CN111524712B - Preparation method of three-dimensional porous structure dye-sensitized solar cell counter electrode - Google Patents
Preparation method of three-dimensional porous structure dye-sensitized solar cell counter electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a three-dimensional porous structure dye-sensitized solar cell counter electrode, which belongs to the technical field of solar cells and is characterized in that a CuS nano crystal material with a special rose-shaped structure is synthesized by a gradual liquid phase reflux heating method, a gelling agent with a thickening function is added to prepare a semi-solid colloidal ropy body, a CuS film is prepared by a rolling method, and a three-dimensional porous structure counter electrode with high catalytic activity is obtained after the CuS film is subjected to heat treatment, wherein the highest cell efficiency of the counter electrode prepared by the invention reaches 5.0 percent, the corresponding open-circuit voltage is 0.69V, and the short-circuit current density is 9.7mA/cm2(ii) a Under the same assembly and test conditions, the performance was comparable to the 5.8% cell efficiency of a commercial platinum counter electrode, with a large boost space.
Description
Technical Field
The invention relates to a preparation method of a dye-sensitized solar cell counter electrode based on a three-dimensional porous structure, and belongs to the technical field of solar cell preparation.
Background
With the rapid increase of global energy demand, fossil fuel combustion causes a series of environmental problems, seriously threatens the survival of human beings, and the development of new energy has become an international consensus. The dye-sensitized solar cell is a novel solar energy utilization technology, and can be flexibly applied to various scenes in life by virtue of low cost, simple preparation process, wide color selection range and small shape design limitation, and is particularly combined with buildings to realize photovoltaic building integration.
Dye-sensitized solar cell and method for producing the same3the/I redox reaction couple is used as a medium for transferring charges between the photoanode and the counter electrode. During the cycle of regeneration of this medium, the oxidized substance (I)2Or I3) Electrons obtained at the counter electrode are reduced to I again-. During the processThe influence on the electrode is very obvious, and in order to reduce the energy loss on the electrode in the reduction process, the electrode is optimized and modified to improve the catalytic performance of the electrode, so that the significance of improving the final battery efficiency is great. The increase of the specific surface area, the conductivity and the electrochemical stability of the counter electrode are main ideas for improving the catalytic efficiency of the counter electrode. Since platinum metal is used as a counter electrode to oxidize and reduce the electrolyte (I)3 -/I-) Has high catalytic activity and is a common counter electrode material at present. However, platinum metal as a counter electrode has the following disadvantages: (1) the reserves are low, the price is high, and the industrialization is not suitable; (2) the preparation of the platinum counter electrode by pyrolysis cannot meet the preparation requirement of the flexible battery; (3) is easy to be combined with3 -And is corroded by the reaction, reducing the catalytic performance. In addition, the conventional platinum counter electrode has a smooth surface and a small specific surface area, so that the catalytic active sites are limited, and therefore, the search for a counter electrode material capable of replacing platinum metal and a structure with a large specific surface area is particularly urgent. The copper sulfide used as the counter electrode material of the dye-sensitized solar cell has the advantages of good conductivity, stable chemical property, rich raw material reserves, low price, suitability for large-scale production and the like. Therefore, the research on the preparation process of the copper sulfide counter electrode is very significant. The document Chen and the like adopts a magnetron sputtering method to sputter a layer of copper film on the pretreated FTO glass, then the copper film is put into a rapid annealing furnace filled with nitrogen for vulcanization, the temperature is kept at 200 ℃ for 30min, the temperature is kept at 300 ℃ for 30min to obtain a copper sulfide film, and finally the efficiency of the obtained battery device is 4.6%. Although the film prepared by the method is uniform, the specific surface area is small due to smooth surface, the active sites are limited, the used equipment is expensive and requires a high vacuum environment, the magnetron sputtering method for preparing the copper sulfide film in a large area is difficult and high in cost, and the chamber needs to be vacuumized again after the sample enters and exits, so that the required time is long. Zhang et al uses copper nitrate trihydrate and thioacetamide as raw materials, and disodium ethylene diamine tetraacetate (EDTA-2Na) as a complexing agent, and adopts a microwave method to react for 30min at 120 ℃ on FTO glass, and a copper sulfide film is obtained by deposition, and finally the copper sulfide film is assembled into a dye-sensitized cell to obtain the cell efficiency of 1.05%. Although the time used in this method is relatively short, the method is characterized byThe reaction process is severe, the thickness of the deposited film is difficult to control, the crystallinity is relatively poor, and the cell efficiency is low.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a preparation method of a three-dimensional porous structure dye-sensitized solar cell counter electrode and application of the counter electrode in a dye-sensitized solar cell, which specifically comprise the following steps:
(1) adding a copper source and a sulfur source into a reaction container, adding a solvent, and ultrasonically stirring uniformly to completely dissolve the raw materials to obtain a copper-sulfur compound precursor solution, wherein the molar ratio of the copper source to the sulfur source is 1: 1-1: 5.
(2) And (2) carrying out two-step heating reaction on the solution obtained in the step (1).
(3) After the two-step heating reaction is finished, naturally cooling to room temperature, adding absolute ethyl alcohol with the volume of 1.5 times of the mixed solution, centrifuging, pouring out the supernatant, then adding the absolute ethyl alcohol, repeatedly washing and precipitating until the supernatant is colorless; the centrifugation process is a conventional method, the preferred centrifugation speed is 10000-12000r/min, the centrifugation time is 4-6min, and the washing is repeated for 3-4 times.
(4) And (4) putting the precipitate obtained in the step (3) into a drying oven for drying to obtain rosette CuS crystal powder.
(5) Adding the obtained copper sulfide nano powder into a mortar, adding a gelling agent to prepare a semi-solid colloidal sticky body, and fully grinding the obtained mixture for 10-20min to obtain the semi-solid CuS colloidal sticky body.
(6) Fixing and reserving the periphery of a 3M adhesive tape with the thickness of 18um for clean FTO glass, and keeping the middle of the adhesive tape at 0.2cm2The area of (a); and (4) adding the CuS viscous body obtained in the step (5) onto FTO glass, repeatedly rolling for 2-3 times by using a glass rod, and removing the 3M adhesive tape to obtain the uniform CuS film.
(7) Putting the obtained copper sulfide thin film into an annealing furnace filled with sulfur powder, and carrying out vulcanization annealing treatment to reduce sulfur atom loss and air oxidation to obtain a CuS crystal three-dimensional porous structure dye-sensitized solar cell counter electrode; the temperature in the vulcanization annealing is set to be two stages of preheating and drying and constant temperature annealing, the water vapor and redundant gelling agent are preheated and dried, and then the constant temperature annealing is carried out to promote crystallization and further remove residual organic matters.
Preferably, in step (1) of the present invention, the copper source is one of copper chloride dihydrate, copper acetate monohydrate or copper sulfate pentahydrate; the sulfur source is one of thiourea, n-dodecyl mercaptan or carbon disulfide; the solvent is one or two of ethylene glycol and isopropanol.
Preferably, the two heating reactions in step (2) of the present invention are: firstly, the precursor solution is heated to the temperature of 120-plus-150 ℃ and is insulated for 20-50min, and then is heated to the temperature of 150-plus-200 ℃ and is insulated for 30-120 min.
Preferably, magnetic stirring is carried out in the two-step heating reaction process in the step (2) of the invention, and the magnetic stirring speed is 250-600 r/min.
Preferably, the drying temperature is 50-70 ℃, and the drying time is 8-24 h.
Preferably, the gelling agent of the present invention is one of glycerol and triethanolamine.
Preferably, the preheating and drying temperature of the copper sulfide film is 80-120 ℃, and the annealing time is 10-20 min; the annealing temperature of the copper sulfide film is 200-300 ℃, and the annealing time is 10-20 min.
All operations described in the present invention are carried out in an atmospheric environment.
The invention has the beneficial effects that:
the three-dimensional porous structure synthesized by the method has high catalytic activity on the counter electrode, the special structure has a light trapping effect in the aspect of optics, and the porous structure has a larger specific surface area relative to a smooth film plane when being used as the counter electrode of the dye-sensitized solar cell, so that electrolyte ions can be in full contact with the counter electrode, more active sites can be provided for electrocatalytic reaction, and oxidized I in the electrolyte can be accelerated-The obtained electrons are reduced, and the reduction and regeneration of the oxidized dye molecules are promoted, so that the cycle period of the battery is shortened, the electron hole recombination probability is reduced, and the overall conversion efficiency of the battery is finally improved. In addition, the invention selects FTO conductive glass as a substrate, and electrons pass throughThe longitudinal transmission to the substrate is communicated with an external circuit, so that the porous structure is also very favorable for electron transportation. The invention obviously improves the bonding performance of the CuS film and the FTO glass substrate through the gradual heating vulcanization treatment, and the crystallinity of the CuS crystal is better. In addition, the highest cell efficiency of the counter electrode prepared by the method reaches 5.0 percent, the corresponding open-circuit voltage is 0.69V, and the short-circuit current density is 9.7mA/cm2. Under the same assembly and test conditions, the performance is comparable to the cell efficiency of a commercial platinum counter electrode of 5.8%, and the boost space is large.
In conclusion, the three-dimensional porous structure counter electrode based on the rosette CuS crystal prepared by the method has the characteristics of large specific surface area, high catalytic performance, stable chemical property and the like, and the preparation method is simple and practical, good in controllability, low in cost, short in preparation period, low in cost of used equipment and very suitable for industrial production.
Drawings
FIG. 1 is an XRD pattern of a CuS counter electrode prepared in example 1;
FIG. 2 is an SEM image of a CuS crystal powder prepared in example 1;
FIG. 3 is a SEM image of the surface macro topography of a CuS counter electrode prepared in example 1;
FIG. 4 is an SEM image of the surface microstructure of a CuS counter electrode prepared in example 1;
fig. 5 is an I-V curve for a dye-sensitized solar cell for a CuS counter electrode and a commercial Pt counter electrode prepared in each example.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the above description.
Example 1
(1) Weighing 2mmol of CuCl22H2O, 2mmol of thiourea is added into a three-neck flask, then 40mL of ethylene glycol is added, and the mixture is stirred evenly by ultrasonic wave until the thiourea is completely dissolved.
(2) Putting the mixed solution obtained in the step (1) into a magnetic stirring heater, installing a condensing pipe, introducing cold water, then carrying out first-step heating, setting the temperature to be 130 ℃, stirring at the speed of 300r/min, and keeping the temperature for 30 min; and heating in the second step, setting the temperature to 150 ℃, stirring at 300r/min, and keeping the temperature for 30 min.
(3) After the two-step heating reaction is finished, naturally cooling the obtained solution to room temperature, subpackaging the solution into centrifuge tubes, adding absolute ethyl alcohol (the volume ratio of the absolute ethyl alcohol to the mixed solution is 1.5), uniformly mixing, placing the centrifuge tubes into a centrifuge for centrifugation, wherein the centrifugation speed is 10000r/min, the centrifugation time is 5min, and pouring out the supernatant after the centrifugation; add test tube volume 75% absolute ethanol, repeat washing 3 times.
(4) And (4) putting the precipitate obtained in the step (3) into a drying oven for drying at the drying temperature of 50 ℃ for 24 hours to obtain rosette CuS crystal powder.
(5) 1g of the rosette CuS crystal powder obtained in step (4) was put in a mortar, and 1ml of glycerin was added.
(6) And (4) fully grinding the mixture obtained in the step (5) for 10min to obtain a semi-solid colloidal viscous body.
(7) Fixing and reserving the periphery of a 3M adhesive tape with the thickness of 18um for clean FTO glass, and keeping the middle of the adhesive tape at 0.2cm2The area of (a).
(8) And (4) adding the CuS viscous body obtained in the step (6) onto FTO glass, repeatedly rolling for 3 times by using a glass rod, and removing the 3M adhesive tape to obtain a uniform CuS film.
(9) Placing the prepared CuS film into a rapid annealing furnace, and adding 10g of sulfur powder into the annealing furnace; setting annealing parameters, starting annealing, and performing first-step preheating and drying treatment at the temperature of 80 ℃ for 10 min; then carrying out the second annealing treatment, wherein the temperature is 250 ℃, and the annealing time is 10 min; and cooling and taking out to finally obtain the flower-shaped CuS crystal-based three-dimensional porous structure dye-sensitized solar cell counter electrode T1.
Example 2
(1) Weighing 2mmol of CuCl22H2O, 2mmol of n-dodecyl mercaptan is added into a three-neck flask, then 60mL of ethylene glycol is added, and the mixture is stirred evenly by ultrasound till the mixture is completely dissolved.
(2) Putting the mixed solution obtained in the step (1) into a magnetic stirring heater, installing a condenser pipe, introducing cold water, then carrying out first-step heating, setting the temperature to be 120 ℃, stirring at a speed of 400r/min, and keeping the temperature for 50 min; and (4) carrying out second-step heating, setting the temperature to be 170 ℃, stirring at the speed of 400r/min, and keeping the temperature for 60 min.
(3) After the two-step heating reaction is finished, naturally cooling the obtained solution to room temperature, subpackaging the solution into centrifuge tubes, adding absolute ethyl alcohol (the volume ratio of the absolute ethyl alcohol to the mixed solution is 1.5), uniformly mixing, placing the centrifuge tubes into a centrifuge for centrifugation, wherein the centrifugation speed is 10000r/min, the centrifugation time is 5min, and pouring out the supernatant after the centrifugation; then, anhydrous ethanol in a volume of 75% of the volume of the test tube was added thereto, and the washing was repeated 3 times.
(4) And (4) putting the precipitate obtained in the step (3) into a drying oven for drying at the drying temperature of 70 ℃ for 8 hours to obtain the rosette CuS crystal powder.
(5) 1g of the rosette CuS crystal powder obtained in step (4) was put in a mortar, and 1ml of glycerin was added.
(6) And (4) fully grinding the mixture obtained in the step (5) for 10min to obtain a semi-solid colloidal viscous body.
(7) Fixing and reserving the periphery of the clean FTO glass by using a 3M adhesive tape with the thickness of 18 mu M and the middle of the clean FTO glass by 0.2cm2The area of (a).
(8) And (4) adding the CuS viscous body obtained in the step (6) onto FTO glass, repeatedly rolling for 3 times by using a glass rod, and removing the 3M adhesive tape to obtain a uniform CuS film.
(9) Placing the prepared CuS film into a rapid annealing furnace, and adding 10g of sulfur powder into the annealing furnace; setting annealing parameters, starting annealing, and performing first-step preheating and drying treatment at the temperature of 80 ℃ for 10 min; then carrying out the second annealing treatment, wherein the temperature is 250 ℃, and the annealing time is 15 min; and taking out after cooling, and finally obtaining the flower-shaped CuS crystal-based three-dimensional porous structure dye-sensitized cell counter electrode T2.
Example 3
(1) Weighing 2mmol of CuCl22H2O, 2mmol of carbon disulfide is added into a three-neck flask, and then 60mL of ethylene glycol is added and stirred evenly by ultrasound till the carbon disulfide is completely dissolved.
(2) Putting the mixed solution obtained in the step (1) into a magnetic stirring heater, installing a condensing pipe, introducing cold water, then carrying out first-step heating, setting the temperature to be 120 ℃, stirring at a speed of 400r/min, and keeping the temperature for 50 min; and (4) carrying out second-step heating, setting the temperature to be 200 ℃, stirring at the speed of 400r/min, and keeping the temperature for 60 min.
(3) After the two-step heating reaction is finished, naturally cooling the obtained solution to room temperature, subpackaging the solution into centrifuge tubes, adding absolute ethyl alcohol (the volume ratio of the absolute ethyl alcohol to the mixed solution is 1.5), uniformly mixing, placing the centrifuge tubes into a centrifuge for centrifugation, wherein the centrifugation speed is 10000r/min, the centrifugation time is 5min, and pouring out the supernatant after the centrifugation; then, anhydrous ethanol in a volume of 75% of the volume of the test tube was added thereto, and the washing was repeated 3 times.
(4) And (4) drying the precipitate obtained in the step (3) in a drying oven at the drying temperature of 60 ℃ for 8-24h to obtain flower-shaped CuS crystal powder.
(5) 2g of the rose-like CuS crystal powder obtained in step (4) was put in a mortar, and 1ml of glycerin was added.
(6) And (4) fully grinding the mixture obtained in the step (5) for 10min to obtain a semi-solid colloidal viscous body.
(7) Fixing and reserving the periphery of a 3M adhesive tape with the thickness of 18um for clean FTO glass, and keeping the middle of the adhesive tape at 0.2cm2The area of (a).
(8) And (4) adding the CuS viscous body obtained in the step (6) onto FTO glass, repeatedly rolling for 3 times by using a glass rod, and removing the 3M adhesive tape to obtain a uniform CuS film.
(9) Placing the prepared CuS film into a rapid annealing furnace, and adding 10g of sulfur powder into the annealing furnace; setting annealing parameters, starting annealing, and performing first-step preheating and drying treatment at the temperature of 100 ℃ for 150 min; then carrying out the second annealing treatment at the temperature of 300 ℃ for 10 min; and taking out after cooling, and finally obtaining the flower-shaped CuS crystal-based three-dimensional porous structure dye-sensitized cell counter electrode T3.
Example 4
(1) Weighing 2mmol of CuCl22H2O, 2mmol of thiourea is added into a three-neck flask, then 40mL of glycol is added, and the mixture is stirred evenly by ultrasonic until the thiourea is completely dissolved.
(2) Putting the mixed solution obtained in the step (1) into a magnetic stirring heater, installing a condensing pipe, introducing cold water, then carrying out first-step heating, setting the temperature to be 130 ℃, stirring at a speed of 600r/min, and keeping the temperature for 30 min; and (5) carrying out second-step heating, setting the temperature to be 170 ℃, stirring at the speed of 600r/min, and keeping the temperature for 60 min.
(3) And after the two-step heating reaction is finished, naturally cooling the obtained solution to room temperature, subpackaging the obtained solution into centrifuge tubes, adding absolute ethyl alcohol (the volume ratio of the absolute ethyl alcohol to the mixed solution is 1.5), uniformly mixing, placing the centrifuge tubes into a centrifuge for centrifugation, wherein the centrifugation speed is 10000r/min, the centrifugation time is 5min, and pouring out the supernatant after centrifugation. Add 75% absolute ethanol to the tube volume and repeat the wash 3 times.
(4) Putting the precipitate obtained in the step (3) into a drying oven for drying at the drying temperature of 50-70 ℃ for 8-24h to obtain flower-shaped CuS crystal powder;
(5) 3g of the rosette CuS crystal powder obtained in step (4) was placed in a mortar, and 1ml of glycerol was added.
(6) And (4) fully grinding the mixture obtained in the step (5) for 10min to obtain a semi-solid colloidal viscous body.
(7) Fixing and reserving the periphery of the clean FTO glass by using a 3M adhesive tape with the thickness of 18 mu M and the middle of the clean FTO glass by 0.2cm2The area of (a).
(8) And (4) adding the CuS viscous body obtained in the step (6) onto FTO glass, repeatedly rolling for 3 times by using a glass rod, and removing the 3M adhesive tape to obtain a uniform CuS film.
(9) Placing the prepared CuS film into a rapid annealing furnace, and adding 10g of sulfur powder into the annealing furnace; setting annealing parameters, starting annealing, and performing first-step preheating and drying treatment at the temperature of 120 ℃ for 20 min; then carrying out the second annealing treatment at 200 ℃ for 10 min; and taking out after cooling, and finally obtaining the flower-shaped CuS crystal-based three-dimensional porous structure dye-sensitized cell counter electrode T4.
The XRD test result of the CuS counter electrode prepared by the embodiment of the invention is shown in figure 1, and the pure CuS counter electrode is obtained by the method shown in figure 1; the micro-morphology of the CuS nanocrystalline powder obtained by the invention is shown in FIG. 2, and the prepared CuS crystal has a rosette structure formed by self-assembling very thin nanosheets and has a plurality of contact surfaces; the macroscopic morphology of the surface of the CuS counter electrode obtained by the method is shown in FIG. 3, and the pore-shaped structures on the surface of the prepared CuS counter electrode are uniformly distributed; the microscopic morphology of the surface of the CuS counter electrode is shown in fig. 4, and it can be seen from the figure that the surface of the prepared CuS thin film counter electrode contains a large number of longitudinal micron-sized pores to form a network pore structure, which is beneficial for the sufficient contact between the electrolyte and the counter electrode, and the figure of embodiment 1 is used for illustration, and the figures of other embodiments are similar to those of embodiment 1.
Example 5
The counter electrodes (T1, T2, T3 and T4) prepared in the embodiments 1 to 4 are prepared into dye-sensitized solar cells, and the specific steps are as follows:
preparation of the photo-anode: first, a clean FTO substrate is placed into TiCl at 80 deg.C4Soaking the solution (0.05mol/L) for 40 min; commercial TiO is then knife coated2Slurry (P25, dysol, australia) was coated on the above pretreated FTO substrate; selecting 0.20cm2The portion of (a) serves as a photo-anode region; will be coated with TiO2The FTO glass of (a) is gradually heated to 500 ℃ (ramp rate 2 ℃/min) on a heating stage and then sintered at that temperature for 30 minutes to form TiO2A film; TiO 22The total thickness of the film was about 18 μm.
Assembling the DSSC: subjecting the heat-treated TiO to a heat treatment2Photoanode, performing TiCl4Soaking in the solution to absorb more dye; thereafter, the 80 ℃ baked TiO2Immersing the photoanode in absolute ethanol solution containing 0.3mol/L of N719 dye (Dyesol, Australia) at room temperature for 24h in dark condition; TiO 22The photoanode and various prepared counter electrodes (T1, T2, T3, T4) are assembled into a DSSC; a commercial electrolyte (purchased from oppivitt new energy limited, camput, loungen) was injected into the gap between the two electrodes by a syringe, and the hole was sealed with a hot melt adhesive after the injection of the electrolyte, to obtain a final dye-sensitized solar cell.
The dye-sensitized cells assembled with the counter electrodes (T1, T2, T3, T4) obtained in each example were subjected to I-V tests at AM1.5/25 ℃ using an electrochemical workstation, and compared with a platinum counter electrode under the same conditions.
The results of the I-V test of dye-sensitized solar cells assembled with the counter electrodes (T1, T2, T3, T4) prepared in the respective examples and a commercial Pt counter electrode (purchased from new energy source, opavit, inc., ying, loungen) under the same conditions are shown in fig. 5.
Under the same conditions, the open-circuit voltage of the Pt counter electrode is 0.77V, and the short-circuit current density is 10.8mA/cm2And the battery efficiency reaches 5.8 percent.
Under the same conditions, the open-circuit voltage of the T1 counter electrode obtained in example 1 reaches 0.69V, and the short-circuit current reaches 9.7mA/cm2And the battery efficiency reaches 5.0%.
Under the same conditions, the open-circuit voltage of the T2 counter electrode obtained in example 2 reaches 0.68V, and the short-circuit current reaches 9.5mA/cm2And the battery efficiency reaches 4.8 percent.
Under the same conditions, the open-circuit voltage of the T3 counter electrode obtained in example 3 reaches 0.66V, and the short-circuit current reaches 9.5mA/cm2And the battery efficiency reaches 4.6 percent.
Under the same conditions, the open-circuit voltage of the T4 counter electrode obtained in example 4 reaches 0.65V, and the short-circuit current reaches 9.0mA/cm2And the battery efficiency reaches 4.3 percent.
According to the test results, under the same test and assembly conditions, the maximum cell efficiency of the dye-sensitized solar cell counter electrode with the CuS crystal three-dimensional porous structure reaches 5.0%, and is very close to the common Pt electrode efficiency of 5.8%, compared with the cell efficiency of copper sulfide counter electrodes of other research groups, the cell counter electrode with the CuS crystal three-dimensional porous structure is higher in efficiency; the specific surface area of the counter electrode is greatly increased, the contact between the redox couple and the counter electrode is improved, and the electron transport between the counter electrode and the photo-anode is optimized; although the conversion efficiency of the platinum counter electrode is different from the current highest conversion efficiency (8 percent) of the platinum counter electrode, the battery efficiency can be further improved if the conditions are improved in consideration of poor preparation conditions and no dust or inert gas protection; therefore, the data comparison shows that the CuS crystal-based three-dimensional porous structure dye-sensitized solar cell counter electrode has a series of advantages of high catalytic activity, cycle stability, low cost and the like and is a favorable alternative electrode for replacing a platinum electrode.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.
Claims (7)
1. A preparation method of a three-dimensional porous structure dye-sensitized solar cell counter electrode is characterized by comprising the following steps:
(1) adding a copper source and a sulfur source into a reaction container, adding a solvent, and ultrasonically stirring uniformly to completely dissolve the raw materials to obtain a copper-sulfur compound precursor solution, wherein the molar ratio of the copper source to the sulfur source is 1: 1-1: 5;
(2) carrying out two-step heating reaction on the solution obtained in the step (1);
(3) after the two-step heating reaction is finished, naturally cooling to room temperature, adding absolute ethyl alcohol for centrifugation, pouring out the supernatant, then adding absolute ethyl alcohol, repeatedly washing and precipitating, and cleaning;
(4) putting the precipitate obtained in the step (3) into a drying oven for drying to obtain copper sulfide nano powder;
(5) adding the obtained copper sulfide nano powder into a mortar, and adding a gelling agent to prepare a semi-solid colloidal sticky body; fully grinding the obtained mixture for 10-20min to obtain a semi-solid CuS colloidal viscous body;
(6) fixing the periphery of clean FTO glass, then adding the semi-solid CuS colloidal sticky body obtained in the step (5) onto the FTO glass, and repeatedly rolling for 2-3 times by using a glass rod to obtain a uniform copper sulfide thin film;
(7) putting the obtained copper sulfide thin film into an annealing furnace filled with sulfur powder, carrying out vulcanization annealing treatment to reduce sulfur atom loss and air oxidation, enhancing the crystallinity of CuS on an FTO substrate, and obtaining a CuS crystal three-dimensional porous structure dye-sensitized solar cell counter electrode, wherein the temperature in the vulcanization annealing is set to be two stages of preheating drying and constant temperature annealing;
the annealing temperature of the CuS film is 200-300 ℃, and the annealing time is 10-30 min.
2. The method for preparing the counter electrode of the dye-sensitized solar cell with the three-dimensional porous structure according to claim 1 is characterized in that: in the step (1), the copper source is one of copper chloride dihydrate, copper acetate monohydrate or copper sulfate pentahydrate; the sulfur source is one of thiourea, n-dodecyl mercaptan or carbon disulfide; the solvent is one or two of ethylene glycol and isopropanol.
3. The method for preparing the counter electrode of the dye-sensitized solar cell with the three-dimensional porous structure according to claim 1 is characterized in that: the two-step heating reaction in the step (2) comprises the following steps: firstly, the precursor solution is heated to the temperature of 120-plus-150 ℃ and is insulated for 20-50min, and then is heated to the temperature of 150-plus-200 ℃ and is insulated for 30-120 min.
4. The method for preparing a counter electrode of a dye-sensitized solar cell with a three-dimensional porous structure according to claim 1 or 3, characterized in that: magnetic stirring is carried out in the two-step heating reaction process in the step (2), and the magnetic stirring speed is 250-600 r/min.
5. The method for preparing the counter electrode of the dye-sensitized solar cell with the three-dimensional porous structure according to claim 1 is characterized in that: in the step (4), the drying temperature is 50-70 ℃, and the drying time is 8-24 h.
6. The method for preparing the counter electrode of the dye-sensitized solar cell with the three-dimensional porous structure according to claim 1 is characterized in that: the gelling agent is one of glycerol and triethanolamine.
7. The method for preparing the counter electrode of the dye-sensitized solar cell with the three-dimensional porous structure according to claim 1 is characterized in that: the preheating and drying temperature of the CuS film is 80-120 ℃, and the time is 10-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010286437.1A CN111524712B (en) | 2020-04-13 | 2020-04-13 | Preparation method of three-dimensional porous structure dye-sensitized solar cell counter electrode |
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