CN110600270B - Preparation method of photoanode of dye-sensitized solar cell - Google Patents
Preparation method of photoanode of dye-sensitized solar cell Download PDFInfo
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- CN110600270B CN110600270B CN201910623365.2A CN201910623365A CN110600270B CN 110600270 B CN110600270 B CN 110600270B CN 201910623365 A CN201910623365 A CN 201910623365A CN 110600270 B CN110600270 B CN 110600270B
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- 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
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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
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- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a preparation method of a dye-sensitized solar cell photo-anode, which comprises the following steps: preparing slurry; step (2) preparation of the adsorption layer coating: with fluorine-doped SnO2Transparent conductive glass (FTO) is taken as a substrate, and the TiO obtained in the step (1) is treated2Coating the nanoparticle slurry on the substrate; preparing a scattering layer coating: preparing the mesoporous spherical TiO obtained in the step (1)2And TiO2The nanoparticle mixture slurry was coated on the adsorption layer in (2), and the thickness of the coating was controlled to 4-10 μm. The utilization rate of light is improved, and the photoelectric conversion efficiency of the cell is obviously improved.
Description
Technical Field
The invention relates to the preparation of a dye-sensitized solar cell photo-anode in the field of new energy materials, in particular to a method for preparing a dye-sensitized solar cell photo-anode by TiO2The nano particles are an adsorption layer and mesoporous spherical TiO2And TiO2A preparation method of a double-coating photo-anode taking a mixture of nano-particles as a scattering layer.
Background
With the increasing severity of energy crisis, greenhouse effect, environmental pollution and other problems, people pay more attention to the development and utilization of renewable energy, and solar energy is the most potential new energy. As a renewable energy source, solar energy has great advantages: compared with fossil fuel, the solar energy is inexhaustible; compared with nuclear energy, solar energy is safer and does not cause any pollution to the environment; compared with water energy and wind energy, the solar energy has low use cost and is not limited by regions.
Dye-sensitive solar cells are a device for converting solar energy into electrical energy, produced by O' Regan and by 1991
It is first proposed. Photoanodes are of great interest as the most important component of dye-sensitive solar cells. The main material of the photo-anode is TiO2ZnO, and SnO2And the like. Generally, the materials used by people are nano materials, the size of the nano materials is less than 100nm, the scattering effect on light is poor, the utilization rate of light is poor, and finally the conversion rate of the dye-sensitive solar cell is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a dye-sensitized solar cell photo-anode, which is used for preparing a double-coating (an adsorption layer and a scattering layer) dye-sensitized solar cell photo-anode and improving the photoelectric conversion efficiency of the cell.
The invention is realized by the following technical scheme: a preparation method of a dye-sensitized solar cell photo-anode comprises the following steps:
(1) preparing slurry;
(2) preparing an adsorption layer coating: with fluorine-doped SnO2Transparent conductive glass (FTO) is taken as a substrate, and the TiO obtained in the step (1) is treated2Coating the nanoparticle slurry on the substrate;
(3) preparing a scattering layer coating: preparing the mesoporous spherical TiO obtained in the step (1)2And TiO2The nanoparticle mixture slurry was coated on the adsorption layer in (2), and the thickness of the coating was controlled to 4-10 μm.
Preferably, the step (1) is specifically:
1.000g of TiO were weighed2Nano particle (size 5-100nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (the mesoporous spherical TiO)2The diameter is 150-3000nm, and the pore size is 2-50 nm; the TiO is2The size of the nano particles is 10-30nm, wherein the mesoporous spherical TiO2And said TiO2The mass ratio of the nano particles is 1:1-9:1), 0.500g of ethyl cellulose and 4.060g of terpineol, and then 75ml of ethanol is added to be used as a dispersing agent;
firstly, carrying out ultrasonic treatment for 0.5 hour, then putting the mixture into a ball mill, and carrying out ball milling for 24 hours at 300 revolutions per minute;
after ball milling, evaporating the suspension for 1 hour by using a rotary evaporator at the rotating speed of 60 revolutions per minute, and removing most of the dispersing agent;
and then, putting the obtained slurry into an agate mortar for grinding for 1 hour to finish the preparation of the slurry.
Preferably, the step (2) is specifically: with fluorine-doped SnO2Transparent conductive glass FTO isThe FTO is wiped clean by a lens wiping paper and 50mmol/L TiCl is put in4Treating the solution at 70 ℃ for 40 minutes;
and (3) coating the slurry obtained in the step (1) on the FTO substrate by using a coating machine, and treating the electrode at 125 ℃ for 5 minutes and drying to complete coating of the adsorption layer coating, wherein the thickness of the adsorption layer is controlled to be 10-16 mu m.
Preferably, the step (3) is specifically: the electrode coated with the adsorption layer in the step (2) is used again with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes;
then, the mesoporous spherical TiO is coated by a film coater2And TiO2Coating the mixture slurry of the nano particles on the adsorption layer coating in the step (2);
then, the electrode is treated for 5 minutes and dried at 125 ℃, and the thickness of the scattering layer is controlled to be 4-10 mu m;
and finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Advantageous effects
The invention has the beneficial effects that the TiO is prepared2The nano particles are an adsorption layer and mesoporous spherical TiO2And TiO2The mixture of the nano particles is a scattering double-coating photo-anode, and the nano particles are used as the photo-anode of the dye-sensitized solar cell, so that the utilization rate of light is improved compared with a single coating, and the photoelectric conversion efficiency of the cell is obviously improved.
A photoanode adsorption layer made of TiO2The nano particles are composed, have high specific surface area, can adsorb a large amount of dye, and can convert most of photons into electrons.
A light anode scattering layer made of mesoporous spherical TiO2And TiO2Mixture of nanoparticles, mesoporous spherical TiO2The method mainly plays two roles:
firstly, due to the size effect, the light passing through the adsorption layer has a better scattering effect, and the utilization rate of the light can be improved;
and secondly, due to the existence of the mesopores, the dye can be adsorbed, so that the photoelectric conversion efficiency is further improved.
TiO in photoanode scattering layer2The nanoparticles serve two main functions:
firstly, the mesoporous spherical TiO can be filled2The space between them, TiO2The connection between the electrodes is tighter, and the internal resistance of the electrodes is reduced;
second, TiO2The nano particles can also absorb part of dye, so that the photoelectric conversion efficiency is further improved.
Drawings
FIG. 1 is a schematic view of a double coated photoanode:
0 represents: FTO;
1 represents: TiO 22An adsorption layer coating;
2 represents: TiO 22And coating the scattering layer.
FIG. 2 is TiO2Scanning electron microscopy of nanoparticles.
FIG. 3 is a mesoporous spherical TiO2Scanning electron microscope pictures.
Fig. 4 is a voltage-current graph.
Detailed Description
The invention is further described below with reference to the following figures and specific examples. It is to be understood that the embodiments discussed herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the purview of this application and scope of the appended claims
Example 1
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size 20nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 1600nm, and the pore size is 35 nm; TiO 22The size of the nano-particles is 10nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 1:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension is spunAnd (3) carrying out evaporation treatment for 1 hour by an evaporator at the rotating speed of 60 revolutions per minute to remove most of the dispersing agent, and then putting the obtained slurry into an agate mortar for grinding for 1 hour to finish the preparation of the slurry.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 10 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 4 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 2
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size 20nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 540nm, and the pore size is 30 nm; TiO 22The size of the nano particles is 20nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 2:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 10 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 6 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 3
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size 20nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 800nm, and the aperture size is 52 nm; TiO 22The size of the nano-particles is 30nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 4:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2Nano-particlesThe particle slurry was coated on the above substrate, and the thickness of the coating layer was controlled to 10 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 6 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 4
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size 10nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 210nm, and the pore size is 8 nm; TiO 22The size of the nano-particles is 10nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 2:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 12 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 8 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 5
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size 10nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 350nm, and the pore size is 18 nm; TiO 22The size of the nano-particles is 30nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 2:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 10 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2Coating the slurry of the nanoparticle mixture on the adsorption layer coating in (2), the coatingThe thickness of (2) was controlled to 6 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 6
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size 10nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 540nm, and the pore size is 30 nm; TiO 22The size of the nano-particles is 10nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 9:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 12 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 8 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 7
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticle (size of 8nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 350nm, and the pore size is 18 nm; TiO 22The size of the nano-particles is 10nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 9:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 12 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 10 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 8
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticles (size 50nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 210nm, and the pore size is 8 nm; TiO 22The size of the nano-particles is 10nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 9:1), 0.500g of ethyl cellulose and 4.060g of terpineol, then 75ml of ethanol is added to be used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, then the mixture is placed into a ball mill, the rotation speed per minute is 300, and the ball milling is carried out for 24 hours. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 12 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 8 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
Example 9
(1) Preparation of the slurry
1.000g of TiO were weighed2Nanoparticles (size 80nm) or mesoporous spherical TiO2And TiO2Mixture of nanoparticles (mesoporous spherical TiO)2The diameter is 1600nm, and the pore size is 35 nm; TiO 22The size of the nano-particles is 10nm, and the mesoporous spherical TiO2And TiO2The mass ratio of the nano particles is 9:1), 0.500g of ethyl cellulose and 4.060g of terpineol are added, and then 75ml of ethanol is added for separationAnd (3) performing ultrasonic treatment on the powder for 0.5 hour, then putting the powder into a ball mill, and performing ball milling for 24 hours at 300 revolutions per minute. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporator at a rotation speed of 60 rpm to remove most of the dispersant, and the resulting slurry was put into an agate mortar and ground for 1 hour to complete the slurry preparation.
(2) Preparation of adsorbent layer coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 10 μm. And (3) treating the electrode at 125 ℃ for 5 minutes and drying to finish the coating of the adsorption layer.
(3) Production of a coating for a scattering layer
The electrode in (2) was again charged with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes. Then, the mesoporous spherical TiO is coated by a film coater2And TiO2The slurry of the nanoparticle mixture was coated on the adsorption layer coating in (2), and the thickness of the coating was controlled to 6 μm. The electrode was then dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
FIG. 1 is a schematic view of a double coated photoanode: 0 represents: FTO; 1 represents: TiO 22An adsorption layer coating; 2 represents: TiO 22And coating the scattering layer. FIG. 2 is TiO2Scanning electron microscopy of nanoparticles. FIG. 3 is a mesoporous spherical TiO2Scanning electron microscope pictures.
Fig. 4 is a voltage-current graph.
Comparative example
(1) Preparation of the slurry
1.000g of TiO were weighed2Nano particles (with the size of 20nm), 0.500g of ethyl cellulose and 4.060g of terpineol are added, 75ml of ethanol is used as a dispersing agent, ultrasonic treatment is firstly carried out for 0.5 hour, and then the mixture is put into a ball mill for ball milling for 24 hours at 300 revolutions per minute. After ball milling, the suspension was evaporated for 1 hour using a rotary evaporatorAt the rotation speed of 60 revolutions per minute, most of the dispersant is removed, and then the obtained slurry is put into an agate mortar for grinding for 1 hour, thus finishing the preparation of the slurry.
(2) Production of the coating
FTO is used as a substrate. Firstly, wiping the FTO clean with a piece of lens wiping paper, and putting 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes to facilitate the application of the coating. Then, the TiO in (1) is coated by a film coater2The nanoparticle slurry was coated on the above substrate, and the thickness of the coating was controlled to 16 μm. The electrode was dried by treatment at 125 ℃ for 5 minutes. And finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the single-coating photo-anode.
Battery assembly
(1) Dye adsorption
And (3) putting the prepared photo-anode into a 0.5mM N719 solution, and soaking for 24 h. And (3) washing off the dye physically adsorbed on the surface of the anode by using absolute ethyl alcohol, and drying in a forced air drying oven at 50 ℃ to finish the preparation of the whole photoanode working electrode.
(2) Counter electrode
The invention uses a pure platinum sheet as the counter electrode, with dimensions of both 2.5cm by 2.5cm and 1.0cm by 1.0 cm.
(3) Counter electrode
The electrolyte used herein is a Z960 type electrolyte: 0.03M I20.05M LiI, 0.5M 4-tert-butylpyridine, 0.1M guanidinium thiocyanate, 1M dimethylimidazole iodide (DMII), solvent in a volume ratio of 85: 15 acetonitrile and valeronitrile.
(4) Dye-sensitized solar cell testing
The light source used in the test was a 150W bromine tungsten lamp, which was calibrated to an incident light intensity of 100W m using a standard Si cell prior to use-2. The electrical signals of the batteries were collected by a chemical workstation (IM6e, germany) to obtain a current-voltage curve. The scanning speed is 10mV s-1。
The photo-anodes in the above examples and comparative examples were dropped with 1 to 2 drops of the electrolyte, and tightly clamped together with a clamp and a platinum electrode, and performance tests were performed. The results are shown in Table 1.
TABLE 1 parameters of photoelectrode and conversion efficiency in examples and comparative examples
Note: in the tables, `- ` is shown to be unusable.
As can be seen from table 1, the double-coating photoelectric conversion efficiency is higher than the single-coating efficiency in each example except example 9, and thus it can be confirmed that the present invention can effectively improve the photoelectric conversion efficiency of the dye-sensitized solar cell.
The size of the nanoparticles used in example 9 was too large, so that the amount of dye adsorbed was smaller than that in the comparative example, resulting in lower photoelectric conversion efficiency in this example.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.
Claims (3)
1. A preparation method of a dye-sensitized solar cell photo-anode is characterized by comprising the following steps: (1) preparing slurry; (2) preparing an adsorption layer coating: with fluorine-doped SnO2Transparent conductive glass (FTO) is taken as a substrate, and the TiO obtained in the step (1) is treated2Coating the nanoparticle slurry on the substrate; (3) preparing a scattering layer coating: preparing the mesoporous spherical TiO obtained in the step (1)2And TiO2Coating the nano particle mixture slurry on the adsorption layer in the step (2), wherein the thickness of the coating is controlled to be 4-10 mu m; the step (1) is specifically: 1.000g of TiO were weighed2Nanoparticles of 5-100nm size or mesoporous spherical TiO2And TiO2Mixture of nanoparticles, in which the mesoporous spherical TiO2The diameter is 150-3000nm, the pore size is 2-50nm, wherein the TiO2The size of the nano particles is 10-30nm, wherein the mesoporous spherical TiO2And said TiO2The mass ratio of the nano particles is 1:1-9: 1; 0.500g of ethyl cellulose; 4.060g terpineol; then 75ml of ethanol is added as a dispersing agent; firstly, carrying out ultrasonic treatment for 0.5 hour, then putting the mixture into a ball mill, and carrying out ball milling for 24 hours at 300 revolutions per minute; after ball milling, evaporating the suspension for 1 hour by using a rotary evaporator at the rotating speed of 60 revolutions per minute, and removing most of the dispersing agent; and then, putting the obtained slurry into an agate mortar for grinding for 1 hour to finish the preparation of the slurry.
2. The method for preparing the photoanode of the dye-sensitized solar cell according to claim 1, wherein the step (2) comprises: with fluorine-doped SnO2Using transparent conductive glass FTO as a substrate, wiping the FTO clean by using a lens wiping paper, and putting 50mmol/L TiCl4Treating the solution at 70 ℃ for 40 minutes; and (3) coating the slurry obtained in the step (1) on the FTO substrate by using a coating machine, and treating the electrode at 125 ℃ for 5 minutes and drying to complete coating of the adsorption layer coating, wherein the thickness of the adsorption layer is controlled to be 10-16 mu m.
3. The method for preparing the photoanode of the dye-sensitized solar cell according to claim 2, wherein the step (3) comprises: the electrode coated with the adsorption layer in the step (2) is used again with 50mmol/L TiCl4The solution was treated at 70 ℃ for 40 minutes; then, the mesoporous spherical TiO is coated by a film coater2And TiO2Coating the mixture slurry of the nano particles on the adsorption layer coating in the step (2); then, the electrode is treated for 5 minutes and dried at 125 ℃, and the thickness of the scattering layer is controlled to be 4-10 mu m; and finally, putting the dried electrode into a muffle furnace, and calcining for 30 minutes at 500 ℃ to finish the preparation of the double-coating photo-anode.
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