CN117255598A - Perovskite solar car film and preparation method thereof - Google Patents
Perovskite solar car film and preparation method thereof Download PDFInfo
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- CN117255598A CN117255598A CN202310857828.8A CN202310857828A CN117255598A CN 117255598 A CN117255598 A CN 117255598A CN 202310857828 A CN202310857828 A CN 202310857828A CN 117255598 A CN117255598 A CN 117255598A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 230000005525 hole transport Effects 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000013013 elastic material Substances 0.000 claims abstract description 15
- 125000006281 4-bromobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Br)C([H])([H])* 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000004020 conductor Substances 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000004544 sputter deposition Methods 0.000 claims abstract description 8
- -1 formamidine ion Chemical class 0.000 claims description 27
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 15
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 7
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- RPNMGUBLKCLAEK-UHFFFAOYSA-N 2-(4-chlorophenyl)sulfanyl-n,n-diethylethanamine;hydrochloride Chemical compound [Cl-].CC[NH+](CC)CCSC1=CC=C(Cl)C=C1 RPNMGUBLKCLAEK-UHFFFAOYSA-N 0.000 claims description 3
- 101100243399 Caenorhabditis elegans pept-2 gene Proteins 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229910001419 rubidium ion Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 80
- 239000000243 solution Substances 0.000 description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 12
- 238000000137 annealing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910001417 caesium ion Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L8/00—Electric propulsion with power supply from forces of nature, e.g. sun or wind
- B60L8/003—Converting light into electric energy, e.g. by using photo-voltaic systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Power Engineering (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a perovskite solar car film and a preparation method thereof, and belongs to the technical field of solar car films. S1, arranging a wire slot on the surface of a flexible substrate, and filling elastic materials into the wire slot to obtain a pretreated flexible substrate; s2, sputtering conductive materials on the pretreated flexible substrate to form a conductive layer; s3, forming an electron transport layer on the conductive layer; s4, coating perovskite precursor solution on the electron transport layer to form a perovskite layer; the perovskite precursor solution comprises a perovskite material, 4-bromobenzyl iodized amine and a solvent; and S5, sequentially forming a hole transport layer and an electrode layer on the perovskite layer to obtain the perovskite solar car film. The perovskite solar car film has a large application prospect by improving the stability of the perovskite body and the mechanical property of the device substrate, can cover the whole car body, and has a simple production process and practical application value.
Description
Technical Field
The invention belongs to the technical field of solar car films, and particularly relates to a perovskite solar car film and a preparation method thereof.
Background
Perovskite materials with crystal structures are widely used in various fields because of the advantages of high extinction coefficient, wide light absorption range, long carrier diffusion distance, band gap adjustability, bipolar transmission and the like. The conventional application is as a building photovoltaic outer wall, a digital product small-area solar power generation screen and a solar power generation window of a vehicle.
Currently, global energy is intense, and the automobile industry, which is one of the main energy consumption bodies, faces the challenge of how to realize green sustainable development. The use of perovskite solar cells in the automotive field is known, for example patent CN 212047105U, providing an automotive window with perovskite solar cells, but with an effective area only suitable for glass windows, and therefore with limited power generation efficiency. In addition, existing perovskite solar cells for use on vehicle bodies are disadvantageous in that they are generally rigid substrates, hamper the use of non-planar areas of the vehicle body, and are relatively complex in process. In summary, how to integrate the perovskite solar cell on the car body, utilize solar energy to supply power for the car, alleviate the traditional energy consumption of car, become the problem that needs to solve.
Disclosure of Invention
The first object of the invention is to provide a method for preparing perovskite solar car film, comprising the following steps,
s1, arranging a wire slot on the surface of a flexible substrate, and filling elastic materials into the wire slot to obtain a pretreated flexible substrate;
s2, sputtering a conductive material on the pretreated flexible substrate in the S1 to form a conductive layer;
s3, coating an electron transport material on the conductive layer in the S2 to form an electron transport layer;
s4, coating perovskite precursor solution on the electron transport layer in the S3 to form a perovskite layer; the perovskite precursor solution comprises a perovskite material, a stable cross-linking agent and a solvent; the perovskite material is ABX 3 Perovskite, the cation at A-position is selected from methyl ammonium ion CH 3 NH 3 + (MA + ) Formamidine ion HC (NH) 2 ) 2 + (FA + ) Cesium ions Cs + And rubidium ions Rb + One or more of the following; the cation at B position is selected from Pb ion 2+ Tin ion Sn 2+ And germanium ions Ge 2+ One or more of the following; the anion at the X position is selected from iodide I - Bromine ions Br - And chloride ions Cl - One or more of the following; the stabilizing cross-linking agent is selected from 4-bromobenzyl iodinated amine (4-BBAI);
and S5, sequentially forming a hole transport layer and an electrode layer on the perovskite layer in the S4 to obtain the perovskite solar car film.
In one embodiment of the present invention, in S1, the material of the flexible substrate is selected from one or more of polyethylene terephthalate (PET), polyimide (PI) and polyethylene naphthalate (PEN); the elastic material is selected from polyurethane and/or polydimethylsiloxane PDMS.
In one embodiment of the invention, in S1, the flexible substrate has a thickness of 50 μm to 125 μm.
In one embodiment of the present invention, in S1, the width of the wire groove is 20 μm to 50 μm and the depth is smaller than the thickness of the flexible substrate.
In one embodiment of the invention, in S1, the shape of the wire chase is selected from a straight line and/or a wavy line.
In one embodiment of the present invention, in S1, the wire grooves are formed by laser scribing and/or mechanical scribing.
In one embodiment of the present invention, in S1, the filling amount of the elastic material is adjusted according to the width and depth of the wire slot, and may be fully spread or spot coated.
In one embodiment of the invention, in S2, the conductive material is selected from Indium Tin Oxide (ITO) and/or fluorine doped SnO 2 (FTO)。
In one embodiment of the present invention, in S3, the electron transport material is selected from TiO 2 、SnO 2 、ZnO、C 60 PCBM, ICBA or CPTA; the thickness of the electron transport layer is 20nm-30nm.
In one embodiment of the present invention, in S4, the concentration of the perovskite material in the perovskite precursor solution is 0.8mol/L to 1.2mol/L, and the concentration of the stabilizing cross-linking agent is 5mol/L to 20mol/L.
In one embodiment of the present invention, in S4, the solvent is selected from one or more of 2-mercaptoethanol (2-ME), γ -butyrolactone (γ -GBL), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
Further, the solvent is selected from the group consisting of N, N-Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO).
In one embodiment of the present invention, in S5, the material of the hole transport layer is selected from CuI, cuSCN, niO x One or more of PSS, spiro-MeOTAD, PTAA and P3 HT; the thickness of the hole transport layer is 40nm-50nm.
In one embodiment of the present invention, in S5, the material of the electrode layer is selected from gold, silver or aluminum; the thickness of the electrode layer is 80nm-100nm.
The second object of the invention is to provide the perovskite solar car film prepared by the method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The perovskite precursor solution adopted by the preparation method of the invention is added with the stable cross-linking agent 4-bromobenzyl iodized amine (4-BBAI), halogen anions bromine and iodine are introduced, the solution can coordinate with B-site cations in perovskite to play an anchoring role, a layer of 2D structure is formed at the upper interface of perovskite and is combined with a perovskite 3D structure, the 3D/2D structure increases the stability of a functional layer, and in addition, the introduced cations NH 3 + Can inhibit migration and decomposition of organic amine cations in the perovskite material containing the organic amine cations, and effectively improve the stability of the perovskite material.
(2) The perovskite solar car film adopts a pretreated flexible substrate, so that the flexible substrate has a stretching-resistant structure, namely, scribing is carried out on the flexible substrate, a wire groove with the depth smaller than the thickness of the substrate is formed, and elastic materials are filled in the wire groove. When the car film is attached to a car, the car film can be stretched, and the wire grooves and elastic materials in the wire grooves can buffer partial stress so as to adapt to different curved surfaces, and at the moment, the mechanical performance of the car film is stable due to the existence of the stretch-resistant structure in the flexible substrate. After the test, the pretreated substrate can bear 3% of stretching, the device is not seriously damaged when being stretched by external force, and the efficiency of the device is basically stable, so that the problem of poor stability of the flexible car cover during actual mounting is solved to a certain extent.
(3) The perovskite solar car film has a large application prospect by improving the stability of the perovskite body and the mechanical property of the device substrate, can cover the whole car body, has a simple production process and has practical application value.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a structural formula of 4-bromobenzyl iodinated amine (4-BBAI) in an embodiment of the present invention;
FIG. 2 is an SEM characterization of perovskite layer according to example 1 of the invention;
FIG. 3 is a SEM characterization of the invention under tensile conditions of a perovskite layer according to example 1;
FIG. 4 is a SEM characterization of the invention under tensile conditions of a perovskite layer according to comparative example 1;
fig. 5 is an SEM characterization of the invention under tensile conditions based on the perovskite layer of comparative example 2.
Detailed Description
In order to solve the technical problems, the invention provides a perovskite solar car film and a preparation method thereof. The perovskite solar car film has a semitransparent appearance, when sunlight is incident on the perovskite layer from the electrode layer, photo-generated carriers are generated, electrons and holes are respectively transmitted to the conductive layer and the electrode layer, and finally, photocurrent is generated through a circuit connecting the conductive layer and the electrode layer, so that power supply for a car body is realized.
The first object of the invention is to provide a method for preparing perovskite solar car film, comprising the following steps,
s1, arranging a wire slot on the surface of a flexible substrate, and filling elastic materials into the wire slot to obtain a pretreated flexible substrate;
s2, sputtering a conductive material on the pretreated flexible substrate in the S1 to form a conductive layer;
s3, coating an electron transport material on the conductive layer in the S2 to form an electron transport layer;
s4, coating perovskite precursor solution on the electron transport layer in the S3 to form a perovskite layer; the perovskite precursor solution comprises a perovskite material, a stable cross-linking agent and a solvent; the perovskite material is ABX 3 Perovskite, the cation at A-position is selected from methyl ammonium ion CH 3 NH 3 + (MA + ) Formamidine ion HC (NH) 2 ) 2 + (FA + ) Cesium ions Cs + And rubidium ions Rb + One or more of the following; the cation at B position is selected from Pb ion 2+ Tin ion Sn 2+ And germanium ions Ge 2+ One or more of the following; the anion at the X position is selected from iodide I - Bromine ions Br - And chloride ions Cl - One or more of the following; the stabilizing cross-linking agent is selected from 4-bromobenzyl iodinated amine (4-BBAI);
and S5, sequentially forming a hole transport layer and an electrode layer on the perovskite layer in the S4 to obtain the perovskite solar car film.
In one embodiment of the present invention, in S1, the material of the flexible substrate is selected from one or more of polyethylene terephthalate (PET), polyimide (PI) and polyethylene naphthalate (PEN); the elastic material is selected from polyurethane and/or polydimethylsiloxane PDMS.
Further, in S1, the material of the flexible substrate is selected from polyethylene terephthalate (PET).
In one embodiment of the invention, in S1, the flexible substrate has a thickness of 50 μm to 125 μm.
Further, in S1, the thickness of the flexible substrate is 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, or any thickness between any two values.
In one embodiment of the present invention, in S1, the width of the wire groove is 20 μm to 50 μm and the depth is smaller than the thickness of the flexible substrate.
In one embodiment of the invention, in S1, the shape of the wire chase is selected from a straight line and/or a wavy line.
In one embodiment of the present invention, in S1, the wire grooves are formed by laser scribing and/or mechanical scribing.
In one embodiment of the present invention, in S1, the filling amount of the elastic material is adjusted according to the width and depth of the wire slot, and may be fully spread or spot coated.
In one embodiment of the invention, in S2, the conductive material is selected from Indium Tin Oxide (ITO) and/or fluorine doped SnO 2 (FTO)。
Further, in S2, the conductive material is selected from fluorine doped SnO 2 (FTO)。
In one embodiment of the present invention, in S3, the electron transport material is selected from TiO 2 、SnO 2 、ZnO、C 60 PCBM, ICBA or CPTA; the thickness of the electron transport layer is 20nm-30nm.
In one embodiment of the present invention, in S4, the concentration of the perovskite material in the perovskite precursor solution is 0.8mol/L to 1.2mol/L, and the concentration of the stabilizing cross-linking agent is 5mol/L to 20mol/L.
In one embodiment of the present invention, in S4, the solvent is selected from one or more of 2-mercaptoethanol (2-ME), γ -butyrolactone (γ -GBL), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).
Further, the solvent is selected from the group consisting of N, N-Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO).
In one embodiment of the inventionIn an embodiment, in S5, the hole transport layer material is selected from CuI, cuSCN, niO x One or more of PSS, spiro-MeOTAD, PTAA and P3 HT; the thickness of the hole transport layer is 40nm-50nm.
In one embodiment of the present invention, in S5, the material of the electrode layer is selected from gold, silver or aluminum; the thickness of the electrode layer is 80nm-100nm.
The second object of the invention is to provide a perovskite solar car film prepared by the method
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, the primary devices employed in the examples are roll-to-roll devices unless otherwise indicated.
Example 1
The invention relates to a perovskite solar car film and a preparation method thereof, which specifically comprise the following steps:
s1, preparing perovskite precursor solution:
s11, weighing FAI and PbI 2 Dissolving in a mixed solution of DMF and DMSO (volume ratio of 4:1), and stirring at 65 ℃ overnight to obtain a mixed solution;
s12, weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
s13, adding the equal volume of CsI solution into the mixed solution to obtain a perovskite solution, wherein the perovskite system is Cs 0.05 FA 0.95 PbI 3 The concentration of perovskite is 0.8mol/L;
s14, adding the stable cross-linking agent 4-bromobenzyl iodized amine shown in the figure 1 into the perovskite solution, and uniformly mixing to obtain a perovskite precursor solution, wherein the concentration of the 4-bromobenzyl iodized amine is 8mol/L;
s2, pretreatment of a flexible substrate:
s21, scribing a linear wire groove on a polyethylene terephthalate (PET) flexible substrate with the thickness of about 125 mu m by adopting a laser scribing mode, wherein the width of the wire groove is about 45 mu m, and the depth of the wire groove is about 50 mu m;
and S22, filling polyurethane elastic materials into the wire grooves to finish pretreatment of the flexible substrate.
S3, sputtering a conductive material FTO on the pretreated flexible substrate to form a conductive layer;
s4, coating deionized water dispersion liquid of FTO on the conductive layer, and annealing and drying at 150 ℃ for 25min to form an electron transport layer with the thickness of about 25 nm;
s5, coating perovskite precursor solution on the electron transport layer, and annealing and drying at 110 ℃ for 15min to form a perovskite layer;
s6, forming a Spiro-MeOTAD hole transport layer with the thickness of about 45nm on the perovskite layer;
and S7, forming an Ag electrode layer with the thickness of about 90nm on the hole transport layer to obtain the perovskite solar car film.
Example 2
The invention relates to a perovskite solar car film and a preparation method thereof, which specifically comprise the following steps:
s1, preparing perovskite precursor solution:
s11, weighing FAI and PbI 2 Dissolving in a mixed solution of DMF and DMSO (volume ratio of 4:1), and stirring at 65 ℃ overnight to obtain a mixed solution;
s12, weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
s13, adding the equal volume of CsI solution into the mixed solution to obtain a perovskite solution, wherein the perovskite system is Cs 0.05 FA 0.95 PbI 3 The concentration of perovskite is 0.8mol/L;
s14, adding the stable cross-linking agent 4-bromobenzyl iodized amine shown in the figure 1 into the perovskite solution, and uniformly mixing to obtain a perovskite precursor solution, wherein the concentration of the 4-bromobenzyl iodized amine is 5mol/L;
s2, pretreatment of a flexible substrate:
s21, scribing a linear wire groove on a polyethylene terephthalate (PET) flexible substrate with the thickness of about 125 mu m by adopting a laser scribing mode, wherein the width of the wire groove is about 45 mu m, and the depth of the wire groove is about 50 mu m;
and S22, filling polyurethane elastic materials into the wire grooves to finish pretreatment of the flexible substrate.
S3, sputtering a conductive material FTO on the pretreated flexible substrate to form a conductive layer;
s4, coating deionized water dispersion liquid of FTO on the conductive layer, and annealing and drying at 150 ℃ for 25min to form an electron transport layer with the thickness of about 25 nm;
s5, coating perovskite precursor solution on the electron transport layer, and annealing and drying at 110 ℃ for 15min to form a perovskite layer;
s6, forming a Spiro-MeOTAD hole transport layer with the thickness of about 45nm on the perovskite layer;
and S7, forming an Ag electrode layer with the thickness of about 90nm on the hole transport layer to obtain the perovskite solar car film.
Comparative example 1 essentially the same as example 1, except that no stabilizing cross-linking agent was added to the perovskite precursor solution
S1, preparing perovskite solution:
s11, weighing FAI and PbI 2 Dissolving in a mixed solution of DMF and DMSO (volume ratio of 4:1), and stirring at 65 ℃ overnight to obtain a mixed solution;
s12, weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
s13, adding the equal volume of CsI solution into the mixed solution to obtain a perovskite solution, wherein the perovskite system is Cs 0.05 FA 0.95 PbI 3 The concentration of perovskite is 0.8mol/L;
s2, pretreatment of a flexible substrate:
s21, scribing a linear wire groove on a polyethylene terephthalate (PET) flexible substrate with the thickness of about 125 mu m by adopting a laser scribing mode, wherein the width of the wire groove is about 45 mu m, and the depth of the wire groove is about 50 mu m;
and S22, filling polyurethane elastic materials into the wire grooves to finish pretreatment of the flexible substrate.
S3, sputtering a conductive material FTO on the pretreated flexible substrate to form a conductive layer;
s4, coating deionized water dispersion liquid of FTO on the conductive layer, and annealing and drying at 150 ℃ for 25min to form an electron transport layer with the thickness of about 25 nm;
s5, coating perovskite solution on the electron transport layer, and annealing and drying at 110 ℃ for 15min to form a perovskite layer;
s6, forming a Spiro-MeOTAD hole transport layer with the thickness of about 45nm on the perovskite layer;
and S7, forming an Ag electrode layer with the thickness of about 90nm on the hole transport layer to obtain the perovskite solar car film.
Comparative example 2 is substantially the same as comparative example 1 except that the flexible substrate was not subjected to pretreatment
S1, preparing perovskite solution:
s11, weighing FAI and PbI 2 Dissolving in a mixed solution of DMF and DMSO (volume ratio of 4:1), and stirring at 65 ℃ overnight to obtain a mixed solution;
s12, weighing CsI, dissolving in DMSO, and stirring at 70 ℃ for about 2.5 hours to obtain CsI solution;
s13, adding the equal volume of CsI solution into the mixed solution to obtain a perovskite solution, wherein the perovskite system is Cs 0.05 FA 0.95 PbI 3 The concentration of perovskite is 0.8mol/L;
s2, sputtering a conductive material FTO on a polyethylene terephthalate (PET) flexible substrate with the thickness of about 125 mu m to form a conductive layer;
s3, coating deionized water dispersion liquid of FTO on the conductive layer, and annealing and drying at 150 ℃ for 25min to form an electron transport layer with the thickness of about 25 nm;
s4, coating perovskite solution on the electron transport layer, and annealing and drying at 110 ℃ for 15min to form a perovskite layer;
s5, forming a Spiro-MeOTAD hole transport layer with the thickness of about 45nm on the perovskite layer;
and S6, forming an Ag electrode layer with the thickness of about 90nm on the hole transport layer to obtain the perovskite solar car film.
Test example 1
The perovskite layer was SEM-characterized based on example 1, and the results are shown in fig. 2. As can be seen from fig. 2, since the stable cross-linking agent 4-bromobenzyl iodized amine (4-BBAI) is added in the perovskite precursor solution, a layer of 2D structure is formed at the upper interface of the perovskite, and is combined with the perovskite 3D structure, the 3D/2D structure increases the stability of the functional layer, and when the perovskite precursor solution is used as a car cover, the perovskite layer can be kept not to break under certain stretching.
Test example 2
The perovskite layer prepared based on example 1, comparative examples 1-2 was stretched by 3%, and the perovskite layer under the stretching condition was subjected to SEM characterization, and the results are shown in fig. 3-5. As can be seen from fig. 3-5, after the addition of 4-bromobenzyl iodized amine (4-BBAI), the tensile property of the perovskite film is obviously improved compared with that of a sample without the addition of 4-BBAI, and no crack is generated; this is because when 4-BBAI is added, halogen anions bromine and iodine are introduced, which can coordinate with lead ions in perovskite to play an anchoring role, a layer of 2D structure is formed at the upper interface of perovskite, and is combined with perovskite 3D structure, and the 3D/2D structure increases the stability of the functional layer, and in addition, the introduced cation NH 3 + Can inhibit migration and decomposition of organic amine cations in the perovskite material containing the organic amine cations, and effectively improve the stability of the perovskite material.
Test example 3
The perovskite solar car films before and after stretching were tested for electrical properties based on example 1, comparative examples 1-2, and the results are shown in table 1:
TABLE 1
As can be seen from Table 1, the PCE of the device was reduced after stretching by 3%, but the device efficiency remained substantially stable due to the addition of 4-bromobenzyl iodinated amine (4-BBAI) and pretreatment of the flexible substrate, without serious damage to the device during external stretching. In contrast, the degradation of device performance without substrate pretreatment and with 4-BBAI added is more pronounced. This is because when 4-BBAI is added, halogen anions bromine and iodine are introduced, which can coordinate with lead ions in perovskite to play an anchoring role, and form a layer on the upper interface of perovskite2D structure combined with perovskite 3D structure, such 3D/2D structure increases stability of functional layer, and additionally, introduced cation NH 3 + The migration and decomposition of organic amine cations in the perovskite material containing the organic amine cations can be inhibited, and the stability of the perovskite material is effectively improved; on the other hand, the flexible substrate is pretreated and also buffers a portion of the tensile stress. When the car membrane is stretched by external force, the wire groove and the elastic material in the wire groove can buffer partial stress so as to adapt to different tensile forces, and at the moment, the car membrane is relatively stable due to the existence of the stretch-resistant structure in the flexible substrate.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A preparation method of a perovskite solar car film is characterized by comprising the following steps,
s1, arranging a wire slot on the surface of a flexible substrate, and filling elastic materials into the wire slot to obtain a pretreated flexible substrate;
s2, sputtering a conductive material on the pretreated flexible substrate in the S1 to form a conductive layer;
s3, coating an electron transport material on the conductive layer in the S2 to form an electron transport layer;
s4, coating perovskite precursor solution on the electron transport layer in the S3 to form a perovskite layer; the perovskite precursor solution comprises a perovskite material, a stable cross-linking agent and a solvent; the perovskite material is ABX 3 Perovskite, wherein the cation at the A site is selected from one or more of methyl ammonium ion, formamidine ion, cesium ion and rubidium ion; the B-site cations are selected from one or more of lead ions, tin ions and germanium ions; the anion at the X position is selected from one or more of iodide ions, bromide ions and chloride ions; the saidThe stabilizing cross-linking agent is selected from 4-bromobenzyl iodized amine;
and S5, sequentially forming a hole transport layer and an electrode layer on the perovskite layer in the S4 to obtain the perovskite solar car film.
2. The method for producing a perovskite solar car film according to claim 1, wherein in S1, the material of the flexible substrate is one or more selected from polyethylene terephthalate, polyimide and polyethylene naphthalate; the elastic material is selected from polyurethane and/or polydimethylsiloxane.
3. The method for producing a perovskite solar car film according to claim 1, wherein in S1, the thickness of the flexible substrate is 50 μm to 125 μm.
4. The method for producing a perovskite solar car film according to claim 1, wherein in S1, the width of the wire groove is 20 μm to 50 μm and the depth is smaller than the thickness of the flexible substrate.
5. The method of claim 1, wherein in S2 the conductive material is selected from indium tin oxide and/or fluorine doped SnO 2 。
6. The method for producing a perovskite solar car film according to claim 1, wherein in S3, the electron transport material is selected from the group consisting of TiO 2 、SnO 2 、ZnO、C 60 PCBM, ICBA or CPTA; the thickness of the electron transport layer is 20nm-30nm.
7. The method for producing a perovskite solar car film according to claim 1, wherein in S4, the concentration of perovskite material in the perovskite precursor solution is 0.8mol/L to 1.2mol/L, and the concentration of the stabilizing cross-linking agent is 5mol/L to 20mol/L.
8. The method of claim 1, wherein in S5, the hole transport layer is selected from CuI, cuSCN, niO x One or more of PSS, spiro-MeOTAD, PTAA and P3 HT; the thickness of the hole transport layer is 40nm-50nm.
9. The method for producing a perovskite solar car film according to claim 1, wherein in S5, the material of the electrode layer is selected from gold, silver or aluminum; the thickness of the electrode layer is 80nm-100nm.
10. A perovskite solar car film prepared by the method of any one of claims 1-9.
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