CN108922785B - Preparation method of counter electrode material of dye-sensitized solar cell - Google Patents
Preparation method of counter electrode material of dye-sensitized solar cell Download PDFInfo
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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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention belongs to the technical field of preparation of green renewable clean energy, and particularly relates to a preparation method of a counter electrode material of a dye-sensitized solar cell. The invention uses emulsifier OP-10, liquid paraffin, etc. as raw materials to obtain oil-in-water emulsion, the oil-in-water emulsion is mixed with sodium metasilicate nonahydrate solution for reaction to obtain counter electrode slurry, the counter electrode slurry is frozen and centrifugally collected to precipitate, and is mixed with dispersed gel-like coating and sprayed on the surface of FTO conductive glass to obtain the dye-sensitized solar cell counter electrode material.
Description
Technical Field
The invention belongs to the technical field of preparation of green renewable clean energy, and particularly relates to a preparation method of a counter electrode material of a dye-sensitized solar cell.
Background
With the rapid development of society, the demand of human beings for energy is increasing day by day, however, the energy crisis and environmental pollution problems caused by excessive exploitation and use of fossil energy have gradually emerged and become the leading factors restricting the sustainable and healthy development of economy and society at present. Therefore, the development of renewable energy is one of effective approaches to solve the above problems. Solar energy is one of the most promising energy sources as an inexhaustible, pollution-free and clean natural green energy source.
The dye-sensitized solar cell is a novel solar cell, and compared with the traditional silicon solar cell, the dye-sensitized solar cell has the advantages of wide raw material source, low cost, high theoretical conversion efficiency, capability of generating power on cloudy days or indoor light sources and the like, thereby becoming an attention product of the novel solar cell. The dye-sensitized solar cell mainly comprises a photo-anode, a dye, an electrolyte, a counter electrode and the like. The counter electrode is used as a core part and mainly used for collecting electrons transmitted from the photo-anode through an external circuit and transferring the electrons to the electrolyte to reduce and regenerate the electrons. Generally, the following conditions are required for the electrode material: (1) good stability, no reaction with substances in the electrolyte; (2) good conductivity; (3) has better catalytic capability to electrolyte.
At present, platinum is the most commonly used catalyst for the counter electrode of the dye-sensitized solar cell, and other commonly used materials comprise carbon materials, conductive polymers, carbides, sulfides, nitrides of transition metals and the like. Platinum has good conductivity and excellent electrocatalytic performance, and is the most common counter electrode material of the existing dye-sensitized solar cell. However, the platinum counter electrode is corroded by the electrolyte in the long-term working process to reduce the efficiency of the cell, and the platinum is used as a noble metal material, so that the expensive price is not favorable for the industrial production of the dye-sensitized solar cell. In order to further reduce the cost, in recent years, research and development of counter electrode materials of dye-sensitized solar cells by different research institutes at home and abroad mainly focuses on non-platinum counter electrode catalytic materials (such as carbon materials, conductive polymers and the like). But the caking property of the carbon material and the conductive substrate is poor, and the conductive film is easy to fall off from the conductive substrate, so that the stability of the battery is influenced; the conductive polymer material has poor thermal stability, poor corrosion resistance, low photoelectric conversion efficiency and poor repeatability and stability, and further popularization and application of the material in the fields of chemistry and electrochemistry are hindered. Carbon nanomaterials are low in price, stable in performance, high in conductivity and good in electrocatalytic activity, and thus are widely studied as counter electrodes. However, the carbon nanomaterial is easily agglomerated, and the electrochemical performance of the carbon nanomaterial is weakened to a certain extent, so that the application range of the carbon nanomaterial is limited.
Therefore, on the basis of overcoming the defects, the development of the alternative platinum electrode catalytic material with high performance, high efficiency, low cost and long-term stability is an important way for promoting the industrialization process of the dye-sensitized solar cell.
Disclosure of Invention
The invention mainly solves the technical problems, and provides a preparation method of a counter electrode material of a dye-sensitized solar cell aiming at the defects that most of Pt counter electrode catalytic materials developed at present have low photoelectric conversion efficiency, carbon nano materials are easy to agglomerate when being applied to the counter electrode material, and the electrocatalysis efficiency of the counter electrode material is low.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a counter electrode material of a dye-sensitized solar cell is characterized by comprising the following specific preparation steps:
(1) placing 12-15 g of paranitroaniline in a beaker, adding 35-40 mL of hydrochloric acid with the mass fraction of 20%, heating, raising the temperature, keeping the temperature and stirring until the solid is completely dissolved, then placing the beaker in an ice bath condition for rapidly cooling, stirring at the rotating speed of 300-400 r/min, adding 40-50 mL of sodium nitrite aqueous solution, reacting, adding 4-5 g of sulfamic acid in the beaker, performing suction filtration, and separating to obtain a filtrate, namely paranitroaniline diazonium salt solution;
(2) placing 10-12 g of multi-walled carbon nanotubes in a three-neck flask, adding 200-300 mL of deionized water, placing the three-neck flask in an ultrasonic disperser, ultrasonically dispersing for 30-35 min, dropwise adding 40-50 mL of p-nitroaniline diazonium salt solution and 4-5 g of tungsten carbide into the three-neck flask by using a dropping funnel, reacting while dropwise adding until dropwise adding is finished, carrying out suction filtration on reaction liquid in the three-neck flask, sequentially cleaning filter residues for 3-4 times by using deionized water and absolute ethyl alcohol until the filtrate is colorless, and collecting to obtain a filtrate;
(3) putting the filtrate in a rotary evaporator, carrying out rotary evaporation for 10-15 min at the rotating speed of 80-90 r/min to obtain organic dispersed carbon nanotubes, adding 10-15 g of polyethylene glycol 10000 and 100-120 mL of toluene into a four-neck flask, heating, stirring until the solid is dissolved, cooling, adding 0.8-1.0 g of toluene-2, 4-diisocyanate and 0.4-0.5 mL of dibutyltin dilaurate, reacting, heating again, reacting, adding 30-40 g of organic dispersed carbon nanotubes, and mixing to obtain a dispersed gel-like coating;
(4) placing 40-45 mL of liquid paraffin, 10-12 mL of emulsifier OP-10 and 200-220 mL of hydrochloric acid into a three-neck flask, starting a stirrer, stirring at a rotating speed of 250-300 r/min, dropwise adding 200mL of sodium metasilicate nonahydrate solution into the three-neck flask by using a constant-pressure dropping funnel, stirring for reaction, naturally cooling to room temperature, and discharging to obtain counter electrode slurry;
(5) and (2) placing the dispersed gel-like coating into a high-speed refrigerated centrifuge for centrifugal treatment, standing, collecting precipitates, mixing the precipitates, counter electrode slurry and titanium dioxide to obtain a gel-like coating, and spraying the gel-like coating on the surface of FTO (fluorine-doped tin oxide) conductive glass by using a spray gun to form a photoelectric conversion electrode film so as to obtain the counter electrode material of the dye-sensitized solar cell.
The mass fraction of the hydrochloric acid in the step (1) is 20%, the temperature after heating is 70-80 ℃, the temperature after the beaker is placed under an ice bath condition and is rapidly cooled is 0-5 ℃, the mass fraction of the sodium nitrite aqueous solution is 5%, and the reaction time is 30-35 min.
And (3) carrying out ultrasonic dispersion at the temperature of 50-55 ℃, the ultrasonic frequency of 25-30 kHz, and the dropping rate of the dropping funnel of 3-4 mL/min.
The temperature of the rotary evaporation in the step (3) is 80-85 ℃, the temperature of the four-neck flask after heating is 70-80 ℃, the temperature after cooling is 40-50 ℃, the reaction time is 4-5 h, the temperature after heating is 70-75 ℃, and the reaction time is 10-12 h.
The mass fraction of the hydrochloric acid in the step (4) is 5%, the dropping speed of the constant-pressure dropping funnel is 2-3 mL/min, the mass fraction of the sodium metasilicate nonahydrate solution is 40%, and the stirring reaction time is 2-3 h.
The rotating speed of the high-speed refrigerated centrifuge in the step (5) is 5000-7000 r/min, the centrifugal treatment time is 10-30 min, the standing time is 3-4 h, the mixing mass ratio of the precipitate, the counter electrode slurry and the titanium dioxide is 6: 2: 1, the caliber of the spray gun is 1.0-1.5 mm, the vertical distance between the control nozzle and the FTO conductive glass is 15-20 cm, the spraying pressure is 0.15-0.30 MPa, and the thickness of the photoelectric conversion electrode film is 0.1-0.2 mm.
The invention has the beneficial effects that:
(1) the invention acidifies and dissolves an emulsifier OP-10, liquid paraffin and hydrochloric acid, then carries out homogeneous emulsification under a heating state to obtain an oil-in-water emulsion, mixes the oil-in-water emulsion and sodium metasilicate nonahydrate solution for reaction to obtain a counter electrode slurry, mixes the counter electrode slurry, freezes, centrifugalizes and collects precipitates and a dispersed gel-like coating to form a gel-like coating, sprays the gel-like coating on the surface of FTO conductive glass to form a photoelectric conversion electrode film, and obtains a dye-sensitized solar cell counter electrode material, the photoelectric conversion electrode film of the invention is formed by distributing the liquid paraffin and polyethylene glycol 10000 in a hole structure of an organic dispersed carbon nano-tube to form a thermal phase change capsule structure, blocks an outer hole of the organic dispersed carbon nano-tube by taking tungsten carbide as an electrocatalytic active agent, and attaches the electrocatalytic active agent on the surface of the organic dispersed carbon nano, the electrocatalysis efficiency of the counter electrode material is improved, so that the counter electrode material is modified on the surface of the carbon nano tube material by utilizing the paranitroaniline diazonium salt, and the paranitroaniline is introduced into the surface of the counter electrode material through a free radical reaction, so that the carbon nano tube material has good dispersibility and is not easy to agglomerate in the gel-like coating, wherein the compatibility of the carbon nano tube material with other organic components is improved after the carbon nano tube material is modified, and due to the high thermal conductivity and the high specific surface area of the carbon nano tube material, the distribution of thermal phase change substances in the phase change material is more uniform, the convection heat dissipation of the counter electrode material is reduced, and the photoelectric conversion;
(2) the invention is based on the support shaping function of the hard segment in the linear macromolecule framework, uses polyethylene glycol as the soft segment, uses the dye molecule with two equal reactive groups (hydroxyl and amino) as the hard segment, synthesizes the photo-thermal conversion organic shaping phase change energy storage material by a gradual polycondensation method, realizes the phase change temperature adjustment, shaping phase change energy storage and high energy storage density of the material, uses high latent heat polyethylene glycol 10000 and liquid paraffin which is easy to generate phase change at normal temperature, leads the thermal phase change structure material formed on the surface to have high energy storage efficiency and latent heat value, adds titanium dioxide into the obtained coating, on one hand, the invention has the extinction function and reduces the heat loss of light reflection in the electrode material, on the other hand, the titanium dioxide as the photo-thermal absorption catalyst can be compounded with silicon dioxide in the thermal phase change microcapsule, and Ti-O-Si bonds prevent the mutual contact among particles, the crystal form and the crystal grain growth are inhibited, so that the surface of the titanium dioxide becomes rough, the pore structures among the crystal grains are increased, the defects are increased, the specific surface area of the surface is increased, the area for absorbing light and heat is increased, the forbidden band energy gap of the titanium dioxide is narrowed, the red shift is generated, the titanium dioxide can absorb and convert the light energy of a longer wave band, the photoelectric conversion efficiency of the electrode material is improved, and the electrode material has a wide application prospect.
Detailed Description
Placing 12-15 g of paranitroaniline in a beaker, adding 35-40 mL of 20% hydrochloric acid by mass, heating to 70-80 ℃, keeping the temperature and stirring until the solid is completely dissolved, then placing the beaker in an ice bath condition, rapidly cooling to 0-5 ℃, stirring at a rotating speed of 300-400 r/min, adding 40-50 mL of 5% sodium nitrite aqueous solution, reacting for 30-35 min, adding 4-5 g of sulfamic acid in the beaker, performing suction filtration, and separating to obtain a filtrate, namely the paranitroaniline diazonium salt solution; placing 10-12 g of multi-walled carbon nanotubes in a three-neck flask, adding 200-300 mL of deionized water, placing the three-neck flask in an ultrasonic disperser, ultrasonically dispersing for 30-35 min at the temperature of 50-55 ℃ and the frequency of 25-30 kHz, dropwise adding 40-50 mL of paranitroaniline diazonium salt solution and 4-5 g of tungsten carbide into the three-neck flask at the speed of 3-4 mL/min by using a dropping funnel, reacting while dropwise adding, after dropwise adding is finished, filtering reaction liquid in the three-neck flask, sequentially cleaning filter residues for 3-4 times by using deionized water and absolute ethyl alcohol until the filtrate is colorless, and collecting to obtain the filtrate; putting the filtrate in a rotary evaporator, carrying out rotary evaporation at the temperature of 80-85 ℃ and the rotating speed of 80-90 r/min for 10-15 min to obtain organic dispersed carbon nanotubes, adding 10-15 g of polyethylene glycol 10000 and 100-120 mL of toluene into a four-necked flask, heating to 70-80 ℃, stirring until the solid is dissolved, cooling to 40-50 ℃, adding 0.8-1.0 g of toluene-2, 4-diisocyanate and 0.4-0.5 mL of dibutyltin dilaurate, reacting for 4-5 h, heating to 70-75 ℃, reacting for 10-12 h, adding 30-40 g of organic dispersed carbon nanotubes, and mixing to obtain a dispersed gel-like coating; placing 40-45 mL of liquid paraffin, 10-12 mL of emulsifier OP-10 and 200-220 mL of hydrochloric acid with the mass fraction of 5% in a three-neck flask, starting a stirrer, stirring at the rotating speed of 250-300 r/min, dropwise adding 200mL of sodium metasilicate nonahydrate solution with the mass fraction of 40% into the three-neck flask at the dropwise adding speed of 2-3 mL/min by using a constant-pressure dropping funnel, stirring and reacting for 2-3 h, naturally cooling to room temperature, and discharging to obtain counter electrode slurry; placing the dispersed gel-like coating into a high-speed refrigerated centrifuge with the rotating speed of 5000-7000 r/min for centrifugal treatment for 10-30 min, standing for 3-4 h, collecting precipitates, mixing the precipitates, counter electrode slurry and titanium dioxide according to the mass ratio of 6: 2: 1 to obtain the gel-like coating, spraying the gel-like coating on the surface of FTO conductive glass by using a spray gun with the caliber of 1.0-1.5 mm and controlling the vertical distance between a spray nozzle and the FTO conductive glass to be 15-20 cm, and spraying the gel-like coating under the pressure of 0.15-0.30 MPa to form a photoelectric conversion electrode film with the diameter of 0.1-0.2 mm, thereby obtaining the counter electrode material of the dye-sensitized solar cell.
Example 1
Placing 12g of paranitroaniline in a beaker, adding 35mL of hydrochloric acid with the mass fraction of 20%, heating to 70 ℃, keeping the temperature and stirring until the solid is completely dissolved, placing the beaker in an ice bath condition, rapidly cooling to 0 ℃, stirring at the rotating speed of 300r/min, adding 40mL of sodium nitrite aqueous solution with the mass fraction of 5%, reacting for 30min, adding 4g of sulfamic acid in the beaker, carrying out suction filtration, and separating to obtain a filtrate, namely the paranitroaniline diazonium solution; placing 10g of multi-walled carbon nanotube into a three-neck flask, adding 200mL of deionized water, placing the three-neck flask into an ultrasonic disperser, ultrasonically dispersing for 30min at the temperature of 50 ℃ and the frequency of 25kHz, dropwise adding 40mL of p-nitroaniline diazonium salt solution and 4g of tungsten carbide into the three-neck flask at the speed of 3mL/min by using a dropping funnel, reacting while dropwise adding, after dropwise adding is finished, carrying out suction filtration on reaction liquid in the three-neck flask, sequentially washing filter residues for 3 times by using deionized water and absolute ethyl alcohol until the filtrate is colorless, and collecting to obtain the filtrate; putting the filtrate in a rotary evaporator, carrying out rotary evaporation for 10min at the rotating speed of 80r/min at the temperature of 80 ℃ to obtain organic dispersed carbon nanotubes, adding 10g of polyethylene glycol 10000 and 100mL of toluene into a four-neck flask, heating to 70 ℃, stirring until the solid is dissolved, cooling to 40 ℃, adding 0.8g of toluene-2, 4-diisocyanate and 0.4mL of dibutyltin dilaurate, reacting for 4h, heating to 70 ℃, reacting for 10h, adding 30g of organic dispersed carbon nanotubes, and mixing to obtain a dispersed gel-like coating; placing 40mL of liquid paraffin, 10mL of emulsifier OP-10 and 200mL of hydrochloric acid with the mass fraction of 5% in a three-neck flask, starting a stirrer, stirring at the rotating speed of 250r/min, dropwise adding 200mL of sodium metasilicate nonahydrate solution with the mass fraction of 40% into the three-neck flask at the dropwise adding speed of 2mL/min by using a constant-pressure dropping funnel, stirring for reacting for 2 hours, naturally cooling to room temperature, and discharging to obtain counter electrode slurry; and (2) placing the dispersed gel-like coating into a high-speed refrigerated centrifuge with the rotation speed of 5000r/min for centrifugal treatment for 10min, standing for 3h, collecting precipitates, mixing the precipitates, counter electrode slurry and titanium dioxide according to the mass ratio of 6: 2: 1 to obtain a gel-like coating, using a spray gun with the caliber of 1.0mm, controlling the vertical distance of a nozzle from FTO conductive glass to be 15cm, and spraying the gel-like coating on the surface of the FTO conductive glass at the pressure of 0.15MPa to form a photoelectric conversion electrode film with the thickness of 0.1mm to obtain the counter electrode material of the dye-sensitized solar cell.
Example 2
Putting 13g of paranitroaniline into a beaker, adding 37mL of hydrochloric acid with the mass fraction of 20%, heating to 75 ℃, keeping the temperature and stirring until the solid is completely dissolved, then putting the beaker into an ice bath condition, quickly cooling to 3 ℃, stirring at the rotating speed of 350r/min, adding 45mL of sodium nitrite aqueous solution with the mass fraction of 5%, reacting for 33min, adding 4g of sulfamic acid into the beaker, carrying out suction filtration, and separating to obtain a filtrate, namely the paranitroaniline diazonium solution; placing 11g of multi-walled carbon nanotubes in a three-neck flask, adding 250mL of deionized water, placing the three-neck flask in an ultrasonic disperser, ultrasonically dispersing for 33min at the temperature of 53 ℃ and the frequency of 27kHz, dropwise adding 45mL of p-nitroaniline diazonium salt solution and 4g of tungsten carbide into the three-neck flask at the speed of 3mL/min by using a dropping funnel, reacting while dropwise adding until dropwise adding is finished, carrying out suction filtration on reaction liquid in the three-neck flask, sequentially washing filter residues for 3 times by using deionized water and absolute ethyl alcohol until the filtrate is colorless, and collecting to obtain the filtrate; putting the filtrate in a rotary evaporator, carrying out rotary evaporation for 13min at the rotating speed of 85r/min at 83 ℃ to obtain organic dispersed carbon nanotubes, adding 13g of polyethylene glycol 10000 and 110mL of toluene into a four-neck flask, heating to 75 ℃, stirring until the solid is dissolved, cooling to 45 ℃, adding 0.9g of toluene-2, 4-diisocyanate and 0.4mL of dibutyltin dilaurate, reacting for 4h, heating to 73 ℃, reacting for 11h, adding 35g of organic dispersed carbon nanotubes, and mixing to obtain a dispersed gel-like coating; putting 43mL of liquid paraffin, 11mL of emulsifier OP-10 and 210mL of hydrochloric acid with the mass fraction of 5% into a three-neck flask, starting a stirrer, stirring at the rotating speed of 270r/min, dropwise adding 200mL of sodium metasilicate nonahydrate solution with the mass fraction of 40% into the three-neck flask at the dropwise adding speed of 2mL/min by using a constant-pressure dropping funnel, stirring for reacting for 2 hours, naturally cooling to room temperature, and discharging to obtain counter electrode slurry; placing the dispersed gel-like coating into a high-speed refrigerated centrifuge with the rotating speed of 6000r/min for centrifugal treatment for 20min, standing for 3h, collecting precipitates, mixing the precipitates, counter electrode slurry and titanium dioxide according to the mass ratio of 6: 2: 1 to obtain the gel-like coating, using a spray gun with the caliber of 1.3mm, controlling the vertical distance of a nozzle from FTO conductive glass to be 17cm, and spraying the gel-like coating on the surface of the FTO conductive glass at the pressure of 0.21MPa to form a photoelectric conversion electrode film with the thickness of 0.1mm to obtain the counter electrode material of the dye-sensitized solar cell.
Example 3
Placing 15g of paranitroaniline in a beaker, adding 40mL of hydrochloric acid with the mass fraction of 20%, heating to 80 ℃, keeping the temperature and stirring until the solid is completely dissolved, placing the beaker in an ice bath condition, rapidly cooling to 5 ℃, stirring at the rotating speed of 400r/min, adding 50mL of sodium nitrite aqueous solution with the mass fraction of 5%, reacting for 35min, adding 5g of sulfamic acid in the beaker, carrying out suction filtration, and separating to obtain a filtrate, namely the paranitroaniline diazonium solution; placing 12g of multi-walled carbon nanotubes in a three-neck flask, adding 300mL of deionized water, placing the three-neck flask in an ultrasonic disperser, ultrasonically dispersing for 35min at the temperature of 55 ℃ and the frequency of 30kHz, dropwise adding 50mL of p-nitroaniline diazonium salt solution and 5g of tungsten carbide into the three-neck flask at the speed of 4mL/min by using a dropping funnel, reacting while dropwise adding, after dropwise adding is finished, carrying out suction filtration on reaction liquid in the three-neck flask, sequentially washing filter residues for 4 times by using deionized water and absolute ethyl alcohol until the filtrate is colorless, and collecting to obtain the filtrate; putting the filtrate in a rotary evaporator, carrying out rotary evaporation for 15min at the rotating speed of 90r/min at the temperature of 85 ℃ to obtain organic dispersed carbon nanotubes, adding 15g of polyethylene glycol 10000 and 120mL of toluene into a four-neck flask, heating to 80 ℃, stirring until the solid is dissolved, cooling to 50 ℃, adding 1.0g of toluene-2, 4-diisocyanate and 0.5mL of dibutyltin dilaurate, reacting for 5h, heating to 75 ℃, reacting for 12h, adding 40g of organic dispersed carbon nanotubes, and mixing to obtain a dispersed gel-like coating; putting 45mL of liquid paraffin, 12mL of emulsifier OP-10 and 220mL of hydrochloric acid with the mass fraction of 5% into a three-neck flask, starting a stirrer, stirring at the rotating speed of 300r/min, dropwise adding 200mL of sodium metasilicate nonahydrate solution with the mass fraction of 40% into the three-neck flask at the dropping speed of 3mL/min by using a constant-pressure dropping funnel, stirring for reacting for 3 hours, naturally cooling to room temperature, and discharging to obtain counter electrode slurry; placing the dispersed gel-like coating into a high-speed refrigerated centrifuge with the rotation speed of 7000r/min for centrifugal treatment for 30min, standing for 4h, collecting precipitates, mixing the precipitates, counter electrode slurry and titanium dioxide according to the mass ratio of 6: 2: 1 to obtain a gel-like coating, using a spray gun with the caliber of 1.5mm, controlling the vertical distance of a nozzle from FTO conductive glass to be 20cm, and spraying the gel-like coating on the surface of the FTO conductive glass at the pressure of 0.3MPa to form a photoelectric conversion electrode film with the thickness of 0.2mm to obtain the counter electrode material of the dye-sensitized solar cell.
Comparative example
The dye-sensitized solar cell counter electrode material prepared by the invention and the dye-sensitized solar cell counter electrode material in the comparative example are subjected to cell performance test by taking the dye-sensitized solar cell counter electrode material produced by a company in the city of Xian as the comparative example, and the solar light intensity is tested to be 50mW/cm2The results are shown in table 1:
TABLE 1 measurement results of Properties
According to the data in table 1, the counter electrode material of the dye-sensitized solar cell prepared by the invention has a three-dimensional porous structure and a large specific surface area, is beneficial to the permeation of electrolyte and the transmission of electrons, and has high photoelectric conversion efficiency. The preparation method is simple and effective, low in preparation cost, mild and controllable in preparation conditions, beneficial to large-scale production and wide in application prospect.
Claims (6)
1. A preparation method of a counter electrode material of a dye-sensitized solar cell is characterized by comprising the following specific preparation steps:
(1) placing 12-15 g of paranitroaniline in a beaker, adding 35-40 mL of hydrochloric acid with the mass fraction of 20%, heating, raising the temperature, keeping the temperature and stirring until the solid is completely dissolved, then placing the beaker in an ice bath condition for rapidly cooling, stirring at the rotating speed of 300-400 r/min, adding 40-50 mL of sodium nitrite aqueous solution, reacting, adding 4-5 g of sulfamic acid in the beaker, performing suction filtration, and separating to obtain a filtrate, namely paranitroaniline diazonium salt solution;
(2) placing 10-12 g of multi-walled carbon nanotubes in a three-neck flask, adding 200-300 mL of deionized water, placing the three-neck flask in an ultrasonic disperser, ultrasonically dispersing for 30-35 min, dropwise adding 40-50 mL of p-nitroaniline diazonium salt solution and 4-5 g of tungsten carbide into the three-neck flask by using a dropping funnel, reacting while dropwise adding until dropwise adding is finished, carrying out suction filtration on reaction liquid in the three-neck flask, sequentially cleaning filter residues for 3-4 times by using deionized water and absolute ethyl alcohol until the filtrate is colorless, and collecting to obtain a filtrate;
(3) putting the filtrate in a rotary evaporator, carrying out rotary evaporation for 10-15 min at the rotating speed of 80-90 r/min to obtain organic dispersed carbon nanotubes, adding 10-15 g of polyethylene glycol 10000 and 100-120 mL of toluene into a four-neck flask, heating, stirring until the solid is dissolved, cooling, adding 0.8-1.0 g of toluene-2, 4-diisocyanate and 0.4-0.5 mL of dibutyltin dilaurate, reacting, heating again, reacting, adding 30-40 g of organic dispersed carbon nanotubes, and mixing to obtain a dispersed gel-like coating;
(4) placing 40-45 mL of liquid paraffin, 10-12 mL of emulsifier OP-10 and 200-220 mL of hydrochloric acid into a three-neck flask, starting a stirrer, stirring at a rotating speed of 250-300 r/min, dropwise adding 200mL of sodium metasilicate nonahydrate solution into the three-neck flask by using a constant-pressure dropping funnel, stirring for reaction, naturally cooling to room temperature, and discharging to obtain counter electrode slurry;
(5) and (2) placing the dispersed gel-like coating into a high-speed refrigerated centrifuge for centrifugal treatment, standing, collecting precipitates, mixing the precipitates, counter electrode slurry and titanium dioxide to obtain a gel-like coating, and spraying the gel-like coating on the surface of FTO (fluorine-doped tin oxide) conductive glass by using a spray gun to form a photoelectric conversion electrode film so as to obtain the counter electrode material of the dye-sensitized solar cell.
2. The method for preparing the counter electrode material of the dye-sensitized solar cell according to claim 1, wherein the method comprises the following steps: the mass fraction of the hydrochloric acid in the step (1) is 20%, the temperature after heating is 70-80 ℃, the temperature after the beaker is placed under an ice bath condition and is rapidly cooled is 0-5 ℃, the mass fraction of the sodium nitrite aqueous solution is 5%, and the reaction time is 30-35 min.
3. The method for preparing the counter electrode material of the dye-sensitized solar cell according to claim 1, wherein the method comprises the following steps: and (3) carrying out ultrasonic dispersion at the temperature of 50-55 ℃, the ultrasonic frequency of 25-30 kHz, and the dropping rate of the dropping funnel of 3-4 mL/min.
4. The method for preparing the counter electrode material of the dye-sensitized solar cell according to claim 1, wherein the method comprises the following steps: the temperature of the rotary evaporation in the step (3) is 80-85 ℃, the temperature of the four-neck flask after heating is 70-80 ℃, the temperature after cooling is 40-50 ℃, the reaction time is 4-5 h, the temperature after heating is 70-75 ℃, and the reaction time is 10-12 h.
5. The method for preparing the counter electrode material of the dye-sensitized solar cell according to claim 1, wherein the method comprises the following steps: the mass fraction of the hydrochloric acid in the step (4) is 5%, the dropping speed of the constant-pressure dropping funnel is 2-3 mL/min, the mass fraction of the sodium metasilicate nonahydrate solution is 40%, and the stirring reaction time is 2-3 h.
6. The method for preparing the counter electrode material of the dye-sensitized solar cell according to claim 1, wherein the method comprises the following steps: the rotating speed of the high-speed refrigerated centrifuge in the step (5) is 5000-7000 r/min, the centrifugal treatment time is 10-30 min, the standing time is 3-4 h, the mixing mass ratio of the precipitate, the electrode slurry and the titanium dioxide is 6: 2: 1, the caliber of a spray gun is 1.0-1.5 mm, the vertical distance between a control nozzle and FTO conductive glass is 15-20 cm, the spraying pressure is 0.15-0.30 MPa, and the thickness of a photoelectric conversion electrode film is 0.1-0.2 mm.
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