阅读说明：本技术 一种太阳能电池吸收层材料的制备方法及应用 (Preparation method and application of solar cell absorption layer material ) 是由 王乐 王子延 梁培 邾强强 张宏 曹丽 常鹏 于 2020-05-21 设计创作，主要内容包括：本发明公开了一种太阳能电池吸收层材料的制备方法及在制备高吸收系数的钙钛矿太阳能电池中应用。制备方法是将CsCl加入二甲亚砜中,等其完全溶解之后加入异丙醇,将沉淀过滤,真空干燥得到处理过的CsCl；按照Cs<Sub>2</Sub>PdCl<Sub>6</Sub>对应元素的摩尔比,将PdCl<Sub>2</Sub>和处理过的CsCl配置成前驱体溶液；通过Cs<Sub>2</Sub>PdCl<Sub>6</Sub>空位缺陷的调控得到含Cl空位缺陷较少的产物,将上述溶液旋涂于电子传输层上,在120-200℃退火2-5min,即可合成得到吸收系数高达10×10<Sup>5</Sup>的Cs<Sub>2</Sub>PdCl<Sub>6</Sub>材料制作的太阳能电池吸收层。(The invention discloses a preparation method of a solar cell absorption layer material and application of the solar cell absorption layer material in preparation of a perovskite solar cell with a high absorption coefficient. The preparation method comprises the steps of adding CsCl into dimethyl sulfoxide, adding isopropanol after the CsCl is completely dissolved, filtering precipitates, and drying in vacuum to obtain treated CsCl; according to Cs 2 PdCl 6 Corresponding to the molar ratio of the elements, adding PdCl 2 And the treated CsCl is configured as a precursor solution; by Cs 2 PdCl 6 Regulating and controlling the vacancy defect to obtain a product with less Cl vacancy defect, and spin-coating the above solution on an electron transportAnnealing the layer at 120-200 ℃ for 2-5min to obtain the absorption coefficient up to 10 × 10 5 Cs of (A) 2 PdCl 6 The solar cell absorbing layer is made of the material.)

1. The preparation method of the solar cell absorption layer material is characterized by comprising the following steps of:

1) preparation of Cs₂PdCl₆A material;

2) the prepared Cs₂PdCl₆Dissolving the material in HCl aqueous solution, fully dissolving, filtering and washing to obtain washed Cs₂PdCl₆Similarly, CsCl powder is dissolved in HCl aqueous solution, heated for 30-90 minutes at 100-140 ℃, cooled, and added with washed Cs₂PdCl₆Mixing the materials, heating to 70-90 ℃, continuing for 10-30 minutes until the solution turns to be purple red, heating to 130-170 ℃, directly adding water for washing, washing until the supernatant is transparent, and drying to obtain the solar cell absorption layer material.

2. The method for preparing the material of the solar cell absorption layer according to claim 1, wherein in the step 1), Cs is prepared₂PdCl₆The material specifically comprises:

adding CsCl into dimethyl sulfoxide, dissolving, adding isopropanol, filtering the precipitate, and vacuum drying to obtain treated CsCl powder; taking PdCl₂Preparing the powder and the treated CsCl powder into a precursor solution, and annealing the precursor solution to obtain Cs₂PdCl₆A material.

3. The method for preparing a solar cell absorber layer material according to claim 2, wherein in step 1), the PdCl is added₂The molar ratio of powder to treated CsCl powder was 1: 1.5 to 2.5.

4. The method for preparing the solar cell absorption layer material according to claim 2, wherein the annealing conditions in step 1) are as follows: annealing at 130-220 ℃ for 2-10 min.

5. The method for preparing the material of the solar cell absorption layer according to claim 2, wherein the HCl mass percent of the HCl aqueous solution in the step 2) is 5-15%.

6. The method according to claim 2, wherein the dissolved Cs is dissolved in step 2)₂PdCl₆Aqueous HCl solution of material, aqueous HCl solution of dissolved CsCl powder and PdCl in step 1)₂The ratio of the powder usage is 8-12 ml: 8-12 ml: 1 mol.

7. The method for preparing the material of the solar cell absorption layer according to claim 2, wherein in the step 2), the CsCl powder is dissolved in the HCl aqueous solution and then heated at 110-130 ℃ for 45-75 minutes;

adding washed Cs₂PdCl₆Mixing the materials, heating to 75-85 deg.c for 15-25 min until the solution turns to purple red, heating to 140-160 deg.c and flushing with water.

8. The application of the solar cell absorbing layer material prepared by the preparation method according to any one of claims 1 to 7 in preparing a perovskite solar cell with a high absorption coefficient.

9. The application according to claim 8, wherein said application comprises in particular:

A) preparing an electron transport layer on transparent conductive glass;

B) dissolving a solar cell absorption layer material in a dimethyl sulfoxide solution, spin-coating the solar cell absorption layer material on an electron transport layer, and annealing to obtain a solar cell absorption layer;

C) and preparing a hole transport layer and anode metal on the solar cell absorption layer to obtain the perovskite solar cell.

10. Use according to claim 9,

in the step A), an electron transport layer is prepared on the transparent conductive glass, and the method specifically comprises the following steps:

TiO is used as electron transport layer material₂Dispersing in a solvent to obtain an electron transport layer solution, then coating the electron transport layer solution on transparent conductive glass, and annealing to obtain an electron transport layer;

in the step B), annealing is carried out for 2-10 min at 130-220 ℃.

Technical Field

The invention relates to the technical field of perovskite solar cells, in particular to a preparation method of a solar cell absorption layer material and application of the solar cell absorption layer material in preparation of a perovskite solar cell with a high absorption coefficient.

Background

With the development of solar cell technology, solar cells are developed from the earliest monocrystalline silicon cell, polycrystalline silicon cell and amorphous silicon cell to a thin film solar cell, and after the perovskite solar cell is a thin film solar cell, a great research is carried out, compared with the traditional silicon-based solar cell, the conversion efficiency of the perovskite solar cell can reach 22%, which is twice of the conversion efficiency of the solar cell used in the current market, the use cost of the solar cell can be greatly reduced, the solar cell which occupies the mainstream in the current market takes silicon and cadmium telluride as materials, and the conversion efficiency reaches the current conversion efficiency for more than 10 years; whereas perovskites have only spent as little as 4 years of research.

At present, perovskite solar cells mainly used contain lead element, and the lead element has certain toxicity, is not suitable for being developed and used for a long time, and has certain obstruction on other applications such as electronic and optoelectronic semiconductors⁵On the other hand, the light absorption coefficient determines the absorption efficiency of solar cells with respect to sunlight, and therefore, it is required to improve the light absorption coefficient.

Therefore, increasing the light absorption coefficient of solar cells and solving the toxicity problem are the common concerns in the industry.

Disclosure of Invention

To overcome the deficiencies of the prior art, the present invention uses Cs₂PdCl₆Production of solar energy from vacancy defect variant perovskite materialAn absorption layer of the energy battery, comprising an absorption layer material Cs₂PdCl₆Synthesis and regulation of vacancy defects.

The invention is realized by the following technical scheme:

1. absorbent material Cs₂PdCl₆Synthesis of (2)

Adding CsCl into dimethyl sulfoxide, adding isopropanol after the CsCl is completely dissolved, filtering the precipitate, and drying in vacuum to obtain treated CsCl; according to Cs₂PdCl₆Corresponding to the molar ratio of the elements, adding PdCl₂And the treated CsCl is configured as a precursor solution; spin coating the solution on the electron transport layer, and annealing at 120-200 deg.C for 2-5min to obtain Cs₂PdCl₆The solar cell absorbing layer is made of the material.

2.Cs₂PdCl₆Control of vacancy defects

The prepared Cs₂PdCl₆Dissolving the powder in 10% HCl solution, dissolving, filtering, washing, dissolving CsCl powder in 10% HCl solution, heating at 120 deg.C for 60 min, cooling to room temperature, and collecting Cs₂PdCl₆And mixing the solutions, heating to 80 ℃, continuing for 20 minutes until the solution turns to be purple red, heating to 150 ℃, directly adding water for washing, washing until the supernatant is transparent, and drying for 24 hours to obtain the solar cell absorbing layer material (product containing few Cl vacancy defects).

A preparation method of a solar cell absorption layer material comprises the following steps:

1) preparation of Cs₂PdCl₆A material;

2) the prepared Cs₂PdCl₆Dissolving the material in HCl aqueous solution, fully dissolving, filtering and washing to obtain washed Cs₂PdCl₆Similarly, CsCl powder is dissolved in HCl aqueous solution, heated for 30-90 minutes at 100-140 ℃, cooled, and added with washed Cs₂PdCl₆Mixing the materials, heating to 70-90 deg.c for 10-30 min until the solution turns to purple red, heating to 130-170 deg.c, washing with water and washing to the upper partAnd (4) the clear solution is transparent and is dried to obtain the solar cell absorbing layer material (namely, the product containing few Cl vacancy defects).

In step 1), Cs is prepared₂PdCl₆The material specifically comprises:

adding CsCl into dimethyl sulfoxide, dissolving, adding isopropanol, filtering the precipitate, and vacuum drying to obtain treated CsCl powder; taking PdCl₂Preparing the powder and the treated CsCl powder into a precursor solution, and annealing the precursor solution to obtain Cs₂PdCl₆A material.

The PdCl₂The molar ratio of powder to treated CsCl powder was 1: 1.5 to 2.5, most preferably 1: 2.

the annealing conditions are as follows: annealing at 130-220 ℃ for 2-10 min, and most preferably at 150-200 ℃ for 5 min.

In the step 2), the HCl mass percent of the HCl aqueous solution is 5-15%, and the most preferable is 10%.

Said dissolved Cs₂PdCl₆Aqueous HCl solution of material, aqueous HCl solution of dissolved CsCl powder and PdCl in step 1)₂The ratio of the powder usage is 8-12 ml: 8-12 ml: 1mol, most preferably 10 ml: 10 ml: 1 mol.

The CsCl powder is dissolved in an HCl aqueous solution and then heated at 110 to 130 ℃ for 45 to 75 minutes, and most preferably, the CsCl powder is dissolved in an HCl aqueous solution and then heated at 120 ℃ for 60 minutes.

Adding washed Cs₂PdCl₆Mixing the materials, heating to 75-85 deg.C, keeping for 15-25 min until the solution turns to purple red, heating to 140-160 deg.C, directly washing with water, and most preferably adding washed Cs₂PdCl₆Mixing the materials, heating to 80 deg.C for 20 min until the solution turns to purple red, heating to 150 deg.C, and directly washing with water.

The drying time is 18 h-30 h, more preferably 22 h-26 h, and most preferably 24 h.

The battery assembled by the product with less Cl vacancy defects prepared by the method has better air stability. The solar cell absorption layer material is applied to the preparation of a perovskite solar cell with a high absorption coefficient, and the application specifically comprises the following steps:

A) preparing an electron transport layer on transparent conductive glass;

B) dissolving the material of the solar cell absorption layer in dimethyl sulfoxide solution, spin-coating on the electron transport layer, and annealing to obtain the perovskite absorption layer (namely Cs)₂PdCl₆Solar cell absorber layers made of materials);

C) and preparing a hole transport layer and anode metal on the perovskite absorption layer to obtain the perovskite solar cell.

In the step A), an electron transport layer is prepared on the transparent conductive glass, and the method specifically comprises the following steps:

TiO is used as electron transport layer material₂Dispersing in a solvent to obtain an electron transport layer solution, then coating the electron transport layer solution on transparent conductive glass, and annealing to obtain the electron transport layer.

The solvent is dimethylformamide or a solvent with a volume ratio of 4: 1 of dimethylformamide and dimethyl sulfoxide.

In the step B), annealing is carried out at 130-220 ℃ for 2-10 min, and further preferably at 150-200 ℃ for 3-5 min.

The perovskite solar cell comprises transparent conductive glass, and an electron transport layer, a solar cell absorption layer (namely a perovskite absorption layer), a hole transport layer and anode metal which are sequentially arranged on the transparent conductive glass.

Compared with the prior art, the invention has the following advantages:

the light absorption coefficient can be up to 10 × 10⁵Above Cs₂PdCl₆The material has a forbidden band width of 1.4-1.5 eV, can be used for preparing a multi-junction solar cell, has a high light absorption coefficient, and can make an absorption layer of the solar cell thin. The defect regulating technology is used during the synthesis of material, so that the Cl atom vacancy defect may be reduced and after the defect is reduced, the Cl atom vacancy defect may be eliminatedThe material has better absorption capacity, and when Cl atoms gradually replace Br atoms, the absorption coefficient of the material is gradually increased, so that the absorption coefficient can be improved by reducing the vacancy defects of the Cl atoms. Meanwhile, the lead-containing perovskite which is widely used at present can be replaced, and the toxicity of the material is reduced.

Drawings

Fig. 1 is a schematic structural view of a perovskite solar cell according to the present invention.

FIG. 2 is an atomic structural diagram of a light-absorbing layer material for a solar cell according to the present invention.

FIG. 3 is a graph of the optical absorption coefficient and photon energy for example 1 of the present invention.

FIG. 4 is an XRD pattern, SEM pattern and synthesized product of a sample of example 2 of the present invention.

Detailed Description

The present invention will be described in detail with reference to the specific embodiments shown in the drawings, which are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to the specific embodiments are included in the scope of the present invention. Examples are not specifically defined, and the percentages appearing are percentages by mass.

The invention discloses a perovskite solar cell with a high absorption coefficient and no toxicity, which aims to solve the problems of poor absorption coefficient and toxicity of the perovskite solar cell in the prior art and can effectively improve the absorption coefficient of an absorption layer of the solar cell.

The present invention will be described in detail below with reference to the accompanying drawings.

Referring to fig. 1, fig. 1 is a schematic structural diagram of a perovskite solar cell of the present invention. As shown, the solar cell includes: and an electron transport layer 4, a perovskite absorption layer 3, a hole transport layer 2, and an anode metal 1 disposed on a transparent conductive glass 5.

The invention relates to a method for manufacturing an absorption layer of a perovskite solar cell by using a material with a high absorption coefficient. Step 1, isAdding CsCl into dimethyl sulfoxide, adding isopropanol after the CsCl is completely dissolved, filtering the precipitate, and drying in vacuum to obtain treated CsCl; according to Cs₂PdCl₆Corresponding to the molar ratio of the elements, adding PdCl₂And the treated CsCl is prepared into a precursor solution, the solution is annealed for 2-5min at the temperature of 120-200 ℃, and then the Cs can be synthesized₂PdCl₆A material. Step 2, preparing the Cs₂PdCl₆Dissolving the powder in 10% HCl solution, dissolving, filtering, washing, dissolving CsCl powder in 10% HCl solution, heating at 120 deg.C for 60 min, cooling to room temperature of 25 deg.C, and collecting Cs₂PdCl₆And mixing the solutions, heating to 80 ℃, continuing for 20 minutes until the solution turns to be purple red, heating to 150 ℃, directly adding water for washing, washing until the supernatant is transparent, and drying for 24 hours to obtain a product with less Cl vacancy defects. The battery assembled by the product with less Cl vacancy defects prepared by the method has better air stability.