CN111326658A - Perovskite solar cell with nickel grid flexible electrode and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of solar cells, and discloses a nickel-mesh flexible electrode perovskite solar cell and a preparation method thereof. According to the preparation method, a nickel mesh flexible thin film with high transmittance and an environment-stable micro-nano structure is used as a transparent electrode of the perovskite type solar cell. Furthermore, the conductivity and the uniformity of the film of the high-conductivity organic poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonic acid) are improved, the mechanical stability of the flexible perovskite device can be effectively improved, and nickel oxide formed by nickel ions under the action of air can be used as an effective hole transport material, so that the charge transport of the device is facilitated. The finally prepared photovoltaic device has better stability of indoor and outdoor energy conversion efficiency under the bending condition, and the method is favorable for preparing the efficient and stable flexible perovskite indoor photovoltaic device and is convenient for the development of a flexible intelligent wearable energy supply system.

Description

A kind of perovskite solar cell with nickel grid flexible electrode and preparation method thereof

technical field

The invention belongs to the field of solar cells, in particular to a perovskite solar cell with a nickel grid flexible electrode and a preparation method thereof.

Background technique

Solar cell devices convert solar energy into electrical energy, effectively solving the increasingly severe energy problems, and their environmental friendliness has received extensive attention. Among them, perovskite solar cells have been rapidly developed due to their excellent photovoltaic properties and low cost, and their highest energy conversion efficiency can reach 25.5%. At present, perovskite solar cells with superior performance are mainly based on glass substrates of indium tin oxide or fluorine-doped tin oxide. Due to the limited reserves of metal elements such as indium and tin, the high price, and the pollution to the environment after leakage, the The degree of limitation limits the promotion and industrial application of perovskite solar cells, and the defects of inorganic non-metal oxide indium tin oxide in ductility also limit its service life on flexible devices.

The application of flexible transparent conductive electrodes in flexible photovoltaic devices has strongly promoted the development of flexible wearable and smart IoT terminals. However, the commonly used indium tin oxide flexible transparent electrodes are very easy to fall off during the bending process of the device, which affects the continuity of the electrodes, and ultimately reduces the energy conversion efficiency of photovoltaic devices. Therefore, it is the current research focus of flexible photovoltaic devices to find highly transparent conductive electrodes that are resistant to stretching and bending.

SUMMARY OF THE INVENTION

Technical problems to be solved: The commonly used flexible indium tin oxide transparent electrodes are relatively fragile, lack flexibility, and are easily detached and fractured in the case of bending and stretching, resulting in a significant decrease in the optoelectronic properties and stability of perovskite photovoltaic devices. , and ultimately affect its commercial application. At the same time, traditional silver nanowires and silver mesh transparent electrodes are prone to ion migration due to silver ions, which combine with halogens in perovskite, resulting in rapid degradation of perovskite films. In order to overcome the defects of many mechanical properties of flexible electrodes in current photovoltaic devices, and at the same time optimize the photovoltaic performance of the device, the purpose of the present invention is to provide a novel preparation method of perovskite solar cells with nickel mesh flexible electrodes, using nickel mesh The flexible transparent electrodes prepared by grids can significantly improve the mechanical stability and optoelectronic properties of perovskite devices, and the flexible nickel grid perovskite photovoltaic devices can maintain good electrode continuity during repeated stretching and bending processes. The ions have obvious stability relative to silver ions, and the nickel oxide formed in the air can be used as an effective hole transport material, which is more conducive to the charge transport of the device, and finally realizes the preparation of efficient and stable flexible perovskite solar cells.

In order to achieve the above object, the present invention provides the following technical solutions:

A perovskite solar cell with a nickel grid flexible electrode is characterized in that the perovskite solar cell uses a flexible nickel grid conductive film substrate as a transparent electrode.

Further, the flexible nickel grid conductive film substrate is treated with (3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS).

The preparation method of the perovskite solar cell of the present invention is characterized in that, comprising the following steps:

(1) Dissolve methylammonium iodide and lead iodide in a mixed solution composed of dimethyl sulfoxide and γ-hydroxybutyric acid lactone and stir evenly to obtain a precursor solution of perovskite DMSO-GBL;

(2) PEDOT:PSS of type PH1000 was deposited on the flexible nickel grid electrode, and then PEDOT:PSS of type AI4083 was further deposited to form a uniform hole transport layer film;

(3) depositing a perovskite precursor solution on the hole transport layer thin film, and obtaining a perovskite thin film layer after annealing;

(4) Spin coating, inkjet printing, or roll-to-roll processing [6,6]-phenyl C61 methyl butyrate (PCBM) on the perovskite thin film layer to obtain a uniform electron transport layer ;

(5) The 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP) modified layer is processed on the electron transport layer by vapor deposition or inkjet printing;

(6) The cathode electrode is processed on the 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline modified layer by vapor deposition or inkjet printing.

Further, the thickness of the hole transport layer in the step (2) is 40-50 nm.

Further, in the step (3), the annealing temperature is set to 100° C., and the treatment time is 10 min.

Further, the thickness of the perovskite thin film in the step (3) is 300-350 nm.

Further, the thickness of the electron transport layer in the step (4) is 25-30 nm.

Further, the thickness of the modification layer in the step (5) is 8-12 nm.

Further, in the step (6), the cathode electrode is Ag, Cu or Au, and the thickness of the electrode is 60-100 nm.

Beneficial effects: The present invention provides a perovskite solar cell with a nickel grid flexible electrode and a preparation method thereof. The method adopts a nickel grid with a novel micro-nano structure as a transparent electrode, which has better resistance to stretching and bending. At the same time, the relatively stable nickel element is not prone to ion migration, which reduces the damage to the phase stability of the perovskite, so that the stability of the flexible perovskite device has been significantly improved. By combining the highly conductive PEDOT:PSS with the nickel grid, the conductivity of the nickel grid electrode and the flatness of the film are further improved. Through repeated stretching and bending processes, the flexible nickel grid perovskite photovoltaic device can maintain With better electrode continuity, the nickel oxide formed by the nickel element in the nickel grid in the air can be used as an effective hole transport material, which is more conducive to the charge transport of the device. The preparation method of the invention is simple, is beneficial to improve indoor and outdoor mechanical stability and crystal phase stability of the flexible photovoltaic device, and facilitates the development and application of self-generating flexible smart wearable devices.

Description of drawings

FIG. 1 is a schematic structural diagram of a perovskite solar cell prepared by the preparation method of the present invention.

In the figure: 1 is the substrate; 2 is the anode electrode; 3 is the hole transport layer; 4 is the perovskite thin film layer; 5 and 6 are the electron transport layer; 7 is the cathode electrode.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments, but the embodiments are only exemplary and do not constitute any limitation to the scope of the present invention. It should be understood by those skilled in the art that the details and forms of the technical solutions of the present invention can be modified or replaced without departing from the spirit and scope of the present invention, but these modifications and replacements all fall within the protection scope of the present invention.

Example 1

(1) Provide a transparent conductive substrate of flexible nickel mesh, and carry out standardized cleaning. The flexible nickel mesh is self-made (refer to the following literature for the preparation method: High-Performance, Ultra-Flexible and TransparentEmbedded Metallic Mesh Electrodes by Selective Electrodeposition for All -Solid-State Supercapacitor Applications, Journal of Materials Chemistry A, 2012, DOI: 10.1039/C7TA01947E);

(2) Dissolve methylammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and γ-hydroxybutyric acid lactone with a volume ratio of 3:7 in a molar ratio of 1:1, and stir for 2-8 hours. A 1.2 mol/L perovskite DMSO-GBL solution was obtained;

(3) Ozone the flexible nickel grid for 30 min, then dropwise add PEDOT:PSS PH1000 solution, rotate at 4000 rpm for 40 s, then anneal at 100 °C for 10 min, and then dropwise add PEDOT:PSS AI 4083 The solution was rotated at 4000 rpm for 40 s, and then the annealing temperature was 100 °C for 20 min to obtain a solidified hole transport layer with a thickness of 40-50 nm;

(4) After the perovskite precursor solution was treated with anti-solvent of chlorobenzene, the perovskite layer film was rotated at 4000 rpm for 40 seconds, treated with anti-solvent for 20 seconds, and then annealed at a constant temperature from 100 °C in nitrogen. Treated for 10 min to obtain a perovskite thin film layer with a thickness of 300-350 nm;

(5) Spin coating the electron transport layer PCBM on the perovskite thin film layer, accelerate to 3000rpm and rotate for 40 seconds to obtain a uniform electron transport layer film; its thickness is 50 nm;

(6) The BCP electron transport layer was prepared by evaporation method, and its thickness was 8 nm;

(7) Ag cathode electrode was prepared by evaporation method, and its thickness was 100 nm.

Comparative Example 1

(1) Provide a transparent conductive substrate of flexible silver grid and carry out standardized cleaning;

(2) Dissolve methylammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and γ-hydroxybutyric acid lactone with a volume ratio of 3:7 in a molar ratio of 1:1, and stir for 2-8 hours. A 1.2 mol/L perovskite DMSO-GBL solution was obtained;

(3) Ozone the flexible nickel grid for 30 min, then dropwise add PEDOT:PSS PH1000 solution, rotate at 4000 rpm for 40 s, then anneal at 100 °C for 10 min, and then dropwise add PEDOT:PSS AI 4083 The solution was rotated at 4000 rpm for 40 s, and then the annealing temperature was 100 °C for 20 min to obtain a solidified hole transport layer with a thickness of 40-50 nm;

(4) After the perovskite precursor solution was treated with anti-solvent of chlorobenzene, the perovskite layer film was rotated at 4000 rpm for 40 seconds, treated with anti-solvent for 20 seconds, and then annealed at a constant temperature from 100 °C in nitrogen. Treated for 10 min to obtain a perovskite thin film layer with a thickness of 300-350 nm;

(5) The electron transport layer PCBM was processed by spin coating on the perovskite film, accelerated to 3000rpm and rotated for 40 seconds to obtain a uniform electron transport layer film; its thickness was 50 nm;

(6) The electron transport layer BCP was prepared by evaporation method, and its thickness was 8 nm;

(7) Ag cathode electrode was prepared by evaporation method, and its thickness was 100 nm.

Comparative Example 2

(1) Provide a transparent conductive substrate of flexible ITO and carry out standardized cleaning;

(2) Dissolve methylammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and γ-hydroxybutyric acid lactone with a volume ratio of 3:7 in a molar ratio of 1:1, and stir for 2-8 hours. A 1.2 mol/L perovskite DMSO-GBL solution was obtained;

(3) Ozone the flexible nickel grid for 30 min, then dropwise add PEDOT:PSS PH1000 solution, rotate at 4000 rpm for 40 s, then anneal at 100 °C for 10 min, and then dropwise add PEDOT:PSS AI 4083 The solution was rotated at 4000 rpm for 40 s, and then the annealing temperature was 100 °C for 20 min to obtain a solidified hole transport layer with a thickness of 40-50 nm;

(4) After the perovskite precursor solution was treated with anti-solvent of chlorobenzene, the perovskite layer film was rotated at 4000 rpm for 40 seconds, treated with anti-solvent for 20 seconds, and then annealed at a constant temperature from 100 °C in nitrogen. Treated for 10 min to obtain a perovskite thin film layer with a thickness of 300-350 nm;

(5) The electron transport layer PCBM was processed by spin coating on the perovskite film, accelerated to 3000rpm and rotated for 40 seconds to obtain a uniform electron transport layer film; its thickness was 50 nm;

(6) The electron transport layer BCP was prepared by evaporation method, and its thickness was 8 nm;

(7) Ag cathode electrode was prepared by evaporation method, and its thickness was 100 nm.

The properties of the perovskite solar cells prepared in the above examples and comparative examples are shown in Table 1.

Table 1

By comparing Example 1 and Comparative Examples 1 and 2, it can be seen that the energy conversion efficiency of the flexible nickel grid is almost the same as that of the traditional flexible ITO and silver grids under indoor and outdoor illumination, but when bending 30 °In the case of nickel oxide, it shows better mechanical stability both indoors and outdoors. This shows that the nickel mesh has outstanding mechanical properties compared to other flexible electrodes.

Claims (9)

1. the perovskite solar cell of a nickel grid flexible electrode, is characterized in that, this perovskite solar cell uses the flexible nickel grid conductive thin film substrate as transparent electrode. 2. the perovskite solar cell of a kind of nickel grid flexible electrode according to claim 1, is characterized in that, described flexible nickel grid conductive film substrate is through (3,4-ethylenedioxythiophene): poly(styrene sulfonic acid) for treatment. 3. the preparation method of the described perovskite solar cell of claim 1 or 2, is characterized in that, comprises the following steps: (1) Dissolve methylammonium iodide and lead iodide in a mixed solution composed of dimethyl sulfoxide and γ-hydroxybutyric acid lactone and stir evenly to obtain a precursor solution of perovskite DMSO-GBL; (2) Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) with model PH1000 was deposited on the flexible nickel grid electrode, and then poly(3,4-ethylenedioxythiophene) with model AI4083 was further deposited Oxythiophene): poly(styrene sulfonic acid), forming a uniform hole transport layer film; (3) depositing a perovskite precursor solution on the hole transport layer thin film, and obtaining a perovskite thin film layer after annealing; (4) Spin coating, inkjet printing, or roll-to-roll processing of [6,6]-phenyl C61 methyl butyrate on the perovskite thin film layer to obtain a uniform electron transport layer; (5) The 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline modified layer is processed on the electron transport layer by vapor deposition or inkjet printing; (6) The cathode electrode is processed on the 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline modified layer by vapor deposition or inkjet printing. 4. The preparation method according to claim 2, wherein the thickness of the hole transport layer in the step (2) is 40-50 nm. 5. The preparation method according to claim 2, wherein in the step (3), the annealing temperature is set to 100°C, and the treatment time is 10 min. 6. The preparation method according to claim 2, wherein the thickness of the perovskite film in the step (3) is 300-350 nm. 7. The preparation method according to claim 2, wherein the thickness of the electron transport layer in the step (4) is 25-30 nm. 8. The preparation method according to claim 2, wherein the thickness of the modification layer in the step (5) is 8-12 nm. 9 . The preparation method according to claim 2 , wherein in the step (6), the cathode electrode is Ag, Cu or Au, and the thickness of the electrode is 60-100 nm. 10 .

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