CN113725370A - TiO in solar cell2Passivation method for electron transport layer - Google Patents
TiO in solar cell2Passivation method for electron transport layer Download PDFInfo
- Publication number
- CN113725370A CN113725370A CN202110951538.0A CN202110951538A CN113725370A CN 113725370 A CN113725370 A CN 113725370A CN 202110951538 A CN202110951538 A CN 202110951538A CN 113725370 A CN113725370 A CN 113725370A
- Authority
- CN
- China
- Prior art keywords
- tio
- electron transport
- transport layer
- pbx
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000002161 passivation Methods 0.000 claims abstract description 93
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000010408 film Substances 0.000 claims abstract description 62
- 239000010409 thin film Substances 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- -1 aromatic mercapto Chemical class 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 10
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000001235 sensitizing effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 68
- 239000008151 electrolyte solution Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 18
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 7
- 238000005215 recombination Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 200
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- 229910001887 tin oxide Inorganic materials 0.000 description 12
- 239000000075 oxide glass Substances 0.000 description 11
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000006872 improvement Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005118 spray pyrolysis Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- LZEPVVDVBJUKSG-UHFFFAOYSA-N pterocarpan Chemical compound C1=CC=C2C3COC4=CC=CC=C4C3OC2=C1 LZEPVVDVBJUKSG-UHFFFAOYSA-N 0.000 description 2
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017435 S2 In Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- 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
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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
-
- 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
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses TiO in a solar cell2An electronic transmission layer passivation method belongs to the technical field of solar cells and solves the problem of TiO in the existing solar cell2The passivation layer on the surface of the electron transport layer is easy to be corroded/dissolved rapidly and has poor passivation effect. TiO in the solar cell2The passivation method of the electron transport layer comprises the following steps: in an environment with constant negative pressure and temperature not exceeding 25 ℃, TiO is subjected to a one-step solution method2Preparing PbX on the surface of the electron transport layer2Thin film and by completely covering the TiO2PbX on surface of electron transport layer2The film forms a passivation layer for TiO in the solar cell2And passivating the electron transport layer, wherein X = any one of Cl, Br and I. The TiO in the solar cell provided by the invention2Passivation of electron transport layerChemical method, not only capable of generating photo-generated electrons and I3‑The reverse recombination of ions can effectively block, and the corrosion/dissolution speed of the electrolyte solution to the passivation layer can be reduced, thereby realizing the long-term and high-efficiency operation of the dye-sensitized solar cell.
Description
Technical Field
The embodiment of the application relates to the technical field of solar cells, in particular to TiO in a solar cell2An electron transport layer passivation method.
Background
TiO in the process of generating photocurrent of the dye-sensitized solar cell2Electrons transported in the electron transport layer may be bound to TiO2I in the pores of the electron transport layer3 -The ions are recombined to reduce the photoelectric conversion efficiency, so that it is necessary to block photoelectrons from I3 -And (4) reverse recombination of ions.
At present, TiO is generally passivated by passivating2Electron transport layer to block photoelectrons from I3 -Ion reverse recombination, i.e. in TiO adsorbed dye molecules2Preparing a passivation layer on the surface of the electron transport layer to block the electrolyte solution and the dye molecule-adsorbed TiO with the passivation layer2Direct contact of the electron transport layer. The method for preparing the passivation layer mainly comprises the following steps: 1) atomic Layer Deposition (ALD), e.g., Nazeerudin et Al, using Al (CH)3)3And H2O as a precursor in TiO2Al with the thickness of 1-5nm is deposited on the surface of the film2O3The method has the problems of complex process and high cost, so that the industrial application of the method is limited; 2) single-layer self-assembly (SAM), e.g. Snaith et al, uses a benzoic acid containing a carboxyl group and a benzene ring in its chemical structure as an intermediate, using the carboxyl group and TiO2And benzene ring with C60Compatibility, by the dip process of C60In TiO2The monolayer of the surface is spontaneously assembled, but the monolayer self-assembly method is only suitable for the assembly of organic molecules, and the organic matter is aged and coated by TiO2The problem of catalytic degradation; 3) step-by-Step Ionic Layer Adsorption Reaction (SILAR), e.g. Yong et al first TiO2Soaking the film in CdSO4Physical loading of Zn in solution2+Then, adding TiO2Soaking the film in Na2S·9H2O solution to make Cd2+And S2-In TiO2The reaction on the surface of the film obtains CdS precipitation with the thickness of a few nanometers, but because of Zn2+In TiO2The surface loading capacity completely depends on the random distribution in the soaking process, so that a uniform and full-coverage passivation layer is not easy to realize; 4) one-step solution methods, e.g. Wang Li dynaze et al CsCO3Dropwise addition of an aqueous solution to TiO2After the film is coated, spin coating and natural drying are carried out, and the CsCO can be prepared3Film coated TiO2An electron transport layer. However, since CsCO3The supersaturation degree of the solution is low and the nucleation quantity is small, so that a large amount of solute grows to the surrounding open space by taking crystal nucleus as the center in the drying process, and an incomplete covering microstructure with over-accumulated local solute is easily formed, thereby reducing the influence on TiO2The passivation effect of the electron transport layer greatly limits the photoelectric conversion efficiency of the solar cell, and the electrolyte solution has CsCO (carbon monoxide to carbon dioxide) reaction3The corrosion/dissolution speed of the film is high, and the passivation effect is obviously reduced along with the prolonging of time, so that the output performance of the solar cell is unstable.
Disclosure of Invention
The embodiment of the application aims at providing TiO in a solar cell2The passivation method of the electron transport layer solves the problem of TiO in the prior solar cell2The passivation layer on the surface of the electron transport layer is easy to be corroded/dissolved rapidly and has poor passivation effect.
In order to achieve the above purpose, the technical solution of the embodiment of the present application is:
the embodiment of the application provides TiO in a solar cell2An electron transport layer passivation method comprising:
in an environment with constant negative pressure and temperature not exceeding 25 ℃, TiO is subjected to a one-step solution method2Preparing PbX on the surface of the electron transport layer2Thin film and by completely covering the TiO2The PbX on the surface of the electron transport layer2The film forms a passivation layer for TiO in the solar cell2And passivating the electron transport layer, wherein X = any one of Cl, Br and I.
As a further modification of the embodiments of the present applicationFurther, the TiO mentioned2The electron transport layer is sensitized.
As a further improvement to the examples of this application, the TiO is2The sensitizing treatment of the electron transport layer comprises the following steps:
dissolving a dye sensitizer in an ethanol solvent to prepare a dye sensitizer solution;
adding TiO into the mixture2Keeping the temperature of the electron transport layer at 80 ℃ for 1 hour, putting the electron transport layer into the dye sensitizer solution, soaking the electron transport layer in the dark for 12 hours, taking out the electron transport layer, washing the electron transport layer with ethanol, and drying the electron transport layer with nitrogen to obtain sensitized TiO2An electron transport layer.
As a further improvement in the examples of this application, in TiO2The surface of the electron transport layer is prepared into PbX by a one-step solution method2The film includes:
mixing PbX2Dissolving in N, N-dimethylformamide solvent to obtain PbX2Precursor solution;
to the TiO2The surface of the electron transport layer is coated with PbX in a spin mode2Drying the precursor solution in a constant negative pressure environment at a temperature not higher than 25 ℃ to obtain PbX with a completely covered surface2TiO of thin film2An electron transport layer.
As a further improvement of the embodiments of the present application, the PbX is2The thickness of the film is not more than 10 nm.
As a further improvement of the embodiment of the application, the pressure value of the constant negative pressure environment is less than 1.01 multiplied by 105Pa。
As a further improvement of the embodiment of the present application, the pressure value of the constant negative pressure environment is 3000 Pa.
As a further improvement of the embodiments of the present application, the PbX is2The surface of the film is also loaded with the aromatic mercapto acid.
As a further improvement of the examples of the present application, the PbX is2The surface loading of the film with the mercapto aromatic acid comprises:
dissolving sulfhydryl aromatic acid in a dichloromethane solvent to prepare a sulfhydryl aromatic acid solution;
completely covering the surface with PbX2TiO of thin film2The electron transport layer is put into the sulfhydryl aromatic acid solution to be soaked for 1 hour, taken out, washed by ethanol and dried to obtain PbX with the surface loaded with sulfhydryl aromatic acid2A thin film passivation layer.
As a further refinement of an embodiment herein, the mercaptoaromatic acid is mercaptobenzoic acid.
Compared with the prior art, the advantages or beneficial effects of the embodiments of the present application at least include:
TiO in solar cell provided by embodiment of the application2The passivation method of electron transport layer is to use one-step solution method in TiO at constant negative pressure and temperature not higher than 25 deg.C2Preparing PbX on the surface of the electron transport layer2Thin film and by completely covering the TiO2The PbX on the surface of the electron transport layer2The film forms a passivation layer, thereby realizing the purpose of TiO etching2Passivation of the electron transport layer. Specifically, PbX2During the crystallization process of the precursor, the volatilization amount and nucleation amount of the solvent in unit time can be controlled due to the constant negative pressure and the environment with the temperature not exceeding 25 ℃, so that the precursor can be crystallized on TiO2The surface of the electron transport layer forms uniformly-piled PbX2A thin film passivation layer of raised TiO2The passivation effect of the electron transport layer realizes the effect of photo-generated electrons and I3 -Effective blocking of ion reverse recombination, and PbX2The film passivation layer is not easy to generate chemical reaction in the electrolyte solution, and the PbX reaction of the electrolyte solution is obviously reduced2The corrosion/dissolution speed of the film passivation layer ensures PbX2Passivation layer of film on TiO2The surface of the electron transmission layer can be covered for a long time, and the long-term and high-efficiency operation of the dye-sensitized solar cell is realized. Simultaneously adopts a one-step solution method to prepare TiO2Preparation of PbX on surface of electron transport layer2The thin film passivation layer has the advantages of low cost and easy operation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings used in the description of the embodiments will be briefly introduced below. It is obvious that the drawings in the following description are only some of the embodiments described in the present application, and that other drawings can be derived from these drawings by a person skilled in the art without inventive effort.
FIG. 1 is a schematic structural view of a low pressure pumping apparatus according to an embodiment of the present disclosure;
FIG. 2 is a surface-coated PbI layer provided in the examples of the present application2TiO of thin film passivation layer2Scanning electron micrographs of the electron transport layer;
FIG. 3 is a surface-coated PbI layer provided in the examples of the present application2TiO of thin film passivation layer2A partial transmission electron micrograph of the electron transport layer;
FIG. 4 shows an example of a surface-coated PbI layer2Single TiO of thin film passivation layer2Transmission electron micrographs of the particles;
FIG. 5 is a spectrum representation of Pb element at A in FIG. 2;
FIG. 6 is a graph of the spectral characterization of element I at A in FIG. 2;
fig. 7 is a graph showing a photovoltaic output characteristic of a dye-sensitized cell provided in an example of the present application;
fig. 8 is a graph of the change of the conversion efficiency of the solar cell with time according to the embodiment of the present application.
Reference numerals: 1-preparing a chamber; 2-a low pressure chamber; 3-a vacuum pump; 4-a voltage stabilizer; 5-air pumping controller.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. It should be apparent that the embodiments described below are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Aiming at solving the problem of TiO in the current solar cell2The passivation layer on the surface of the electron transport layer is easy to be corroded/dissolved rapidly and has poor passivation effect, and the embodiment provides a TiO in solar cell2An electron transport layer passivation method.
It will be understood by those skilled in the art that the TiO described in the examples of this application2The electron transport layer refers to TiO in the solar cell2A porous membrane.
TiO in the solar cell2An electron transport layer passivation method comprising:
in an environment with constant negative pressure and temperature not exceeding 25 ℃, TiO is subjected to a one-step solution method2Preparing PbX on the surface of the electron transport layer2Thin film and by completely covering the TiO2The PbX on the surface of the electron transport layer2The film forms a passivation layer for TiO in the solar cell2And passivating the electron transport layer, wherein X = any one of Cl, Br and I.
TiO in the solar cell provided by the embodiment2The passivation method of electron transport layer is to use one-step solution method in TiO at constant negative pressure and temperature not higher than 25 deg.C2Preparing PbX on the surface of the electron transport layer2Thin film and by completely covering the TiO2The PbX on the surface of the electron transport layer2The film forms a passivation layer, thereby realizing the control of TiO2Passivation of the electron transport layer. Specifically, PbX2During the crystallization of the precursor, the temperature is far lower than that of PbX2The boiling point of the solvent of the precursor solution is obviously inhibited, and the volatilization of the solvent at the temperature is obviously inhibited, so that PbX can be prevented2Crystallization is advanced, and the solvent can be prevented from volatilizing rapidly and crystallizing too rapidly, thereby ensuring PbX2The nucleation is uniformly accumulated, and simultaneously, the drying in a constant negative pressure environment can control the nucleation quantity to be the same as the growth time of the crystal nucleus, thereby ensuring that PbX2Uniformly deposited as a film on the TiO2The surface of the electron transport layer forms uniformly-piled PbX2A thin film passivation layer not only improving the TiO content2The passivation effect of the electron transport layer realizes the effect of photo-generated electrons and I3 -Effective blocking of ion reverse recombination, and PbX2The film passivation layer is not easy to generate chemical reaction in the electrolyte solution, and the PbX reaction of the electrolyte solution is obviously reduced2Corrosion/dissolution rate of the film, ensuring PbX2Passivation layer of film on TiO2The surface of the electron transport layer is long-term and stableThe dye-sensitized solar cell can be completely covered in a definite manner, and the long-term high-efficiency operation of the dye-sensitized solar cell is realized. Simultaneously adopts a one-step solution method to prepare TiO2Preparation of PbX on surface of electron transport layer2The thin film passivation layer has the advantages of low cost and easy operation.
In this example, TiO2The electron transport layer is sensitized by a dye sensitizer, which is beneficial to improving TiO2Efficiency of generation of photo-generated electrons in the electron transport layer. In particular, TiO2The electron transport layer has good photochemical stability, but its wide band gap limits the light absorption efficiency, so this example utilizes a dye sensitizer to sensitize TiO2The electron transport layer can broaden its spectral response range, thereby improving TiO2Efficiency of generation of photo-generated electrons in the electron transport layer.
It will be understood by those skilled in the art that dye sensitizers are generally classified into inorganic dye sensitizers and organic dye sensitizers, wherein the inorganic dye sensitizers mainly include ruthenium polypyridines carboxylate, ruthenium polypyridines phosphonate, ruthenium polypyridines polynuclear, other ruthenium complexes, other metal complexes, and the like; the organic dye sensitizer mainly comprises coumarin, merocyanine, porphyrin, polymethine, carotenoid, perylene, cyanine, hemicyanine, pterocarpan pigment, chlorophyll and derivatives thereof. Therefore, the present embodiment can utilize, but is not limited to, the above listed dye sensitizers, and those skilled in the art can select the dye sensitizer according to actual needs, and the present embodiment prefers N719 dye as the sensitizer.
In this example, PbX2The thickness of the film is not more than 10nm, and the blocking of photoelectrons and I can be realized3 -The ions are reversely compounded while the pair TiO is reduced2The effect of photo-generated electron transport efficiency in the electron transport layer. However, it will be appreciated by those skilled in the art that the photogenerated electrons and I are to be realized3 -Effective blocking of reverse recombination of ions, PbX2The thickness of the film should be greater than 0 nm.
In this example, for TiO2The sensitizing treatment of the electron transport layer comprises the following steps:
dissolving a dye sensitizer in an ethanol solvent, and fully stirring to prepare an ethanol solution of the dye sensitizer;
adding TiO into the mixture2Keeping the temperature of the electron transport layer at 80 ℃ for 1 hour, putting the electron transport layer into the dye sensitizer solution, soaking the electron transport layer in the dark for 12 hours, taking out the electron transport layer, washing the electron transport layer with ethanol, and drying the electron transport layer with nitrogen to obtain sensitized TiO2An electron transport layer.
In this example, in TiO2The surface of the electron transport layer is prepared into PbX by a one-step solution method2The film includes:
mixing PbX2Dissolving the powder in N, N-dimethylformamide solvent, stirring, and making into PbX2Precursor solution;
to TiO 22Surface spin coating of electron transport layer with PbX2Drying the precursor solution in a constant negative pressure environment at a temperature not higher than 25 ℃ to obtain PbX2Film-completely coated TiO2An electron transport layer.
This example provides a solution to TiO2Preparing PbX on the surface of the electron transport layer2Film, by using N, N-dimethylformamide as solvent to prepare PbX2Precursor solution, and mixing PbX2The precursor solution is coated on TiO in a spinning way2After the surface of the electron transport layer is coated, drying is carried out in a constant negative pressure environment at a temperature not exceeding 25 ℃. Since the temperature is much lower than the boiling point of N, N-dimethylformamide and volatilization of N, N-dimethylformamide at this temperature is significantly suppressed, PbX2The precursor solution can prevent PbX in the crystallization process2Crystallization is advanced, and the over-rapid crystallization caused by the rapid volatilization of the N, N-dimethylformamide can be prevented, thereby ensuring the PbX2Uniformly nucleating, and simultaneously drying in a constant negative pressure environment can control the nucleating quantity to be constant and the crystal nucleus growth time to be the same, thereby forming uniformly-stacked PbX2A thin film passivation layer not only improving the TiO content2The passivation effect of the electron transport layer realizes the effect of photo-generated electrons and I3 -Effective blocking of ion reverse recombination, and PbX2The film passivation layer is not easy to generate chemical reaction in the electrolyte solution, and the PbX reaction of the electrolyte solution is obviously reduced2Etching/dissolution of thin film passivation layerSpeed of PbX, so that PbX2Passivation layer of film on TiO2The surface of the electron transmission layer can be completely covered stably for a long time, and the long-term and high-efficiency operation of the dye-sensitized solar cell is realized. Simultaneously adopts a one-step solution method to prepare TiO2Preparing PbX on the surface of the electron transport layer2The thin film passivation layer has the advantages of low cost and easy operation.
It should be noted that the constant negative pressure environment in this embodiment may be provided by a low pressure air extraction device. As shown in fig. 1, the low pressure gas exhaust apparatus comprises: the device comprises a preparation chamber 1, a low-pressure chamber 2, a vacuum pump 3, a pressure stabilizing device 4 and an air pumping controller 5. The preparation chamber 1 is connected with the low-pressure chamber through an air pumping controller 5; the low-pressure chamber 2 is respectively connected with a vacuum pump 3 and a pressure stabilizing device 4; the air pumping controller 5 comprises a flow regulating valve, a controller and a pressure sensor, wherein the pressure sensor detects the pressure in the preparation chamber 1 and transmits a signal to the controller, and the controller controls the opening degree of the flow regulating valve according to the received signal; one end of the flow regulating valve is connected with the preparation chamber 1, and the other end is connected with the low-pressure chamber 2. The working principle is as follows: after constant negative pressure is formed in the low-pressure chamber 2 through the vacuum pump 3 and the pressure stabilizing device 4, the preparation chamber 1 is communicated with the low-pressure chamber 2, and the pressure difference between the preparation chamber 1 and the low-pressure chamber 2 is regulated and controlled through the coaction of the flow regulating valve, the controller and the pressure sensor, so that the volatilization speed of a solvent in a boundary layer of the liquid film is accurately regulated and controlled, and mass and heat transfer behaviors, a temperature field, a concentration field and nucleation growth behaviors in the liquid film are regulated and controlled. Of course, this embodiment can also be performed in other constant negative pressure environments, and any device capable of providing a constant negative pressure environment may be used.
Based on the low pressure pumping device, the embodiment is TiO2Preparing PbX on the surface of the electron transport layer2In the process of film forming, firstly, the low-pressure chamber 2 is vacuumized by the vacuum pump 3 to reduce the pressure, and then PbX is added2Spin coating precursor solution to sensitized TiO2The surface of the electron transport layer is covered with PbX2TiO of precursor solution2The electron transport layer is transferred into the low-pressure chamber 2, and the preparation chamber 1 and the low-pressure chamber are controlled by a flow regulating valve, a controller and a pressure sensorDifferential pressure of chamber 2 to cause PbX2N, N-dimethylformamide in the precursor solution is separated out in a differential pressure flow mode, and PbX is separated out2Then cured in situ on the TiO2Surface of the electron transport layer to form a uniform and complete coverage of PbX2And (3) film microstructure.
In this embodiment, the pressure value of the constant negative pressure environment is less than 1.01 × 105Pa, is in favor of PbX2The N, N-dimethylformamide in the precursor solution is separated out in a differential pressure flow mode. In particular, for PbX2The N, N-dimethylformamide solvent in the precursor solution is separated in a differential pressure flowing mode, a certain pressure difference is required between the pressure value of the constant negative pressure environment and the normal atmospheric pressure, but the PbX can be influenced due to the overlarge pressure difference2In-situ curing effect, which is not favorable for forming uniform and full-coverage PbX2The pressure value of the membrane and the constant negative pressure environment can improve the performance requirement of the equipment and increase the cost. A large number of experiments prove that: PbX is applied under a constant negative pressure condition at a pressure value of 3000Pa2The in-situ curing effect is better, so the pressure value under the constant negative pressure condition is preferably 3000Pa in the embodiment.
In this example, PbX2The surface of the film is also loaded with sulfhydryl aromatic acid to lead PbX to be2The passivation time of the film is longer. Specifically, although PbX2The chemical reaction of the film in the electrolyte solution is slow, but the electrolyte solution can still corrode/dissolve PbX2Film, affecting the persistence of the passivation effect, therefore this example is on TiO2Preparing PbX on the surface of the electron transport layer2After the thin film is passivated, strong coordination of lead element and mercapto functional group is utilized to perform the reaction on PbX2The surface of the film is loaded with sulfhydryl aromatic acid, so that the sulfhydryl aromatic acid can prevent the electrolyte solution from acting on PbX2Corrosion/dissolution of the thin film passivation layer and simultaneously can ensure the wettability of the electrolyte solution and the photoanode.
It is to be noted that mercapto group (-SH) in mercapto aromatic acid and PbX2Pb in2+Has strong coordination effect, and can make the mercapto aromatic acid be uniformly adsorbed on PbX2On a film, the same asThe carboxyl (-COOH) in the sulfhydryl aromatic acid has strong hydrophilicity and can enhance the wettability of the electrolyte solution and the photoanode. Therefore, this embodiment is implemented by adding PbX2The film is loaded with the sulfhydryl aromatic acid, which can not only reduce the PbX pair of the electrolyte solution2Corrosion/dissolution of the thin film passivation layer, and the wettability of the electrolyte solution and the photo-anode are enhanced, so that long-term and efficient photo-conversion of the dye-sensitized solar cell is realized. However, in order to prevent introduction of a polyfunctional group from affecting electron transport efficiency, the mercapto aromatic acid is preferably mercaptobenzoic acid.
This example provides a method for preparing a PbX2A method for loading a mercapto aromatic acid on the surface of a film, comprising:
dissolving sulfhydryl aromatic acid in a dichloromethane solvent, and uniformly stirring to prepare a dichloromethane solution of sulfhydryl aromatic acid;
completely covering the surface with PbX2TiO of thin film2The electron transmission layer is put into the sulfhydryl aromatic acid solution to be soaked for 1 hour, taken out, washed by ethanol and dried, and the PbX can be prepared2The surface of the film is uniformly loaded with the mercapto aromatic acid.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
Example 1 provides a TiO2The surface of the electron transport layer is covered with PbI2Thin film passivation layer and PbI2The solar cell with the surface of the thin film passivation layer absorbing mercaptobenzoic acid comprises:
s101-preparation of sensitized TiO2Electron transport layer
S1011: 1.5g of TiO was taken2(P25) powder and 378.75mL of distilled water, and mixing the TiO powder with the water2Grinding the powder in an agate mortar to obtain uniform fine powder, adding the fine powder into distilled water, and uniformly stirring to obtain a suspension; after the suspension was subjected to ultrasonic dispersion treatment, it was stirred uniformly and concentrated to TiO 11.65mL in volume using a rotary evaporator2And (5) sealing and storing the slurry.
S1012: a piece of fluorine-doped tin oxide glass is taken and dried, and then a 3M adhesive tape with the standard thickness of 50 mu M is used for coating the fluorine-doped tin oxide glassMaking a square with an effective area of 1.0cm × 1.0cm on the surface, and cutting TiO with a blade2The slurry was knife-coated on the upper surface of fluorine-doped tin oxide glass to obtain TiO 10 μm thick2Drying the film naturally, and drying the dried TiO2The film is put into a muffle furnace with the heating rate of 15 ℃/min, calcined for 30 to 50 minutes at the temperature of 450 ℃, cooled to the room temperature along with the furnace, and the TiO is obtained2An electron transport layer.
S1013: dissolving an N719 dye sensitizer with the concentration of 0.3mmol/mL in an ethanol solvent, and fully stirring to prepare an ethanol solution of the N719 dye sensitizer; adding TiO into the mixture2Keeping the temperature of the electron transport layer at 80 ℃ for 1 hour, then putting the electron transport layer into an ethanol solution of N719 dye sensitizer, soaking the electron transport layer for 12 hours in a dark place, taking the electron transport layer out, washing the electron transport layer with ethanol, and blowing the electron transport layer by strong nitrogen flow to obtain sensitized TiO2An electron transport layer;
s102-in sensitized TiO2Surface preparation of electron transport layer PbI2Thin film passivation layer
S1021: will PbI2Dissolving the powder in N, N-dimethylformamide solvent, stirring, and making into PbI with concentration of 0.5M2Precursor solution;
s1022: a low-pressure air extractor is used for providing a constant negative pressure environment, and the pressure in the low-pressure chamber 2 is adjusted to 3000Pa for standby through a vacuum pump 3 and a pressure stabilizing device 4; PbI is filtered by a filter head with the aperture of 40 mu m2Dropwise adding the precursor solution to the sensitized TiO2Spin coating the surface of the electron transport layer for 10s at 4000 rpm, and removing excessive PbI2Precursor solution, control of PbI2Precursor solution in TiO2Depositing the surface of the electron transport layer, and spin-coating PbI2Sensitization of TiO precursor solution2Transferring the electron transport layer into the preparation chamber 1, and under the condition of controlling the ambient temperature not to exceed 25 ℃, rapidly separating out the N, N-dimethylformamide in a differential pressure flow mode within a time less than 5s by adjusting the flow regulating valve, the controller and the pressure sensor, wherein PbI2Then cured in situ on the TiO2The surface of the electron transport layer forms a complete covering of PbI2A thin film passivation layer.
S103-in PbI2The surface of the film passivation layer adsorbs mercaptobenzoic acid
S1031: dissolving mercaptobenzoic acid in a dichloromethane solvent, and uniformly stirring to prepare a 0.001mol/L mercaptobenzoic acid dichloromethane solution;
s1032: covering the surface with PbI2TiO of thin film passivation layer2The electron transmission layer is put into a dichloromethane solution of mercaptobenzoic acid for soaking for 1 hour, and is taken out, washed by ethanol and dried to obtain the PbI with the surface covered2Thin film passivation layer and PbI2TiO of film passivation layer surface absorbing mercaptobenzoic acid2An electron transport layer. Wherein, in order to prevent dichloromethane from volatilizing, the sealing property of the system is required to be kept in the soaking treatment process.
S104-assembled battery
And (3) adding S1041: the method comprises the steps of preparing chloroplatinic acid and isopropanol into electrode solution according to a certain proportion, spraying the electrode solution onto fluorine-doped tin oxide glass (FTO) with holes by utilizing a spray pyrolysis method, then putting the FTO into a muffle furnace, preserving heat for 30 minutes at the temperature of 380 ℃, and then cooling along with the furnace to prepare the platinum electrode.
And step S1042: platinum electrode and surface coating PbI2Thin film passivation layer and PbI2TiO of film passivation layer surface absorbing mercaptobenzoic acid2The electron transmission layer is bonded together through a heat sealing film and fixed into a sandwich structure through a hot press to obtain a packaged solar cell, and then an electrolyte solution is introduced into the packaged solar cell through a hole in the back of the counter electrode by using a capillary tube to obtain TiO2The surface of the electron transport layer is covered with PbI2Thin film passivation layer and PbI2The surface of the film passivation layer adsorbs mercaptobenzoic acid. Wherein the electrolyte solution comprises LiI with the concentration of 0.5mol/L and I with the concentration of 0.05mol/L2And 0.3mol/L of 4-tert-butylpyridine.
Example 2
Example 2 provides a TiO2The surface of the electron transport layer is covered with PbI2A solar cell with a thin film passivation layer, comprising:
s201-preparation of sensitized TiO2Electron transport layer
S2011: 1.5g of TiO was taken2(P25) powder and 378.75mL of distilled water, and mixing the TiO powder with the water2Grinding the powder in an agate mortar to obtain uniform fine powder, adding the fine powder into distilled water, and uniformly stirring to obtain a suspension; after subjecting the suspension to ultrasonic dispersion treatment, it was stirred well and concentrated to TiO 11.65mL in volume using a rotary evaporator2And (5) sealing and storing the slurry.
S2012: air-drying a piece of fluorine-doped tin oxide glass, manufacturing a square with an effective area of 1.0cm multiplied by 1.0cm on the upper surface of the fluorine-doped tin oxide glass by using a 3M adhesive tape with a standard thickness of 50 mu M, and then cutting TiO by using a blade2The slurry was knife-coated on the upper surface of fluorine-doped tin oxide glass to obtain TiO 10 μm thick2Drying the film naturally, and drying the dried TiO2The film is put into a muffle furnace with the heating rate of 15 ℃/min, calcined for 30 to 50 minutes at the temperature of 450 ℃, and cooled to the room temperature along with the furnace to obtain TiO2An electron transport layer.
S2013: dissolving an N719 dye sensitizer with the concentration of 0.3mmol/mL in an ethanol solvent, and fully stirring to prepare an ethanol solution of the N719 dye sensitizer; adding TiO into the mixture2The electron transport layer is insulated for 1 hour at the temperature of 80 ℃, then is put into an ethanol solution of N719 dye sensitizer to be soaked for 12 hours in a dark place, is washed by ethanol after being taken out, and is dried by strong nitrogen airflow to obtain the sensitized TiO2An electron transport layer;
s202-in sensitized TiO2Surface preparation of electron transport layer PbI2Thin film passivation layer
S2021: will PbI2Dissolving the powder in N, N-dimethylformamide solvent, stirring, and making into PbI with concentration of 0.5M2Precursor solution;
s2022: a low-pressure air extractor is used for providing a constant negative pressure environment, and the pressure in the low-pressure chamber 2 is adjusted to 3000Pa for standby through a vacuum pump 3 and a pressure stabilizing device 4; PbI is filtered by a filter head with the aperture of 40 mu m2Dropwise adding the precursor solution to the sensitized TiO2Spin coating the surface of the electron transport layer for 10s at 4000 rpm, and removing excessive PbI2Precursor solution, control of PbI2Precursor solution in TiO2Deposition on the electron transport layer and spin-coating with PbI2Sensitization of TiO precursor solution2Transferring the electron transport layer into the preparation chamber 1, and rapidly separating out the N, N-dimethylformamide in a differential pressure flow manner by adjusting the flow regulating valve, the controller and the pressure sensor under the condition that the temperature does not exceed 25 ℃ within a period of less than 5s, wherein PbI2Then cured in situ on the TiO2The surface of the electron transport layer forms a complete covering of PbI2A thin film passivation layer.
S203-assembled Battery
And (3) mixing S2031: the method comprises the steps of preparing chloroplatinic acid and isopropanol into electrode solution according to a certain proportion, spraying the electrode solution onto fluorine-doped tin oxide glass (FTO) with holes by utilizing a spray pyrolysis method, then putting the FTO into a muffle furnace, preserving heat for 30 minutes at the temperature of 380 ℃, and then cooling along with the furnace to prepare the platinum electrode.
And (3) mixing S2032: platinum electrode and surface coating PbI2TiO of thin film passivation layer2The electron transmission layer is bonded together through a heat sealing film and fixed into a sandwich structure through a hot press to obtain a packaged solar cell, and then an electrolyte solution is introduced into the packaged solar cell through a hole in the back of the counter electrode by using a capillary tube to obtain TiO2The surface of the electron transport layer is covered with PbI2A solar cell with a thin film passivation layer. Wherein the electrolyte solution consists of LiI with the concentration of 0.5mol/L, I2 with the concentration of 0.05mol/L and 4-tert-butylpyridine with the concentration of 0.3 mol/L.
Example 3
Example 3 provides an unpassivated TiO2A solar cell of an electron transport layer, comprising:
s301-preparation of sensitized TiO2Electron transport layer
S3011: 1.5g of TiO was taken2(P25) powder and 378.75mL of distilled water, and mixing the TiO powder with the water2Grinding the powder in an agate mortar to obtain uniform fine powder, adding the fine powder into distilled water, and uniformly stirring to obtain a suspension; after subjecting the suspension to ultrasonic dispersion treatment, it was stirred well and concentrated to TiO 11.65mL in volume using a rotary evaporator2And (5) sealing and storing the slurry.
S3012: air-drying a piece of fluorine-doped tin oxide glass, manufacturing a square with an effective area of 1.0cm multiplied by 1.0cm on the upper surface of the fluorine-doped tin oxide glass by using a 3M adhesive tape with a standard thickness of 50 mu M, and then cutting TiO by using a blade2The slurry was knife-coated on the upper surface of fluorine-doped tin oxide glass to obtain TiO 10 μm thick2Drying the film naturally, and drying the dried TiO2The film is put into a muffle furnace with the heating rate of 15 ℃/min, calcined for 30 to 50 minutes at the temperature of 450 ℃, and cooled to the room temperature along with the furnace to obtain TiO2An electron transport layer.
S3013: dissolving N719 dye with the concentration of 0.3mmol/mL in ethanol solvent and fully stirring to prepare ethanol solution of the N719 dye sensitizer; adding TiO into the mixture2Keeping the temperature of the electron transport layer at 80 ℃ for 1 hour, then putting the electron transport layer into an ethanol solution of N719 dye sensitizer for dark soaking for 12 hours, taking out the electron transport layer, washing the electron transport layer with ethanol, and blowing the electron transport layer with strong nitrogen flow to obtain sensitized TiO2An electron transport layer;
s302-assembled battery
And (2) mixing S3021: the method comprises the steps of preparing chloroplatinic acid and isopropanol into electrode solution according to a certain proportion, spraying the electrode solution onto fluorine-doped tin oxide glass (FTO) with holes by utilizing a spray pyrolysis method, then putting the FTO into a muffle furnace, preserving heat for 30 minutes at the temperature of 380 ℃, and then cooling along with the furnace to prepare the platinum electrode.
And (2) mixing S3022: platinum electrode and sensitized TiO2The electron transport layer is bonded together through a heat sealing film and fixed into a sandwich structure through a hot press to obtain a packaged solar cell, and then an electrolyte solution is introduced into the packaged solar cell through a hole on the back of the counter electrode by using a capillary tube to obtain unpassivated TiO2And a solar cell of an electron transport layer. Wherein the electrolyte solution comprises LiI with the concentration of 0.5mol/L and I with the concentration of 0.05mol/L2And 0.3mol/L of 4-tert-butylpyridine.
The inventors covered the surface of the PbI prepared in example 1 with2TiO of thin film passivation layer2The electron transport layer was subjected to electron microscopy characterization, and the results are shown in FIGS. 2-4. Wherein, FIG. 2 shows surface covering PbI2TiO of thin film passivation layer2Scanning of electron transport layersAn electron microscope image; FIG. 3 shows surface covering of PbI2TiO of thin film passivation layer2A partial transmission electron micrograph of the electron transport layer; FIG. 4 shows surface covering of PbI2Single TiO of thin film passivation layer2Transmission electron micrograph of the particles. Meanwhile, the spectrum characterization is performed at a in fig. 2, and the results are shown in fig. 5-6. Wherein, FIG. 5 is a spectrum representation diagram of Pb element at A; FIG. 6 is a graph showing the spectral characterization of the I element at A.
As can be seen from FIGS. 5 and 6, in TiO2The surface of the electron transport layer collects the signals of Pb element and I element, which shows that TiO element2The surface of the electron transport layer is provided with PbI2The presence of a thin film passivation layer.
As can be seen from FIG. 3, TiO2TiO in electron transport layer2The particles are in a tightly packed structure, but due to the low magnification, each TiO is not recognized2PbI with complete coverage of particle surface2A thin film passivation layer.
The individual TiO can be clearly seen in FIG. 42The surface of the particles is coated with a layer of homogeneous PbI with a thickness of about 3nm2A thin film passivation layer.
From the above, it can be seen that the present embodiment utilizes a one-step solution method under a constant negative pressure and a temperature not exceeding 25 ℃ to produce TiO2The surface of the electron transport layer is prepared to be completely covered with TiO2PbI of electron transport layer2A thin film passivation layer.
To prove the beneficial effects of this example, the solar cells prepared in examples 1 to 3 were tested and verified in the stability test of output performance, which is as follows:
the solar cell analyzer is adopted to simulate standard sunlight (AM1.5100mW.cm)-2) The output performance of the solar cells prepared in examples 1 to 3 was measured, and the measured output performance of the solar cells was counted in days, and the results thereof are shown in fig. 7 and 8. Fig. 7 is a graph showing a photovoltaic output characteristic of a solar cell; fig. 8 is a graph showing the change in conversion efficiency of a solar cell with time.
As can be seen from FIG. 7, example 1 and implementationThe photovoltaic conversion efficiency of the solar cell prepared in example 2 is obviously improved compared with that of example 3, which shows that the solar cell prepared in the example is prepared by a one-step solution method under the conditions of constant negative pressure and temperature not exceeding 25 ℃ in TiO2PbI prepared on surface of electron transport layer2The thin film passivation layer has good passivation effect and the surface adsorbs the PbI of the sulfhydryl aromatic acid2The passivation effect of the thin film passivation layer is better.
As can be seen from fig. 8, the photovoltaic conversion efficiency of the solar cells prepared in examples 1 and 2 is significantly improved compared to that of example 3 in a half-month testing period, which indicates that the present example adopts a one-step solution method under the conditions of constant negative pressure and temperature not exceeding 25 ℃ in TiO2PbI prepared on surface of electron transport layer2The thin film passivation layer can delay the performance attenuation of the solar cell and adsorb the PbI of the sulfhydryl aromatic acid2The thin film passivation layer can further retard the performance degradation of the solar cell. Therefore, this example uses a one-step solution method on TiO at a constant negative pressure and a temperature not exceeding 25 ℃2PbI prepared on surface of electron transport layer2The thin film passivation layer can reduce the corrosion/dissolution of the electrolyte solution, so that PbI2Passivation layer of film on TiO2The surface of the electron transmission layer can be completely covered stably for a long time, and the long-term high-efficiency operation of the dye-sensitized solar cell is realized.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. TiO in solar cell2The passivation method of the electron transport layer is characterized by comprising the following steps:
in an environment with constant negative pressure and temperature not exceeding 25 ℃, TiO is subjected to a one-step solution method2Preparing PbX on the surface of the electron transport layer2Thin film and by completely covering the TiO2The PbX on the surface of the electron transport layer2The film forms a passivation layer for TiO in the solar cell2And passivating the electron transport layer, wherein X = any one of Cl, Br and I.
2. The in-solar-cell TiO of claim 12Method for passivating an electron transport layer, characterized in that the TiO is2The electron transport layer is sensitized.
3. The in-solar-cell TiO of claim 22A method for passivating the electron transport layer, characterized in that the TiO is passivated2The sensitizing treatment of the electron transport layer comprises the following steps:
dissolving a dye sensitizer in an ethanol solvent to prepare a dye sensitizer solution;
adding TiO into the mixture2Keeping the temperature of the electron transport layer at 80 ℃ for 1 hour, putting the electron transport layer into the dye sensitizer solution, soaking the electron transport layer in the dark for 12 hours, taking out the electron transport layer, washing the electron transport layer with ethanol, and drying the electron transport layer with nitrogen to obtain sensitized TiO2An electron transport layer.
4. The in-solar-cell TiO of claim 12The method for passivating the electron transport layer is characterized in that the electron transport layer is formed on TiO2The surface of the electron transport layer is prepared into PbX by a one-step solution method2The film includes:
mixing PbX2Dissolving in N, N-dimethylformamide solvent to obtain PbX2Precursor solution;
to the TiO2The surface of the electron transport layer is coated with PbX in a spin mode2Drying the precursor solution in a constant negative pressure environment at a temperature not higher than 25 ℃ to obtain PbX with a completely covered surface2TiO of thin film2An electron transport layer.
5. The TiO of the solar cell of claim 42Method for passivating an electron transport layer, characterized in that said PbX is2The thickness of the film is not more than 10 nm.
6. The TiO of the solar cell of claim 42The passivation method of the electron transport layer is characterized in that the pressure value of the constant negative pressure environment is less than 1.01 multiplied by 105Pa。
7. The TiO of the solar cell of claim 62The passivation method of the electron transport layer is characterized in that the pressure value of the constant negative pressure environment is 3000 Pa.
8. The TiO of the solar cell of claim 42Method for passivating an electron transport layer, characterized in that said PbX is2The surface of the film is also loaded with the aromatic mercapto acid.
9. The in-solar-cell TiO of claim 82A method for passivating an electron transport layer, characterized in that said PbX is passivated2The surface loading of the film with the mercapto aromatic acid comprises:
dissolving sulfhydryl aromatic acid in a dichloromethane solvent to prepare a sulfhydryl aromatic acid solution;
completely covering the surface with PbX2TiO of thin film2The electron transport layer is put into the sulfhydryl aromatic acid solution to be soaked for 1 hour, taken out, washed by ethanol and dried to obtain PbX with the surface loaded with sulfhydryl aromatic acid2A film.
10. The solar cell according to claim 8 or 9, wherein the TiO is selected from the group consisting of2The passivation method of the electron transport layer is characterized in that the mercapto aromatic acid is mercapto benzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110951538.0A CN113725370A (en) | 2021-08-19 | 2021-08-19 | TiO in solar cell2Passivation method for electron transport layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110951538.0A CN113725370A (en) | 2021-08-19 | 2021-08-19 | TiO in solar cell2Passivation method for electron transport layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113725370A true CN113725370A (en) | 2021-11-30 |
Family
ID=78676866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110951538.0A Pending CN113725370A (en) | 2021-08-19 | 2021-08-19 | TiO in solar cell2Passivation method for electron transport layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113725370A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104538551A (en) * | 2014-12-26 | 2015-04-22 | 西安电子科技大学 | Plane perovskite solar cell based on FTO/c-TiO2 cathode and manufacturing method of plane perovskite solar cell |
| CN111640871A (en) * | 2020-06-16 | 2020-09-08 | 西南石油大学 | Perovskite solar cell capable of inhibiting photodecomposition of passivation layer and preparation method |
| CN111834487A (en) * | 2020-07-24 | 2020-10-27 | 西安电子科技大学 | All-inorganic perovskite nanowire self-powered-short wave photoelectric detector and preparation method thereof |
| CN112002812A (en) * | 2020-09-15 | 2020-11-27 | 常州大学 | Method for preparing perovskite solar cell absorption layer based on stepwise thermal evaporation and preparation of perovskite solar cell |
| CN112397650A (en) * | 2020-11-16 | 2021-02-23 | 中国科学院半导体研究所 | Perovskite solar cell PN junction and preparation method thereof |
-
2021
- 2021-08-19 CN CN202110951538.0A patent/CN113725370A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104538551A (en) * | 2014-12-26 | 2015-04-22 | 西安电子科技大学 | Plane perovskite solar cell based on FTO/c-TiO2 cathode and manufacturing method of plane perovskite solar cell |
| CN111640871A (en) * | 2020-06-16 | 2020-09-08 | 西南石油大学 | Perovskite solar cell capable of inhibiting photodecomposition of passivation layer and preparation method |
| CN111834487A (en) * | 2020-07-24 | 2020-10-27 | 西安电子科技大学 | All-inorganic perovskite nanowire self-powered-short wave photoelectric detector and preparation method thereof |
| CN112002812A (en) * | 2020-09-15 | 2020-11-27 | 常州大学 | Method for preparing perovskite solar cell absorption layer based on stepwise thermal evaporation and preparation of perovskite solar cell |
| CN112397650A (en) * | 2020-11-16 | 2021-02-23 | 中国科学院半导体研究所 | Perovskite solar cell PN junction and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 肖黎: ""钙钛矿太阳电池关键材料研究"", 《CNKI博士学位论文全文库》, pages 4 - 5 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Improved performance of quantum dot-sensitized solar cells adopting a highly efficient cobalt sulfide/nickel sulfide composite thin film counter electrode | |
| CN109980092B (en) | Perovskite quantum dot solar cell and preparation method thereof | |
| Song et al. | ZnO/PbS core/shell nanorod arrays as efficient counter electrode for quantum dot-sensitized solar cells | |
| Xu et al. | Preparation and photovoltaic properties of perovskite solar cell based on ZnO nanorod arrays | |
| Thulasi-Varma et al. | Enhanced photovoltaic performance and morphological control of the PbS counter electrode grown on functionalized self-assembled nanocrystals for quantum-dot sensitized solar cells via cost-effective chemical bath deposition | |
| CN107275487B (en) | A kind of perovskite solar battery of efficient stable and preparation method thereof | |
| CN102290248B (en) | Method for preparing efficient compound light anode of dye sensitized solar cell | |
| Kim et al. | Cost-effective and morphology controllable PVP based highly efficient CuS counter electrodes for high-efficiency quantum dot-sensitized solar cells | |
| CN111944161B (en) | Eu-MOFs interface modification layer in perovskite solar cell | |
| CN111755254B (en) | Photoanode based on silver-indium-sulfur quantum dot sensitization, photoelectrochemical cell and preparation method | |
| CN102157265B (en) | Preparation method of composite electrode of dye sensitized solar cell | |
| CN110534652B (en) | Perovskite solar cell and preparation method thereof | |
| Nien et al. | Investigation of Dye-Sensitized Solar Cell With Photoanode Modified by TiO₂-ZnO Nanofibers | |
| CN101022136A (en) | Alkaline-earth metal salt decorative nano crystal semiconductor optical anode, producing method and application thereof | |
| Kim et al. | Sequential dip-spin coating method: fully infiltration of MAPbI3-xClx into mesoporous TiO2 for stable hybrid perovskite solar cells | |
| Lan et al. | Improvement of Photovoltaic Performance of Dye-Sensitized Solar Cell by Post Heat Treatment of Polymer-Capped Nano-Platinum Counterelectrode | |
| CN113097392B (en) | Grain boundary passivation method of perovskite solar cell | |
| CN106531445A (en) | Preparation method for porous carbon material electrode for counter electrode of dye-sensitized solar cell | |
| CN109994610A (en) | A kind of bi-component intermixing formula electron transfer layer and its preparation method and application | |
| CN113725370A (en) | TiO in solar cell2Passivation method for electron transport layer | |
| CN110176542B (en) | Organic-inorganic composite hole transport film for perovskite battery and preparation method thereof | |
| Bahadur et al. | Highly efficient nanocrystalline ZnO thin films prepared by a novel method and their application in dye-sensitized solar cells | |
| CN111710781A (en) | Perovskite photovoltaic cell and preparation method thereof | |
| CN109448998B (en) | Counter electrode of dye-sensitized solar cell and preparation method thereof | |
| CN108832004B (en) | Interface modification method for eliminating hysteresis phenomenon of perovskite battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |