阅读说明：本技术 一种基于染料敏化的太阳能电池及其制备方法 (Solar cell based on dye sensitization and preparation method thereof ) 是由 陈水源 王可 陈桂林 霍冠忠 黄志高 于 2019-08-30 设计创作，主要内容包括：本发明公开了一种基于染料敏化的太阳能电池及其制备方法,包括导电衬底和与导电衬底对置设置的对电极,导电衬底沿接近对电极方向依序贴合设有光阳极膜、染料敏化剂和电解质,光阳极膜包括沿接近对电极方向依序设置的致密层、介孔层和光散射层,致密层由脉冲激光沉积法制备而成,染料敏化剂附着于光散射层表面,本方案通过在利用P25 TiO<Sub>2</Sub>粉末的情况下,以脉冲激光沉积法代替传统的制备工艺,实现了一种制备程序简单,成本低廉,安全无毒的基于染料敏化的太阳能电池及其制备方法,并且该电池有效的提高了电池的光电转换效率。(The invention discloses a solar cell based on dye sensitization and a preparation method thereof, the solar cell comprises a conductive substrate and a counter electrode arranged opposite to the conductive substrate, the conductive substrate is sequentially attached with a photoanode film, a dye sensitizing agent and an electrolyte along the direction close to the counter electrode, the photoanode film comprises a compact layer, a mesoporous layer and a light scattering layer which are sequentially arranged along the direction close to the counter electrode, the compact layer is prepared by a pulse laser deposition method, the dye sensitizing agent is attached to the surface of the light scattering layer, and the scheme utilizes P25 TiO 2 Under the condition of powder, the traditional preparation process is replaced by a pulse laser deposition method, so that the dye sensitization-based sun which is simple in preparation procedure, low in cost, safe and nontoxic is realizedThe energy cell and the preparation method thereof, and the photoelectric conversion efficiency of the cell is effectively improved.)

1. Based onDye-sensitized solar cell, it includes electrically conductive substrate and the counter electrode that sets up with electrically conductive substrate opposition, electrically conductive substrate laminate in proper order along being close to counter electrode direction and be equipped with light anode film, dye sensitizer and electrolyte, its characterized in that: the photoanode membrane comprises a compact layer, a mesoporous layer and a light scattering layer which are sequentially arranged along the direction close to the counter electrode, wherein the compact layer is prepared by a pulse laser deposition method and comprises the following steps: selecting titanium dioxide as a target material, using FTO as a conductive substrate, and under the room temperature environment, using laser energy as 320 mJ, laser frequency as 4 Hz, preparation time as 1 h, and O₂And pressing under the condition of 3 Pa, preparing, taking out after the preparation, putting into a muffle furnace, and sintering for 30min at the temperature of 450 ℃, wherein a dye sensitizer is attached to the surface of the light scattering layer, the dye sensitizer is N719 ruthenium dye, the electrolyte is OPV-AN-I type electrolyte, and the counter electrode is a Pt electrode.

2. The dye-sensitized solar cell according to claim 1, characterized in that: the thickness of the conductive substrate is 1.6mm, the sheet resistance is less than 15 ohm/sq, and the light transmittance is more than or equal to 83%.

3. The dye-sensitized solar cell according to claim 1, characterized in that: the thickness of the titanium dioxide target material is 3 mm, the diameter of the titanium dioxide target material is 30 mm, the purity of the titanium dioxide target material is 99.99%, and the thickness of the compact layer is 200 nm.

4. The dye-sensitized solar cell according to claim 1, characterized in that: the mesoporous layer is a mesoporous film prepared from titanium dioxide.

5. The dye-sensitized solar cell according to claim 4, characterized in that: the mesoporous layer is prepared by a blade coating method and comprises the following components: adding slurry prepared by mixing 1 g of ethyl cellulose and 15 ml of terpineol into 1 g P25 titanium dioxide powder, uniformly grinding, then coating the mixture on the compact layer by a film scraper, standing the mixture for 10min at room temperature, then placing the mixture on a drying table for drying treatment at the temperature of 60 ℃ for 20 min, and finally placing the mixture in a muffle furnace for sintering treatment at the temperature of 450 ℃ for 60 min to obtain the titanium dioxide powder.

6. The dye-sensitized solar cell according to claim 4, characterized in that: the thickness of the mesoporous layer is 10 μm.

7. The dye-sensitized solar cell according to claim 1, characterized in that: the light scattering layer is prepared by a sol-gel method and comprises the following components: and spin-coating the sol with butyl titanate as a titanium source on the mesoporous layer at a rotating speed of 5000 r/min for 60 s, standing at room temperature for 10min, drying on a drying table at 60 ℃ for 20 min, and sintering in a muffle furnace at 450 ℃ for 30 min.

8. The dye-sensitized solar cell according to claim 7, characterized in that: the thickness of the light scattering layer was 1 μm.

9. A preparation method of a solar cell based on dye sensitization is characterized by comprising the following steps: which comprises the following steps:

(1) taking a conductive substrate as a base material, and then preparing a compact layer on the surface of the conductive substrate, wherein the compact layer is prepared by a pulse laser deposition method and comprises the following steps: selecting titanium dioxide with the thickness of 3 mm, the diameter of 30 mm and the purity of 99.99 percent as a target material, using FTO with the thickness of 1.6mm, the sheet resistance of less than 15 ohm/sq and the light transmittance of more than or equal to 83 percent as a conductive substrate, and under the room temperature environment, using laser energy of 320 mJ, laser frequency of 4 Hz, preparation time of 1 h and O₂Preparing under the condition of 3 Pa, taking out the conductive substrate after the preparation is finished, putting the conductive substrate into a muffle furnace, and sintering for 30min at the temperature of 450 ℃, thereby forming a compact layer on the conductive substrate;

(2) preparing a mesoporous layer on the compact layer, wherein the mesoporous layer is prepared by a blade coating method and comprises the following steps: adding slurry prepared by mixing 1 g of ethyl cellulose and 15 ml of terpineol into 1 g P25 titanium dioxide powder, uniformly grinding, then blade-coating the mixture on the compact layer by using a film scraper, standing the mixture at room temperature for 10min, then placing the mixture on a drying table for drying treatment at the temperature of 60 ℃ for 20 min, and finally placing the mixture in a muffle furnace for sintering treatment at the temperature of 450 ℃ for 60 min to obtain the mesoporous layer;

(3) preparing a light scattering layer on the mesoporous layer, wherein the light scattering layer is prepared by a sol-gel method and comprises the following steps: spin-coating the sol of butyl titanate as a titanium source on the mesoporous layer at the rotating speed of 5000 r/min for 60 s, standing at room temperature for 10min, drying on a drying table at the temperature of 60 ℃ for 20 min, and sintering in a muffle furnace at the temperature of 450 ℃ for 30min to form a light scattering layer on the mesoporous layer; the compact layer, the mesoporous layer and the light scattering layer form a photo-anode film;

(4) cutting the photoanode film into a preset specification, putting the photoanode film into a dye sensitizer, sensitizing the photoanode film for 24 hours at AN ambient temperature of 50 ℃, taking the photoanode film out, washing the dye sensitizer remained outside the area of the photoanode film by absolute ethyl alcohol, dropwise adding AN OPV-AN-I type electrolyte, and assembling the FTO conductive substrate, the photoanode film arranged on the FTO conductive substrate, the dye sensitizer and the electrolyte by taking Pt as a counter electrode and a clamp to form the dye-sensitized solar cell.

10. A dye-sensitized solar cell, characterized in that: which is obtained by the production method according to claim 9.

Technical Field

The invention relates to the field of photovoltaic technology and solar cells, in particular to a solar cell based on dye sensitization and a preparation method thereof.

Background

At present, the third generation of novel solar cells are the leading direction of research in the photovoltaic field, and the novel solar cells have the characteristics of being thin-film, rich in raw materials, non-toxic and high in photoelectric conversion efficiency, and the dye-sensitized solar cells serving as novel organic solar cells become research hotspots by virtue of the characteristics of simple manufacturing process, rich and non-toxic raw materials, high photoelectric conversion efficiency and the like. The dye-sensitized solar cell is a typical sandwich structure and consists of a photo-anode, a dye sensitizer, an electrolyte and a counter electrode, wherein the photo-anode is an important factor influencing the photoelectric conversion efficiency of the cell and comprises two parts of transparent conductive glass and a semiconductor nano film, and the transparent conductive glass mainly plays the roles of light transmission and electrode, so the conductive glass has high light transmission coefficient and small resistance; the semiconductor nano film has the main functions of adsorbing dye molecules, transmitting electrons and collecting electrons, so that the photoelectric performance of the cell can be greatly improved by the semiconductor nano film with a large specific area, a smooth interface and a low energy band, and at present, commonly used means for optimizing the performance of a photoanode comprise: ion doping, surface modification, nano composite film and preparation of different microstructure films. Some of the optimization means need to use noble metal, some preparation processes are complicated, and some raw materials are toxic. These factors have somewhat restricted the further development of solar cells. Therefore, the solar energy preparation process is simple, the raw materials are abundant, the cost is low, the conversion efficiency is high, the solar energy preparation process is more suitable for commercial development, and the global problems of resource shortage, environmental pollution, ecological imbalance and the like at present can be solved more favorably.

Disclosure of Invention

Based on the state of the art, the object of the invention is to provide a process which makes it possible to use only P25 TiO as starting material₂Under the condition of powder, a pulse laser deposition method is used for replacing the traditional preparation process, thereby realizing a preparation processThe dye-sensitized solar cell based on the dye sensitization and the preparation method thereof have the advantages of simple sequence, low cost, safety and no toxicity, and the photoelectric conversion efficiency of the cell is effectively improved.

In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:

the utility model provides a solar cell based on dye sensitization, its includes conductive substrate and the counter electrode that sets up with conductive substrate opposition, conductive substrate along being close counter electrode direction laminating in proper order and being equipped with light anode membrane, dye sensitizer and electrolyte, light anode membrane include along being close compact layer, mesoporous layer and the light scattering layer that counter electrode direction set up in proper order, compact layer prepare by the pulsed laser deposition method and form, it includes: selecting titanium dioxide as a target material, using FTO as a conductive substrate, and under the room temperature environment, using laser energy as 320 mJ, laser frequency as 4 Hz, preparation time as 1 h, and O₂And pressing under the condition of 3 Pa, preparing, taking out after the preparation, putting into a muffle furnace, and sintering for 30min at the temperature of 450 ℃, wherein a dye sensitizer is attached to the surface of the light scattering layer, the dye sensitizer is N719 ruthenium dye, the electrolyte is OPV-AN-I type electrolyte, and the counter electrode is a Pt electrode.

Further, the thickness of the conductive substrate is 1.6mm, the sheet resistance is less than 15 ohm/sq, and the light transmittance is more than or equal to 83%.

Further, the thickness of the titanium dioxide target material is 3 mm, the diameter of the titanium dioxide target material is 30 mm, the purity of the titanium dioxide target material is 99.99%, and the thickness of the compact layer is 200 nm.

Furthermore, the mesoporous layer is a mesoporous film prepared from titanium dioxide.

Preferably, the mesoporous layer is prepared by a doctor blade method, and comprises: adding slurry prepared by mixing 1 g of ethyl cellulose and 15 ml of terpineol into 1 g P25 titanium dioxide powder, uniformly grinding, then coating the mixture on the compact layer by a film scraper, standing the mixture for 10min at room temperature, then placing the mixture on a drying table for drying treatment for 20 min at the temperature of 60 ℃, and finally placing the mixture in a muffle furnace for sintering treatment for 60 min at the temperature of 450 ℃.

Preferably, the mesoporous layer has a thickness of 10 μm.

Further, the light scattering layer is prepared by a sol-gel method and comprises the following steps: and spin-coating the sol with butyl titanate as a titanium source on the mesoporous layer at a rotating speed of 5000 r/min for 60 s, standing at room temperature for 10min, drying on a drying table at 60 ℃ for 20 min, and sintering in a muffle furnace at 450 ℃ for 30 min.

Preferably, the thickness of the light scattering layer is 1 μm.

A preparation method of a solar cell based on dye sensitization comprises the following steps:

(1) taking a conductive substrate as a base material, and then preparing a compact layer on the surface of the conductive substrate, wherein the compact layer is prepared by a pulse laser deposition method and comprises the following steps: selecting titanium dioxide with the thickness of 3 mm, the diameter of 30 mm and the purity of 99.99 percent as a target material, using FTO with the thickness of 1.6mm, the sheet resistance of less than 15 ohm/sq and the light transmittance of more than or equal to 83 percent as a conductive substrate, and under the room temperature environment, using laser energy of 320 mJ, laser frequency of 4 Hz, preparation time of 1 h and O₂Preparing under the condition of 3 Pa, taking out the conductive substrate after the preparation is finished, putting the conductive substrate into a muffle furnace, and sintering for 30min at the temperature of 450 ℃, thereby forming a compact layer on the conductive substrate;

(2) preparing a mesoporous layer on the compact layer, wherein the mesoporous layer is prepared by a blade coating method and comprises the following steps: adding slurry prepared by mixing 1 g of ethyl cellulose and 15 ml of terpineol into 1 g P25 titanium dioxide powder, uniformly grinding, then blade-coating the mixture on the compact layer by using a film scraper, standing the mixture at room temperature for 10min, then placing the mixture on a drying table for drying treatment at the temperature of 60 ℃ for 20 min, and finally placing the mixture in a muffle furnace for sintering treatment at the temperature of 450 ℃ for 60 min to obtain the mesoporous layer;

(3) preparing a light scattering layer on the mesoporous layer, wherein the light scattering layer is prepared by a sol-gel method and comprises the following steps: spin-coating the sol of butyl titanate as a titanium source on the mesoporous layer at the rotating speed of 5000 r/min for 60 s, standing at room temperature for 10min, drying on a drying table at the temperature of 60 ℃ for 20 min, and sintering in a muffle furnace at the temperature of 450 ℃ for 30min to form a light scattering layer on the mesoporous layer; the compact layer, the mesoporous layer and the light scattering layer form a photo-anode film;

(4) cutting the photoanode film into a preset specification, putting the photoanode film into a dye sensitizer, sensitizing the photoanode film for 24 hours at AN ambient temperature of 50 ℃, taking the photoanode film out, washing the dye sensitizer remained outside the area of the photoanode film by absolute ethyl alcohol, dropwise adding AN OPV-AN-I type electrolyte, and assembling the FTO conductive substrate, the photoanode film arranged on the FTO conductive substrate, the dye sensitizer and the electrolyte by taking Pt as a counter electrode and a clamp to form the dye-sensitized solar cell.

A solar cell based on dye sensitization is prepared by the preparation method.

By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: the scheme is realized by utilizing P25 TiO₂Under the condition of powder, a pulse laser deposition method is used for replacing the traditional preparation process, the dye sensitization-based solar cell and the preparation method thereof which have the advantages of simple preparation procedure, low cost, safety and no toxicity are realized, and the photoelectric conversion efficiency of the cell is effectively improved.

Drawings

The invention will be further explained with reference to the drawings and the detailed description below:

FIG. 1 is a schematic structural hierarchy diagram of an aspect of the present invention;

fig. 2 is an I-V curve of a battery according to an embodiment of the present invention when subjected to an openness test.

Detailed Description

As shown in FIG. 1, the solar cell of the present invention comprises a conductive substrate 1 and a counter electrode 7 disposed opposite to the conductive substrate 1, wherein the conductive substrate 1 is sequentially bonded with a photo-anode film, a dye sensitizer 5 and an electrolyte 6 along a direction close to the counter electrode 7, and the photo-anode film comprises a dense layer sequentially disposed along the direction close to the counter electrode 72. The mesoporous layer 3 and the light scattering layer 4, the compact layer 2 is prepared by a pulsed laser deposition method, and comprises: selecting titanium dioxide as a target material, using FTO as a conductive substrate 1, under the room temperature environment, using laser energy as 320 mJ, laser frequency as 4 Hz, preparation time as 1 h, and O₂The preparation method comprises the following steps of pressing under the condition of 3 Pa, taking out the obtained product, putting the obtained product into a muffle furnace, and sintering the obtained product for 30min at the temperature of 450 ℃, wherein a dye sensitizer is attached to the surface of a light scattering layer, the dye sensitizer 5 is N719 ruthenium dye, the electrolyte 6 is OPV-AN-I type electrolyte, and the counter electrode is a Pt electrode 7.

Wherein, the effect of compact layer 2 is to strengthen connecting between mesoporous layer 3 and the FTO conductive substrate 1, can prevent effectively that mesoporous layer 3 from attaching to not hard up at conductive substrate 1 after the sintering, the problem that drops. The mesoporous layer 3 mainly functions to adsorb molecules of the dye sensitizer 5, thereby capturing photons. The light scattering layer 4 can enhance the scattering of sunlight, enhance light absorption and improve the utilization rate of the sunlight. The dye sensitizer 5 of the invention is N719 dye, and has the advantages of good stability, high photoelectric conversion rate and the like, dye molecules mainly absorb photons, electrons are excited to generate photogenerated electrons, and the photogenerated electrons are injected into TiO₂In the conduction band. The electrolyte 6 adopts OPV-AN-I electrolyte, is used as a conductive medium in a battery, and can reduce dye molecules in AN excited state to a ground state so as to regenerate the dye molecules. The counter electrode 7 adopts a Pt platinum electrode which forms a battery frame together with the photo-anode, and the Pt platinum electrode has the advantages of low resistance, high electronic conductivity, good stability and the like.

Further, the thickness of the conductive substrate 1 is 1.6mm, the sheet resistance is less than 15 ohm/sq, and the light transmittance is more than or equal to 83%.

Further, the thickness of the titanium dioxide target material is 3 mm, the diameter of the titanium dioxide target material is 30 mm, the purity of the titanium dioxide target material is 99.99%, and the thickness of the compact layer is 200 nm.

Further, the mesoporous layer 3 is a mesoporous film prepared from titanium dioxide; preferably, the thickness of the mesoporous layer 3 is 10 μm.

Further, the light scattering layer 4 is prepared by a sol-gel method; preferably, the thickness of the light scattering layer 4 is 1 μm.

By adopting the technical scheme, the working principle of the invention is as follows:

when sunlight irradiates, dye molecules 5 absorb photons, electrons of the dye molecules are excited and then transition from a ground state to an excited state, then the photons are quickly injected into a TiO2 conduction band and are transmitted to an FTO conductive substrate 1 through a mesoporous layer film 3, the electrons obtained by the excited dye molecules from an oxidation-reduction pair in electrolyte are reduced to the ground state through an external circuit flowing to a Pt counter electrode 7, dye regeneration is completed, the electrolyte is oxidized because of reducing the dye molecules, and finally the electrons flowing back from the counter electrode are received to realize self reduction, and the whole circuit also completes the cycle process of photoelectrochemical reaction.

The preparation method of the solar cell based on dye sensitization in the scheme of the invention comprises the following steps:

(1) taking a conductive substrate 1 as a base material, and then preparing a compact layer 2 on the surface of the conductive substrate, wherein the compact layer 2 is prepared by a pulse laser deposition method and comprises the following steps: selecting titanium dioxide with the thickness of 3 mm, the diameter of 30 mm and the purity of 99.99 percent as a target material, using FTO with the thickness of 1.6mm, the sheet resistance of less than 15 ohm/sq and the light transmittance of more than or equal to 83 percent as a conductive substrate, and under the room temperature environment, using laser energy of 320 mJ, laser frequency of 4 Hz, preparation time of 1 h and O₂Preparing under the condition of 3 Pa, taking out the conductive substrate after the preparation is finished, putting the conductive substrate into a muffle furnace, and sintering for 30min at the temperature of 450 ℃, thereby forming a compact layer 2 on the conductive substrate;

(2) preparing a mesoporous layer 3 on the dense layer 2, wherein the mesoporous layer 3 is prepared by a blade coating method and comprises the following steps: adding slurry prepared by mixing 1 g of ethyl cellulose and 15 ml of terpineol into 1 g P25 titanium dioxide powder, uniformly grinding, then blade-coating the mixture on the compact layer by using a film scraper, standing the mixture at room temperature for 10min, then placing the mixture on a drying table for drying treatment at the temperature of 60 ℃ for 20 min, and finally placing the mixture in a muffle furnace for sintering treatment at the temperature of 450 ℃ for 60 min to obtain the mesoporous layer 3;

(3) preparing a light scattering layer 4 on the mesoporous layer 3, wherein the light scattering layer 4 is prepared by a sol-gel method and comprises the following steps: spin-coating the sol of butyl titanate as a titanium source on the mesoporous layer at the rotating speed of 5000 r/min for 60 s, standing at room temperature for 10min, drying on a drying table at the temperature of 60 ℃ for 20 min, and sintering in a muffle furnace at the temperature of 450 ℃ for 30min to form a light scattering layer on the mesoporous layer; the compact layer, the mesoporous layer and the light scattering layer form a photo-anode film;

(4) the method comprises the following steps of cutting a photoanode film into a preset specification of 0.4 cm x 0.4 cm, putting the photoanode film into a dye sensitizer, sensitizing the photoanode film at AN ambient temperature of 50 ℃ for 24 hours, taking the photoanode film out, washing off the dye sensitizer remained outside the photoanode film area by absolute ethyl alcohol, dropwise adding AN OPV-AN-I type electrolyte, and assembling AN FTO conductive substrate, the photoanode film arranged on the FTO conductive substrate, the dye sensitizer and the electrolyte by taking Pt as a counter electrode and a clamp to form the dye-sensitized solar cell.

(5) The sunlight simulation light source is turned on, and the I-V curve of the battery is measured, as shown in figure 2.

The invention discloses a simple and practical method for researching a dye-sensitized solar cell, which improves TiO₂The preparation process of the solar cell adopts a pulse laser deposition method to replace the traditional methods of spin coating, lifting and the like, so that the light anode compact layer with more uniform particles and good crystallinity is prepared, the connectivity between the mesoporous layer and the substrate is increased, the leakage current is reduced, the light current density and the open-circuit voltage of the cell are greatly improved, and the photoelectric conversion efficiency of the cell is enhanced.

The foregoing is directed to embodiments of the present invention, and equivalents, modifications, substitutions and variations such as will occur to those skilled in the art, which fall within the scope and spirit of the appended claims.