interval is 10 mm; finally, sintering the mixture for 25min at 450 ℃ to obtain a counter electrode;
5) packaging the dye-sensitized solar cell: cutting 60 μm thick resin film into suitable shape, packaging the load photo-anode and counter electrode with the resin film at 110 deg.C under pressure, and filling liquid electrolyte in the resin film via perforated holes under vacuum. Finally, the small holes were sealed with a sarin resin film under pressure at 110 ℃.
Comparative example 2 compared to example 2, the main difference is the use of a different electrolyte. The electrolyte adopted in the comparative example 2 is the most widely used liquid electrolyte at present, and due to the self-fluidity, the electrolyte can be packaged only by adopting a vacuum filling mode when the electrode is punched, the steps are complex, and the risk of electrolyte leakage still exists after the packaging. Embodiment 2 has adopted the quasi solid electrolyte, obtains the thickness and the area of required electrolyte through 3D printing, need not to punch at the counter electrode, can one step of encapsulation avoid the electrolyte to take place the problem of revealing easily simultaneously.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (8)
1. The full-3D printing preparation method of the dye-sensitized solar cell is characterized by comprising the following steps of:
s1, printing the photo-anode slurry on a first transparent conductive substrate by a 3D printing method, and sintering and sensitizing to obtain a photo-anode;
s2, printing the electrolyte on the photo-anode by adopting a 3D printing method to obtain an electrolyte layer;
s3, printing the counter electrode slurry on a second transparent conductive substrate by adopting a 3D printing method, and sintering to obtain a counter electrode;
s4, attaching the electrolyte layer and the counter electrode, and packaging to obtain the dye-sensitized solar cell;
the photoanode slurry is prepared by the following method: adding ethyl cellulose into an ethanol solution, magnetically stirring until the ethyl cellulose is completely dissolved, adding oxide and terpineol, stirring until the oxide and the terpineol are dispersed, then adding absolute ethyl alcohol, carrying out ultrasonic mixing, and carrying out rotary evaporation to remove the solvent to obtain photoanode slurry;
the mass ratio of the ethyl cellulose to the oxide to the terpineol is 1: 2-5: 6-8;
the electrolyte is a quasi-solid electrolyte, and is prepared by the following method: adding a polymer to a solution of LiI, I2Stirring the mixture in acetonitrile solution of 1-propyl-3-methylimidazole iodized salt, 4-tert-butylpyridine and guanidine thiocyanate overnight in the dark to obtain an electrolyte;
the LiI, I2The mol ratio of the 1-propyl-3-methylimidazolium iodide salt to the 4-tert-butylpyridine to the guanidine thiocyanate is 1: 0.4-0.6: 5-7: 4-6: 0.5-1.5; the addition amount of the polymer is 3-7 wt% of the mass of the acetonitrile solution.
2. The method for preparing the full 3D print of the dye-sensitized solar cell according to claim 1, characterized in that said oxide is titanium oxide, zinc oxide or tin oxide.
3. The method for preparing full 3D printing of the dye-sensitized solar cell according to claim 1, characterized in that the polymer is polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride, polyacrylonitrile, polyvinyl chloride or polymethyl methacrylate.
4. The method for preparing the full-3D printing of the dye-sensitized solar cell according to claim 1, wherein the counter electrode paste is prepared by the following method: and adding chloroplatinic acid and ethyl cellulose ethanol solution into terpineol, ultrasonically mixing, and performing rotary evaporation to remove the solvent to obtain the counter electrode slurry.
5. The method for preparing the full 3D printing of the dye-sensitized solar cell according to claim 4, wherein the volume ratio of the ethanol solution of chloroplatinic acid and ethyl cellulose to terpineol is 10: 4-5;
in the ethanol solution, the mass concentration of chloroplatinic acid is 3-7 g/L; the mass concentration of the ethyl cellulose is 0.1-0.15 g/L.
6. The all 3D printing preparation method of the dye-sensitized solar cell according to claim 1, wherein in the steps S1, S2 and S3, the 3D printing method comprises: setting a starting point, and performing 3D printing;
the speed of 3D printing is 15mm/s, 20mm/s, 25mm/s or 30 mm/s;
the line width of the 3D printing is 4mm, 5mm, 6mm, 7mm, 8mm or 10 mm;
the spacing of the 3D printing is 8mm, 10mm, 12mm or 14 mm.
7. The method for preparing the full 3D print of the dye-sensitized solar cell according to claim 1, wherein in step S1, the sintering comprises: sintering at 400-600 ℃ for 30-50 min; the sensitizing comprises: sensitizing for 20-28h in 0.1-1mmol/L N719 photosensitive dye ethanol solution;
in step S3, the sintering includes: sintering at 300-500 deg.C for 30-50 min.
8. A dye-sensitized solar cell, characterized in that the dye-sensitized solar cell is manufactured by the full 3D printing preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910712876.1A CN110444403B (en) | 2019-08-02 | 2019-08-02 | Dye-sensitized solar cell and full-3D printing preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910712876.1A CN110444403B (en) | 2019-08-02 | 2019-08-02 | Dye-sensitized solar cell and full-3D printing preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110444403A CN110444403A (en) | 2019-11-12 |
| CN110444403B true CN110444403B (en) | 2021-11-12 |
Family
ID=68433058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910712876.1A Active CN110444403B (en) | 2019-08-02 | 2019-08-02 | Dye-sensitized solar cell and full-3D printing preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110444403B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035410A (en) * | 2011-10-08 | 2013-04-10 | 索尼公司 | Dye-sensitized photoelectric conversion device and manufacturing method thereof and metal oxide slurry |
| CN106449799A (en) * | 2016-11-18 | 2017-02-22 | 西安联创先进制造专业孵化器有限公司 | Energy-storage type solar cell based on 3D printing technology and manufacture method thereof |
| CN107759958A (en) * | 2017-11-10 | 2018-03-06 | 武汉纺织大学 | A kind of graphene plastic composite |
| CN109187705A (en) * | 2018-10-18 | 2019-01-11 | 宁波诺丁汉大学 | A kind of photoelectrochemistrpool pool |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100994902B1 (en) * | 2010-04-06 | 2010-11-16 | 서울대학교산학협력단 | Flexible dye-sensitized solar cell and preparation method thereof |
-
2019
- 2019-08-02 CN CN201910712876.1A patent/CN110444403B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103035410A (en) * | 2011-10-08 | 2013-04-10 | 索尼公司 | Dye-sensitized photoelectric conversion device and manufacturing method thereof and metal oxide slurry |
| CN106449799A (en) * | 2016-11-18 | 2017-02-22 | 西安联创先进制造专业孵化器有限公司 | Energy-storage type solar cell based on 3D printing technology and manufacture method thereof |
| CN107759958A (en) * | 2017-11-10 | 2018-03-06 | 武汉纺织大学 | A kind of graphene plastic composite |
| CN109187705A (en) * | 2018-10-18 | 2019-01-11 | 宁波诺丁汉大学 | A kind of photoelectrochemistrpool pool |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110444403A (en) | 2019-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bella et al. | Interfacial effects in solid–liquid electrolytes for improved stability and performance of dye-sensitized solar cells | |
| Lenzmann et al. | Recent advances in dye-sensitized solar cells | |
| CN102396101B (en) | Dye-sensitized solar cell and dye-sensitized solar cell module | |
| Ikeda et al. | Conductive polymer–carbon–imidazolium composite: a simple means for constructing solid-state dye-sensitized solar cells | |
| Knödler et al. | Photoelectrochemical cells based on dye sensitized colloidal TiO2 layers | |
| CN100552985C (en) | A kind of manufacture method of large-area nano film solar battery | |
| WO2005112183A1 (en) | Photoelectric conversion element and semiconductor electrode | |
| Pettersson et al. | The monolithic multicell: a tool for testing material components in dye‐sensitized solar cells | |
| JP5139501B2 (en) | Electrolyte composition for dye-sensitized solar cell and dye-sensitized solar cell using the same | |
| WO2009017298A1 (en) | Method of forming porous layer, dye-sensitized solar cell using the same, and method of fabricating the dye-sensitized solar cell | |
| VESCE et al. | Scaling-up of dye sensitized solar modules | |
| JP2003249275A (en) | Dye sensitized solar cell and its manufacturing method | |
| US20110303261A1 (en) | Dye-sensitised solar cells | |
| US20100300537A1 (en) | Dye-sensitized solar cell and organic solvent-free electrolyte for dye-sensitized solar cell | |
| CN110444403B (en) | Dye-sensitized solar cell and full-3D printing preparation method thereof | |
| KR101190002B1 (en) | Semiconductor electrode for dye-sensitized solar cell, preparation method thereof and dye-sensitized solar cell using the same | |
| CN110085428A (en) | A kind of compound light anode of titanium dioxide/graphene and preparation method thereof | |
| KR101131055B1 (en) | Dye sensitized solar cell comprising counter electrode having mesoporous carbon electrode deposited on transparent substrate and preparation method thereof | |
| Lan et al. | A highly efficient electric additive for enhancing photovoltaic performance of dye-sensitized solar cells | |
| KR20110025573A (en) | Dye sensitized solar cell comprising negative electrode including nano oxide layer adsorbed with dye and polyatomic anion and preparation method thereof | |
| JP2005085491A (en) | Dye-sensitized solar cell and its manufacturing process | |
| Vadivel et al. | Photo-Supercapacitor | |
| KR101629799B1 (en) | Method for preparing photo electrodes for high efficient dye-sensitized solar cells | |
| Shi | Application of 3-hexyl-1-methylimidazolium iodide to dye-sensitized solar cells | |
| CN111180213B (en) | Application of cobalt triphosphate-based binary counter electrode in dye-sensitized solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |