CN110265222B - Preparation method of dye-sensitized solar cell with high photoelectric conversion efficiency - Google Patents

Preparation method of dye-sensitized solar cell with high photoelectric conversion efficiency Download PDF

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CN110265222B
CN110265222B CN201810309648.5A CN201810309648A CN110265222B CN 110265222 B CN110265222 B CN 110265222B CN 201810309648 A CN201810309648 A CN 201810309648A CN 110265222 B CN110265222 B CN 110265222B
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melem
solar cell
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朱堂葵
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Yiwu Industrial and Commercial College
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    • 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
    • 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 discloses a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency, which synthesizes a melem material, firstly adopts the melem material to carry out micro-doping on a nanocrystalline semiconductor photo-anode so as to adjust the semiconductor energy band width and enhance the light absorption capacity and range, thereby absorbing more solar photons, obtaining high-efficiency charge separation efficiency and finally achieving the purpose of remarkably improving the photoelectric conversion efficiency of the dye-sensitized solar cell.

Description

Preparation method of dye-sensitized solar cell with high photoelectric conversion efficiency
Technical Field
The invention belongs to the field of dye-sensitized solar cells, and particularly relates to a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency.
Background
Solar energy is an inexhaustible clean energy, and the research and development of solar cells for directly converting solar energy into electric energy through a photoelectric conversion technology is one of the most effective utilization modes of solar energy. The dye-sensitized solar cell (DSSC) has good application prospect and market potential due to the excellent performances of simple process, low cost, high photoelectric conversion efficiency, environmental protection, long service life and the like, and is greatly concerned and developed to a certain extent in recent years. However, currently, there are some important issues to be solved urgently in the research of DSSC, especially the further improvement of the photoelectric conversion efficiency. During the past decade, numerous publications have discussed the preparation of carbon nitride materials, Melem (C)6N7(NH2)3) Is the most common and important triazine derivative and is widely applied to the fields of photocatalysts, organic electronics and light-emitting devices.
Disclosure of Invention
The invention aims to provide a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency, which synthesizes a melem material, firstly adopts the melem material to carry out micro-doping on a nano-crystalline semiconductor photo-anode so as to adjust the semiconductor energy band width and enhance the light absorption capacity and range, thereby absorbing more solar photons, obtaining high-efficiency charge separation efficiency and finally achieving the purpose of remarkably improving the photoelectric conversion efficiency of the dye-sensitized solar cell.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a dye-sensitized solar cell with high photoelectric conversion efficiency is characterized in that a physical method is applied to dope a melem material into a photo-anode material, or a layer of melem material grows in situ on the surface of the photo-anode.
Preferably, the preparation method of melem is as follows:
s1, dispersing melamine in ultrapure water, performing ultrasonic treatment for 30-60min to obtain dispersion liquid, and heating the dispersion liquid to 100-150 ℃ until water is evaporated to obtain solid particles;
s2, calcining the solid particles in a muffle furnace at 250-350 ℃ for 1-2h, washing the obtained product with ultrapure water and acetonitrile in sequence, and drying at 60-75 ℃ for 1-2h to obtain the melem.
Preferably, the dispersion has a concentration of 0.5 to 2 mg/ml.
Preferably, a semiconductor having a particle size of 1 to 50nm is used as the electron transport layer material, and a semiconductor having a particle size of 40 to 1000nm is used as the scattering layer material.
Preferably, the mass percentage of melem to the semiconductor is 0.1 to 1%. Preferably, the semiconductor is selected from TiO2、SnO2、ZnO、LaTiO3、Nb2O5、In2O3、Zn2SnO4、Fe2O3Or CdS.
Preferably, the method comprises the steps of: step (1), preparing a melem material; step (2), preparing a melem-doped semiconductor slurry; and (3) preparing the dye-sensitized solar cell by adopting the melem-doped semiconductor slurry obtained in the step (2).
Preferably, SnO is used2When the photo-anode is used, the method comprises the following steps: preparation of SnO from tin sulfate2Slurry; weighing ethanol, pouring the ethanol into ethyl cellulose, and stirring to obtain liquid ethyl cellulose; adding terpineol and liquid ethyl cellulose into SnO2Concentrating the slurry to be viscous; taking viscous SnO2Putting the mixture into a mortar, adding a certain amount of melem powder, and fully and uniformly grinding; smearing melem-doped SnO by adopting blade coating method2And calcining the slurry at the temperature of 300-550 ℃ for 10-200 minutes to obtain the solar cell photo-anode.
Preferably, each 30ml of ethanol corresponds to 0.5-15 g of ethyl cellulose; tin sulfate: terpineol: the proportion of the liquid ethyl cellulose is 1-50 ml: 1-200 ml: 1 to 200 ml. The absorption of the photo-anode film to visible light is enhanced through the melem micro-doped nano semiconductor photo-anode; the specific surface area of the photo-anode film is increased, and the loading capacity of dye molecules is effectively improved; meanwhile, the large-particle melem material enhances the scattering capacity of the light anode film, enhances the optical path and achieves the purpose of synergistically improving the photoelectric conversion efficiency of the dye-sensitized solar cell
The invention has the following beneficial effects:
(1) the preparation process used in the invention is simple, and the physical method is adopted to mix melem and SnO2Doping, no by-product in the preparation process, and environmental protection.
(2) The invention can generate co-sensitization effect by adding melem, enhance the light absorption intensity and improve the sunlight utilization rate.
(3) SnO can be adjusted through melem doping energy2The energy band increases the response capability of the photo-anode to visible light, and improves photo-generated electrons, thereby improving the photoelectric conversion efficiency of the dye-sensitized solar cell.
(4) According to the invention, through the doping of melem, the specific surface area of the photo-anode is increased, more dyes can be absorbed, and the absorption of sunlight is facilitated.
Drawings
FIG. 1 is a melem diagram: (a) before washing; (b) after washing.
FIG. 2 is a melem NMR spectrum.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings. The reagents used in the invention are obtained by conventional experiments or on the market.
Example 1:
a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency comprises the following steps:
(1) preparing a melem material: dispersing melamine in ultrapure water, performing ultrasonic treatment for 30min to obtain a dispersion liquid with the concentration of 0.5mg/ml, and heating the dispersion liquid to 100 ℃ until water is evaporated to obtain solid particles; calcining the solid particles in a muffle furnace at 250 ℃ for 2h, washing the obtained product with ultrapure water and acetonitrile in sequence, and drying at 60 ℃ for 2h to obtain the melem;
(2) preparing a melem-doped semiconductor slurry: SnO prepared by using tin sulfate2Weighing 30ml of ethanol, pouring the ethanol into 0.9988g of ethyl cellulose, and stirring for 2 hours to obtain liquid ethyl cellulose; adding 15ml of terpineol and ethyl cellulose into SnO2Concentrating the slurry into a viscous state by using a rotary evaporator; weighing 1g of SnO2Putting the slurry and 0.0g of melem powder into a mortar, and fully and uniformly grinding to obtain a compound with the mass fraction of melem of 0.0%;
(3) preparing a dye-sensitized solar cell:
smearing melem-doped SnO by adopting blade coating method2Calcining the slurry at 300 ℃ for 200 minutes to prepare the solar cell photo-anode; preparing a counter electrode by adopting a chloroplatinic acid pyrolysis method; and (3) adopting a heat sealing machine to package the battery, wherein the technological parameters are as follows: the pressure is 0.3MPa, the temperature is 100 ℃, and the time is 1 minute; and injecting liquid electrolyte, sealing holes, and carrying out photoelectric performance test to obtain the photoelectric conversion efficiency of 16.2%.
Example 2:
a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency comprises the following steps:
(1) preparing a melem material: dispersing melamine in ultrapure water, performing ultrasonic treatment for 60min to obtain a dispersion liquid with the concentration of 2mg/ml, and heating the dispersion liquid to 150 ℃ until water is evaporated to obtain solid particles; calcining the solid particles in a muffle furnace at 350 ℃ for 1h, washing the obtained product with ultrapure water and acetonitrile in sequence, and drying at 75 ℃ for 1h to obtain the melem;
(2) preparing a melem-doped semiconductor slurry: SnO prepared by using tin sulfate2Weighing 30ml of ethanol, pouring the ethanol into 0.5g of ethyl cellulose, and stirring for 2 hours to obtain liquid ethyl cellulose; adding 15ml of terpineol and ethyl cellulose into SnO2Concentrating the slurry into a viscous state by using a rotary evaporator; weighing 1g of SnO2Putting the slurry and 0.001g of melem powder into a mortar, and fully and uniformly grinding to obtain a compound with the mass fraction of melem of 0.1%;
(3) preparing a dye-sensitized solar cell:
smearing melem-doped SnO by adopting blade coating method2Calcining the slurry at 550 ℃ for 10 minutes to prepare the solar cell photo-anode; preparing a counter electrode by adopting a chloroplatinic acid pyrolysis method; and (3) adopting a heat sealing machine to package the battery, wherein the technological parameters are as follows: the pressure is 0.3MPa, the temperature is 100 ℃, and the time is 1 minute; and injecting liquid electrolyte, sealing holes, and carrying out photoelectric performance test to obtain the photoelectric conversion efficiency of 18.6%.
Example 3:
a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency comprises the following steps:
(1) preparing a melem material: dispersing melamine in ultrapure water, performing ultrasonic treatment for 40min to obtain a dispersion liquid with the concentration of 1mg/ml, and heating the dispersion liquid to 130 ℃ until water is evaporated to obtain solid particles; calcining the solid particles in a muffle furnace at 300 ℃ for 1-2h, washing the obtained product with ultrapure water and acetonitrile in sequence, and drying at 70 ℃ for 1.3h to obtain the melem;
(2) preparing a melem-doped semiconductor slurry: SnO prepared by using tin sulfate2Weighing 25ml of ethanol, pouring into 13g of ethyl cellulose, and stirring for 2 hours to obtain liquid ethyl cellulose; adding 15ml of terpineol and ethyl cellulose into SnO2Concentrating the slurry into a viscous state by using a rotary evaporator; weighing 1g of SnO2Putting the slurry and 0.01g of melem powder into a mortar, and fully and uniformly grinding to obtain a compound with the mass fraction of melem of 1%;
(3) preparing a dye-sensitized solar cell:
smearing melem-doped SnO by adopting blade coating method2Calcining the slurry at 500 ℃ for 40 minutes to prepare the solar cell photo-anode; preparing a counter electrode by adopting a chloroplatinic acid pyrolysis method; and (3) adopting a heat sealing machine to package the battery, wherein the technological parameters are as follows: the pressure is 0.3MPa, the temperature is 100 ℃, and the time is 1 minute; and injecting liquid electrolyte, sealing holes, and carrying out photoelectric performance test to obtain the photoelectric conversion efficiency of 19%.
Example 4:
a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency comprises the following steps:
(1) preparing a melem material: dispersing melamine in ultrapure water, performing ultrasonic treatment for 55min to obtain a dispersion liquid with the concentration of 1.4mg/ml, and heating the dispersion liquid to 120 ℃ until water is evaporated to obtain solid particles; calcining the solid particles in a muffle furnace at 330 ℃ for 1.8h, washing the obtained product with ultrapure water and acetonitrile in sequence, and drying at 68 ℃ for 1.8h to obtain the melem;
(2) preparing a melem-doped semiconductor slurry: SnO prepared by using tin sulfate2Weighing 25ml of ethanol, pouring the ethanol into 11g of ethyl cellulose, and stirring for 2 hours to obtain liquid ethyl cellulose; adding 15ml of terpineol and ethyl cellulose into SnO2Concentrating the slurry into a viscous state by using a rotary evaporator; weighing 1g of SnO2Putting the slurry and 0.005g of melem powder into a mortar, and fully and uniformly grinding to obtain a compound with the mass fraction of melem of 0.5%;
(3) preparing a dye-sensitized solar cell:
smearing melem-doped SnO by adopting blade coating method2Calcining the slurry at 450 ℃ for 150 minutes to prepare the solar cell photo-anode; preparing a counter electrode by adopting a chloroplatinic acid pyrolysis method; and (3) adopting a heat sealing machine to package the battery, wherein the technological parameters are as follows: the pressure is 0.3MPa, the temperature is 100 ℃, and the time is 1 minute; and injecting liquid electrolyte, sealing holes, and carrying out photoelectric performance test to obtain the photoelectric conversion efficiency of 18.3%.
The melem materials obtained in example 2 and example 3 were selected for elemental analysis and nmr test, and the results of elemental analysis are shown in table 1 and nmr test is shown in fig. 2.
Table 1 elemental analysis table:
Figure GDA0002900303050000071

Claims (8)

1. a preparation method of a dye-sensitized solar cell with high photoelectric conversion efficiency is characterized in that a physical method is applied to dope a melem material into a photo-anode material, or a layer of melem grows in situ on the surface of the photo-anode;
the preparation method of melem is as follows:
s1, dispersing melamine in ultrapure water, performing ultrasonic treatment for 30-60min to obtain dispersion liquid, and heating the dispersion liquid to 100-150 ℃ until water is evaporated to obtain solid particles;
s2, calcining the solid particles in a muffle furnace at 250-350 ℃ for 1-2h, washing the obtained product with ultrapure water and acetonitrile in sequence, and drying at 60-75 ℃ for 1-2h to obtain the melem.
2. The method of claim 1, wherein the concentration of the dispersion is 0.5-2 mg/ml.
3. The method for manufacturing a dye-sensitized solar cell with high photoelectric conversion efficiency according to any one of claims 1-2, characterized in that a semiconductor with a particle size of 1-50nm is used as an electron transport layer material, and a semiconductor with a particle size of 40-1000nm is used as a scattering layer material.
4. The method of claim 3, wherein the mass percentage of melem to semiconductor is 0.1-1%.
5. The method of claim 4, wherein the semiconductor is TiO selected from the group consisting of2、SnO2、ZnO、LaTiO3、Nb2O5、In2O3、Zn2SnO4、Fe2O3Or CdS.
6. The method for preparing a dye-sensitized solar cell with high photoelectric conversion efficiency according to claim 5, characterized in that said method comprises the following steps:
step (1), preparing a melem material; step (2), preparing a melem-doped semiconductor slurry; and (3) preparing the dye-sensitized solar cell by adopting the melem-doped semiconductor slurry obtained in the step (2).
7. The method for preparing a dye-sensitized solar cell with high photoelectric conversion efficiency according to claim 5, characterized in that SnO is used2When the photo-anode is used, the method comprises the following steps: preparation of SnO from tin sulfate2Slurry; weighing ethanol, pouring the ethanol into ethyl cellulose, and stirring to obtain liquid ethyl cellulose; adding terpineol and liquid ethyl cellulose into SnO2Concentrating the slurry to be viscous; taking viscous SnO2Putting the mixture into a mortar, adding a certain amount of melem powder, and fully and uniformly grinding; smearing melem-doped SnO by adopting blade coating method2And calcining the slurry at the temperature of 300-550 ℃ for 10-200 minutes to obtain the solar cell photo-anode.
8. The method for preparing a dye-sensitized solar cell with high photoelectric conversion efficiency according to claim 6 or 7, characterized in that 0.5-15 g of ethyl cellulose is added per 30ml of ethanol; tin sulfate: terpineol: the proportion of the liquid ethyl cellulose is 1-50 ml: 1-200 ml: 1 to 200 ml.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105632773A (en) * 2016-04-01 2016-06-01 北京化工大学 Method for improving photoelectric conversion efficiency of dye-sensitized solar cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105632773A (en) * 2016-04-01 2016-06-01 北京化工大学 Method for improving photoelectric conversion efficiency of dye-sensitized solar cell

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* Cited by examiner, † Cited by third party
Title
Enhanced performance of dye-sensitized solar cells based on organic dopant incorporated PVDF-HFP/PEO polymer blend electrolyte with g-C3N4/TiO2 photoanode;R.A. Senthil等;《Journal of Solid State Chemistry》;20160730;第242卷;第199-206页 *
Melem: A metal-free unit for photocatalytic hydrogen evolution;Sheng Chu等;《international journal o f hydrogen energy》;20140314;第39卷;第13519-13526页 *
Structural and optical properties of carbon nitride polymorphs;Luigi Stagi等;《Diamond & Related Materials》;20160618;第68卷;全文 *

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