CN111326658B - Perovskite solar cell with nickel grid flexible electrode and preparation method thereof - Google Patents
Perovskite solar cell with nickel grid flexible electrode and preparation method thereof Download PDFInfo
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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. The conductivity and the uniformity of the film are further improved through the highly conductive organic poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid), 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
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a nickel-mesh flexible electrode perovskite solar cell and a preparation method thereof.
Background
Solar energy is converted into electric energy by the solar cell device, so that the problem of increasingly severe energy at present is effectively solved, and meanwhile, the characteristic of environmental friendliness receives wide attention. Among them, the perovskite solar cell is rapidly developed due to its excellent photovoltaic characteristics and low cost, and its highest energy conversion efficiency can reach 25.5%. At present, the perovskite solar cell with superior performance is mainly based on a glass substrate of indium tin oxide or fluorine-doped tin oxide, and due to limited reserves and high price of metal elements such as indium, tin and the like and environmental pollution after leakage, the popularization and industrial application of the perovskite solar cell are limited to a great extent, and meanwhile, the service life of the perovskite solar cell on a flexible device is limited due to the defect of ductility of inorganic nonmetal oxide indium tin oxide.
The application of the flexible transparent conductive electrode in the flexible photovoltaic device powerfully promotes the development of energy supply of flexible wearable and intelligent Internet of things terminals. However, the currently used flexible transparent ito electrode is very easy to fall off during the bending process of the device, which affects the continuity of the electrode and finally causes the reduction of the energy conversion efficiency of the photovoltaic device. Therefore, the search for the high-transparency conductive electrode with tensile resistance and bending resistance is the research focus of the current flexible photovoltaic device.
Disclosure of Invention
The technical problem to be solved is as follows: the common flexible indium tin oxide transparent electrode is fragile, lacks flexibility, and is easy to fall off and break under the bending and stretching conditions, so that the photoelectric property and stability of the perovskite photovoltaic device are remarkably reduced, and the commercial application of the perovskite photovoltaic device is influenced finally. Meanwhile, the traditional silver nanowire and silver mesh transparent electrode is very easy to generate ion migration due to silver ions and is combined with halogen in the perovskite, so that the perovskite film is rapidly degraded. In order to overcome the defects of various mechanical properties of flexible electrodes in the conventional photovoltaic devices and simultaneously optimize the photovoltaic performance of the devices, the invention aims to provide a novel preparation method of a perovskite solar cell with nickel mesh flexible electrodes.
In order to achieve the above object, the present invention provides the following technical solutions:
the perovskite solar cell with the nickel mesh flexible electrode is characterized in that the perovskite solar cell takes a flexible nickel mesh conductive thin film substrate as a transparent electrode.
Further, the flexible nickel mesh conductive film substrate is prepared from (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS).
The preparation method of the perovskite solar cell is characterized by comprising the following steps:
(1) Dissolving methyl ammonium iodide and lead iodide into a mixed solution consisting of dimethyl sulfoxide and gamma-hydroxy butyrate lactone, and uniformly stirring to obtain a precursor solution of perovskite DMSO-GBL;
(2) And (3) depositing PEDOT with the model of PH1000 on the flexible nickel grid electrode: PSS, followed by further deposition of PEDOT, model AI 4083: PSS, forming a uniform hole transport layer film;
(3) Depositing a perovskite precursor solution on the hole transport layer thin film, and annealing to obtain a perovskite thin film layer;
(4) Processing [6,6] -phenyl C61 methyl butyrate (PCBM) on the perovskite thin film layer in a spin coating, ink-jet printing or roll-to-roll mode to obtain a uniform electron transport layer;
(5) Processing a 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP) modification layer on the electronic transmission layer by adopting an evaporation or ink-jet printing method;
(6) And processing a cathode electrode on the 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline modification layer by adopting an evaporation or ink-jet printing method.
Further, the thickness of the hole transport layer in the step (2) is 40-50nm.
Further, the annealing temperature in the step (3) is set to be 100 ℃, and the treatment time is 10min.
Further, the thickness of the perovskite thin film in the step (3) is 300-350nm.
Further, the thickness of the electron transport layer in the step (4) is 25-30nm.
Further, the thickness of the modifying layer in the step (5) is 8-12nm.
Further, in the step (6), the cathode electrode is Ag, cu or Au, and the thickness of the electrode is 60-100nm.
Has the advantages that: the invention provides a perovskite solar cell of a nickel mesh flexible electrode and a preparation method thereof. By highly conductive PEDOT: PSS combines together with the nickel net check, and the further electric conductivity that improves nickel net check electrode and the roughness of film, through stretching repeatedly and the process of buckling, flexible nickel net check perovskite photovoltaic device can keep better electrode continuity, and the nickel oxide that the nickel element in the nickel net formed in the air can regard as effectual hole transport material, more is favorable to the charge transport of device. The preparation method is simple, is beneficial to improving the indoor and outdoor mechanical stability of the flexible photovoltaic device and the phase stability of the crystal, and is convenient for the development and application of self-generating flexible intelligent wearing.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite solar cell manufactured by the manufacturing method of the invention.
In the figure: 1 is a substrate; 2 is an anode electrode; 3 is a hole transport layer; 4 is a perovskite thin film layer; 5. 6 is an electron transport layer; and 7, a cathode electrode.
Detailed Description
The present invention is further described below with reference to specific examples, which are only exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
(1) Providing a Transparent conductive substrate of Flexible nickel grids, and carrying out standardized cleaning, wherein the Flexible nickel grids are manufactured by self-manufacturing (the preparation method is shown in the following documents: high-Performance, ultra-Flexible and transient Embedded Metallic Mesh Electrodes by Selective electrochemical Applications for All-Solid-State superparameter Applications, journal of Materials Chemistry A, 2012, DOI: 10.1039/C7TA 01947E);
(2) Dissolving methyl ammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and gamma-hydroxy butyrate lactone with the volume ratio of 3:7 according to the molar ratio of 1:1, and stirring for 2-8 hours to obtain 1.2mol/L perovskite DMSO-GBL solution;
(3) And (3) carrying out ozone treatment on the flexible nickel mesh for 30min, and then dropwise adding PEDOT: PSS PH1000 solution, spin 40s at 4000rpm, then anneal temperature 100 ℃, anneal for 10min, then drop wise PEDOT: PSS AI4083 solution, rotate 40s with the rotational speed of 4000rpm, then anneal the temperature at 100 ℃, anneal for 20min, get the solidified hole transport layer, the thickness is 40-50 nm;
(4) After the perovskite precursor solution is subjected to anti-solvent treatment of chlorobenzene, the perovskite layer thin film is rotated for 40 seconds at the rotating speed of 4000rpm, anti-solvent treatment is carried out when the perovskite layer thin film is 20 seconds, then annealing treatment is carried out, and the perovskite thin film is subjected to constant temperature treatment in nitrogen for 10min at the temperature of 100 ℃ to obtain the perovskite thin film layer, wherein the thickness of the perovskite thin film layer is 300-350 nm;
(5) Spin-coating an electron transport layer PCBM on the perovskite thin film layer, and rotating at the rotating speed of 3000rpm for 40 seconds to obtain a uniform electron transport layer thin film; its thickness is 50 nm;
(6) Preparing a BCP electron transport layer by adopting an evaporation method, wherein the thickness of the BCP electron transport layer is 8 nm;
(7) The cathode electrode Ag is prepared by adopting an evaporation method, and the thickness of the cathode electrode Ag is 100nm.
Comparative example 1
(1) Providing a transparent conductive substrate with a flexible silver grid, and carrying out standardized cleaning;
(2) Dissolving methyl ammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and gamma-hydroxy butyrate lactone with the volume ratio of 3:7 according to the molar ratio of 1:1, and stirring for 2-8 hours to obtain 1.2mol/L perovskite DMSO-GBL solution;
(3) And (3) carrying out ozone treatment on the flexible nickel mesh for 30min, and then dropwise adding PEDOT: PSS PH1000 solution, spin 40s at 4000rpm, then anneal temperature 100 ℃, anneal for 10min, then drop wise PEDOT: PSS AI4083 solution, rotate 40s with the rotational speed of 4000rpm, then anneal the temperature at 100 ℃, anneal for 20min, get the solidified hole transport layer, the thickness is 40-50 nm;
(4) After the perovskite precursor solution is subjected to anti-solvent treatment of chlorobenzene, the perovskite layer thin film is rotated for 40 seconds at the rotating speed of 4000rpm, anti-solvent treatment is carried out when the perovskite layer thin film is 20 seconds, then annealing treatment is carried out, and the perovskite thin film is subjected to constant temperature treatment in nitrogen for 10min at the temperature of 100 ℃ to obtain the perovskite thin film layer, wherein the thickness of the perovskite thin film layer is 300-350 nm;
(5) Processing an electron transport layer PCBM on the perovskite thin film by a spin coating method, accelerating to rotate at the rotating speed of 3000rpm for 40 seconds, and obtaining a uniform electron transport layer thin film; the thickness of the coating is 50 nm;
(6) Preparing an electron transport layer BCP by adopting an evaporation method, wherein the thickness of the electron transport layer BCP is 8 nm;
(7) The cathode electrode Ag is prepared by adopting an evaporation method, and the thickness of the cathode electrode Ag is 100nm.
Comparative example 2
(1) Providing a transparent conductive substrate of flexible ITO, and carrying out standardized cleaning;
(2) Dissolving methyl ammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and gamma-hydroxy butyrate lactone with the volume ratio of 3:7 according to the molar ratio of 1:1, and stirring for 2-8 hours to obtain 1.2mol/L perovskite DMSO-GBL solution;
(3) And (3) carrying out ozone treatment on the flexible nickel mesh for 30min, and then dropwise adding PEDOT: PSS PH1000 solution, spin 40s at 4000rpm, then anneal temperature 100 ℃, anneal for 10min, then drop wise PEDOT: PSS AI4083 solution, rotate 40s with the rotational speed of 4000rpm, then anneal the temperature at 100 ℃, anneal for 20min, get the solidified hole transport layer, the thickness is 40-50 nm;
(4) After the perovskite precursor solution is subjected to anti-solvent treatment of chlorobenzene, the perovskite layer thin film is rotated for 40 seconds at the rotating speed of 4000rpm, anti-solvent treatment is carried out when the perovskite layer thin film is 20 seconds, then annealing treatment is carried out, and the perovskite thin film is subjected to constant temperature treatment in nitrogen for 10min at the temperature of 100 ℃ to obtain the perovskite thin film layer, wherein the thickness of the perovskite thin film layer is 300-350 nm;
(5) Processing an electron transport layer PCBM on the perovskite thin film by a spin coating method, accelerating to rotate at the rotating speed of 3000rpm for 40 seconds, and obtaining a uniform electron transport layer thin film; its thickness is 50 nm;
(6) Preparing an electron transport layer BCP by adopting an evaporation method, wherein the thickness of the electron transport layer BCP is 8 nm;
(7) The cathode electrode Ag is prepared by adopting an evaporation method, and the thickness of the cathode electrode Ag is 100nm.
The properties of the perovskite solar cells prepared in the above examples and comparative examples are shown in table 1.
TABLE 1
As can be seen from comparing example 1 with comparative examples 1 and 2, the energy conversion efficiency under indoor and outdoor light is almost comparable to that of the conventional flexible ITO and silver grids prepared using the flexible nickel grid, but the nickel oxide exhibits better mechanical stability both indoors and outdoors at a bend of 30 °. This demonstrates the outstanding mechanical properties of the nickel mesh relative to other flexible electrodes.
Claims (7)
1. The preparation method of the perovskite solar cell with the nickel grid flexible electrode is characterized in that the perovskite solar cell takes a flexible nickel grid conductive thin film substrate as a transparent electrode, and the flexible nickel grid conductive thin film substrate is prepared from (3,4-ethylenedioxythiophene): poly (styrenesulfonic acid), said preparation method comprising the steps of:
(1) Dissolving methyl ammonium iodide and lead iodide in a mixed solution of dimethyl sulfoxide and gamma-hydroxybutyric lactone at a volume ratio of 1:1 and 3:7, and stirring for 2-8 hours to obtain a 1.2mol/L perovskite DMSO-GBL solution;
(2) And (3) carrying out ozone treatment on the flexible nickel mesh for 30min, and then dropwise adding PEDOT: PSS PH1000 solution, rotated at 4000rpm for 40s, followed by an annealing temperature of 100 ℃, annealing for 10min, followed by dropwise addition of PEDOT: the PSS AI4083 solution is rotated for 40s at the rotation speed of 4000rpm, the annealing temperature is 100 ℃, and the hole transport layer is obtained after annealing for 20 min;
(3) After the perovskite precursor solution is subjected to anti-solvent treatment of chlorobenzene, the perovskite layer thin film rotates at the rotating speed of 4000rpm for 40 seconds, the anti-solvent treatment is carried out after 20 seconds, and then annealing treatment is carried out to obtain the perovskite thin film layer;
(4) Spin-coating an electron transport layer PCBM on the perovskite thin film layer, and rotating at the rotating speed of 3000rpm for 40 seconds to obtain a uniform electron transport layer thin film;
(5) Processing a 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline modification layer on the electronic transmission layer by adopting an evaporation or ink-jet printing method;
(6) And processing a cathode electrode on the 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline modification layer by adopting an evaporation or ink-jet printing method.
2. The method according to claim 1, wherein the hole transport layer in the step (2) has a thickness of 40 to 50nm.
3. The method according to claim 1, wherein the annealing temperature in the step (3) is set to 100 ℃ and the treatment time is 10min.
4. The method according to claim 1, wherein the thickness of the perovskite thin film in the step (3) is 300 to 350nm.
5. The method according to claim 1, wherein the thickness of the electron transport layer in the step (4) is 25 to 30nm.
6. The method according to claim 1, wherein the thickness of the modified layer in the step (5) is 8 to 12nm.
7. The preparation method according to claim 1, wherein in the step (6), the cathode electrode is Ag, cu or Au, and the thickness of the electrode is 60-100nm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540371A (en) * | 2009-04-15 | 2009-09-23 | 河北大学 | Flexible polymer solar battery of anode layer of metal grid and preparation method |
| CN105789448A (en) * | 2016-04-18 | 2016-07-20 | 北京大学 | Thin film preparation method utilizing nanoparticle to improve surface wettability |
| CN105788760A (en) * | 2016-04-22 | 2016-07-20 | 陈初群 | Method of manufacturing transparent conductive electrode |
| CN109912458A (en) * | 2019-02-28 | 2019-06-21 | 苏州大学 | Metal halide perovskite material, preparation method and solar cell device and preparation method thereof |
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| TWI474992B (en) * | 2014-04-29 | 2015-03-01 | Univ Nat Central | Method for preparing perovskite thin film and solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101540371A (en) * | 2009-04-15 | 2009-09-23 | 河北大学 | Flexible polymer solar battery of anode layer of metal grid and preparation method |
| CN105789448A (en) * | 2016-04-18 | 2016-07-20 | 北京大学 | Thin film preparation method utilizing nanoparticle to improve surface wettability |
| CN105788760A (en) * | 2016-04-22 | 2016-07-20 | 陈初群 | Method of manufacturing transparent conductive electrode |
| CN109912458A (en) * | 2019-02-28 | 2019-06-21 | 苏州大学 | Metal halide perovskite material, preparation method and solar cell device and preparation method thereof |
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