CN108807693A - A kind of perovskite solar cell and preparation method thereof of low cost high stability - Google Patents
A kind of perovskite solar cell and preparation method thereof of low cost high stability Download PDFInfo
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- CN108807693A CN108807693A CN201810566438.4A CN201810566438A CN108807693A CN 108807693 A CN108807693 A CN 108807693A CN 201810566438 A CN201810566438 A CN 201810566438A CN 108807693 A CN108807693 A CN 108807693A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 157
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000010410 layer Substances 0.000 claims description 193
- 239000011521 glass Substances 0.000 claims description 91
- 238000004528 spin coating Methods 0.000 claims description 43
- 239000010408 film Substances 0.000 claims description 37
- 239000012528 membrane Substances 0.000 claims description 35
- 238000001816 cooling Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- 230000008595 infiltration Effects 0.000 claims description 6
- 238000001764 infiltration Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000006748 scratching Methods 0.000 claims description 6
- 230000002393 scratching effect Effects 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 239000002346 layers by function Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000011149 active material Substances 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 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 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 238000005260 corrosion Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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- 229910003472 fullerene Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- -1 methyl lead halide Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- 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
- H10K30/81—Electrodes
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- 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
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention provides a kind of perovskite solar cell and preparation method thereof of inexpensive high stability.The battery includes successively from the bottom to top：Conducting base, TiO2Compacted zone, TiO2Mesoporous layer, ZrO2Mesoporous layer, perovskite active layer and conductive carbon electrode layer.The present invention has abandoned expensive hole transmission layer and noble metal electrode from classical perovskite solar battery structure, and has selected cheap hydrophobicity carbon electrode.With Br‑The mixing perovskite CH of doping3NH3Pb(I1‑xBrx)3It is successively prepared using simple whole soln method under the conditions of natural air for active material, perovskite material permeates TiO2And ZrO2Double mesoporous layers, and its surface is covered, conductive carbon paste is finally scratched, low-temperature setting obtains solar cell device.The battery of the present invention has low cost, high power conversion efficiency and stability is strong and cheap preparation method.
Description
Technical field
The present invention relates to technical field of solar batteries, and in particular to a kind of low cost, high power conversion efficiency and stabilization
The strong perovskite solar cell of property and its cheap preparation method.
Background technology
Energy crisis and environmental problem force people to start constantly to seek renewable and environmentally friendly new energy.Wherein too
The use of positive energy more meets the requirement of energy source type.The system of solar cell is concentrated on to the technology of solar energy efficiently used
It makes, wherein perovskite solar cell is the hot spot studied at present.It is applied to film too for the first time from perovskite material in 2009
Sun energy battery (J.Am.Chem.Soc.2009,131：6050-6051), since obtaining 3.8% power-conversion efficiencies, with
The fast development of perovskite solar cell has document report power-conversion efficiencies and has reached 22.1% up to now
(Science, 2017,356：1376-1379).But expensive 2,2 ' are used in classical perovskite solar battery structure,
7,7 '-four [N, N- bis- (4- methoxyphenyls) amino] -9,9 '-spiral shell, two fluorenes (Spiro-MeOTAD) base hole transmission layer and your gold
Belong to (gold or silver) electrode, and prepares and test in the glove box of high-purity.Manufacturing cost is very high, against corrosion under field conditions (factors)
Property difference and decay it is especially fast the shortcomings of limit its actual application prospect.
It is most of to use methyl lead halide (CH in the preparation of perovskite solar cell3NH3PbX3, X=halogens) and
Its mixed halide crystalline material is active layer, and since it is with high extinction coefficient, outstanding bipolarity charge migration is small
Exciton binding energy and band gap are adjustable.In order to improve the performance of perovskite solar cell, based on mesoporous supporting structure device,
Device architecture is simplified, introduces new functional layer and replace some functional layer etc. research, is improved in certain degree
The performance of perovskite solar cell.Such as：Chinese patent application CN105449104A discloses a kind of in air environment neutrality
The perovskite solar cell and preparation method thereof that can stablize, disclosure of which be perovskite sensitizing layer and hole transmission layer it
Between introduce hydrophobic interfaces layer；Although the patent application improves the aerial stability of perovskite solar cell, but also
It is to have used hole transmission layer and metal layer, device cost is relatively high.Chinese patent application CN107154460A discloses one kind
Complete carbon-based perovskite solar cell and its preparation process, disclosure of which are fullerene or derivatives thereof as electron-transport
Layer, and use carbon electrode；But the price of fullerene in the patent application or derivatives thereof is more expensive, limits its industry
Metaplasia is produced.Chinese patent application CN105140402A discloses a kind of calcium of no hole transmission layer and admires mine solar cell and its system
Preparation Method, disclosure of which are spin coating or vapor deposition on compact titanium dioxide layer after vertical-growth layer of titanium dioxide nanotube
Calcium titanium ore bed, then evaporation metal electrode；But admires in calcium in the patent application and one layer of metal electrode is directly deposited on ore bed causes
Phenomena such as device power is low and manufacturing cost is high.Chinese patent application CN105870335A and CN105895804A disclose one
Kind of the simple calcium of preparation process is admired mine solar cell and preparation method thereof, and disclosure of which is to be prepared on FTO electro-conductive glass
Fine and close TiO2After layer, TiO2Slurry, Yb2O3Slurry (or ZrO2Slurry and NiO slurries) and C-material slurry, calcining prepares porous
It after membrane electrode, is put into glove box, perovskite precursor liquid, static heating perovskite solution infiltration is added dropwise, solvent volatilization obtains
Calcium is admired mine solar cell.But the patent application needs to complete in glove box in the part operation of preparation process, and two kinds
Device power transfer efficiency is relatively low, only up to reach 5.6% and 7.5%.
Accordingly, it is desirable to provide a kind of improved technology scheme insufficient for the above-mentioned prior art.
Invention content
It is an object of the invention to overcome the deficiencies in the prior art, it is proposed that it is a kind of low cost, high power conversion efficiency and
The perovskite solar cell of high stability and its under natural air atmospheric condition use cheap preparation method.System of the present invention
Standby perovskite solar cell has power conversion efficiency height, steady in a long-term under the conditions of natural air, and preparation process
Simple and cheap manufacturing cost advantage, can meet large-scale industrialization production requirements.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of perovskite solar cell of low cost high stability, the perovskite solar cell is from the bottom to top successively
Including：Conducting base, TiO2Compacted zone, TiO2Mesoporous layer, ZrO2Mesoporous layer, perovskite active layer and conductive carbon electrode layer.
Perovskite solar cell as described above, it is preferable that the perovskite active layer is the spin coating legal system using a step
Standby perovskite active layer, the perovskite active layer is by Br-The mixing perovskite CH of doping3NH3Pb(I1-xBrx)3Composition, wherein x is
Amount of substance score；Preferably, the mixing perovskite CH3NH3Pb(I1-xBrx)3In x be 0.05~0.35；More preferably, institute
It states the infiltration of perovskite active layer and is filled into TiO2Mesoporous layer and ZrO2In mesoporous layer, and cover ZrO2The surface of mesoporous layer.
Perovskite solar cell as described above, it is preferable that the conducting base is FTO electro-conductive glass；Preferably, described
TiO2The thickness of compacted zone is 10~60nm；The TiO2The thickness of mesoporous layer is 100~300nm；The ZrO2The thickness of mesoporous layer
Degree is 100~300nm；The thickness of the perovskite active layer is 300~700nm；The thickness of the conductive carbon electrode layer be 5~
30μm。
A kind of preparation method of any one of them perovskite solar cell as above, the preparation method include following step
Suddenly：
1) FTO electro-conductive glass/TiO2The preparation of compacted zone membrane electrode
The spin coating TiO in the non-etched portions of FTO electro-conductive glass2After colloidal sol, first preheated processing, then through TiCl4At solution
Reason, is then placed on warm table and calcines, and forms TiO2Compacted zone, to obtain FTO electro-conductive glass/TiO2Compacted zone membrane electrode；
2) FTO electro-conductive glass/TiO2Compacted zone/TiO2The preparation of mesoporous layer film electrode
In FTO electro-conductive glass/TiO prepared by step 1)2Spin coating TiO on compacted zone membrane electrode2Slurry after dry, is placed
In on warm table, after temperature programmed control is heated and is kept the temperature, natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2It is situated between
Aperture layer membrane electrode；
3) FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2The preparation of mesoporous layer film electrode
In FTO electro-conductive glass/TiO prepared by step 2)2Compacted zone/TiO2Mesoporous layer film electrode spin coating ZrO2Slurry is done
After dry, it is positioned on warm table, after temperature programmed control is heated and is kept the temperature, natural cooling, to obtain FTO electro-conductive glass/TiO2It causes
Close layer/TiO2Mesoporous layer/ZrO2Mesoporous layer film electrode；
4) FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2The preparation of mesoporous layer/perovskite thin film electrode
In FTO electro-conductive glass/TiO prepared by step 3)2Compacted zone/TiO2Mesoporous layer/ZrO2It is revolved on mesoporous layer film electrode
Apply perovskite CH3NH3Pb(I1-xBrx)3Precursor liquid is positioned on warm table, heats and keep the temperature crystallization, to obtain FTO conductions
Glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film electrode；
5) perovskite solar cell is obtained
In FTO electro-conductive glass/TiO prepared by step 4)2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film
After scratching conductive carbon paste on electrode, solidification prepares carbon electrode, to obtain stable perovskite solar cell.
Preparation method as described above, it is preferable that in the step 1), the spin coating in the non-etched portions of FTO electro-conductive glass
TiO2After colloidal sol, after 100-150 DEG C of the pre-heat treatment 5-20min, natural cooling；Again through TiCl4Solution treatment 10-40min, sets
In calcining 10-40min on warm table and at 450-550 DEG C, natural cooling forms TiO2Compacted zone, acquisition FTO electro-conductive glass/
TiO2Compacted zone electrode；Preferably, through TiCl4To use deionized water and washes of absolute alcohol, drying after solution treatment respectively again
It is placed on warm table and calcines again afterwards；More preferably, the spin coating TiO in the non-etched portions of FTO electro-conductive glass2Before colloidal sol, first
One section of high temperature gummed tape is pasted in one end of the non-etched portions of FTO electro-conductive glass or deposition protective film is protected, reserved and dispatch from foreign news agency
The electrode of road connection；Preferably, the length of the high temperature gummed tape of stickup or deposition protective film is 2-240mm.
Preparation method as described above, it is preferable that in the step 2), in FTO electro-conductive glass/TiO2Compacted zone membrane electrode
Upper spin coating TiO2Slurry is positioned over after dry on warm table, and temperature programmed control is heated to 450-550 DEG C, after keeping the temperature 10-30min,
Natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer film electrode.
Preparation method as described above, it is preferable that in the step 3), in FTO electro-conductive glass/TiO2Compacted zone/TiO2It is mesoporous
Layer film electrode spin coating ZrO2Slurry is positioned over after dry on warm table, and temperature programmed control is heated to 450-600 DEG C, keeps the temperature 10-
After 30min, natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer film electrode.
Preparation method as described above, it is preferable that in the step 4), in FTO electro-conductive glass/TiO prepared by step 3)2It causes
Close layer/TiO2Mesoporous layer/ZrO2Spin coating perovskite CH on mesoporous layer film electrode3NH3Pb(I1-xBrx)3Precursor liquid is positioned over and adds
In thermal station, it is heated to 80-110 DEG C, crystallization 10-50min is kept the temperature, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2It is mesoporous
Layer/ZrO2Mesoporous layer/perovskite thin film electrode；Preferably, the perovskite CH3NH3Pb(I1-xBrx)3Precursor liquid is with N, N- bis-
Methylformamide is solvent, CH3NH3I、PbI2And PbBr2Obtained by three kinds of solution mixing systems are standby；Preferably, the perovskite
CH3NH3Pb(I1-xBrx)3X is amount of substance score in precursor liquid, and x is 0.05~0.35.
Preparation method as described above, it is preferable that the preparation process of the perovskite solar cell is less than in humidity
It is carried out under the conditions of 50% natural air, each functional layer is successively prepared using whole soln method；Preferably, the step 5)
In, in FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Conductive carbon paste is scratched on mesoporous layer/perovskite thin film electrode
Afterwards, and at 80-120 DEG C cure 5-30min, carbon electrode is prepared, to obtain stable perovskite solar cell.
Preparation method as described above, it is preferable that the heating schedule of described program temperature control is：Under the conditions of moving air, with
5-20 DEG C/min rates heat, and when temperature reaches 280-360 DEG C, keep the temperature 5-20min, continuation is heated to 5-20 DEG C/min rates
450-550℃。
Compared with the immediate prior art, technical solution provided by the invention has the advantages that：
(1) perovskite solar cell provided by the invention has high power conversion efficiency and stability, and the side of preparation
Method is simply and the features such as of low cost.The power conversion efficiency of perovskite solar cell prepared by the present invention reach 8.34% with
On.
(2) perovskite solar cell is prepared using whole solution process, preparation process is complete in natural air atmosphere
At not needing glove box, and do not need other special safeguard measures.
(3) do not include expensive hole mobile material and metal electrode in perovskite solar cell prepared by the present invention,
Manufacturing cost can be greatly lowered.
(4) technical solution provided by the invention selects carbon electrode instead of metal when preparing perovskite solar cell
Electrode.Carbon electrode has hydrophobicity, when perovskite solar cell works under field conditions (factors), improves device corrosion stability, makes it
Long-term stable operation.
Description of the drawings
Fig. 1 is that the calcium of high stability that the specific embodiment of the invention provides is admired mine solar battery structure figure；
Fig. 2 is the J-V indicatrix test charts of the perovskite solar cell prepared by embodiment 1 in the present invention；
Fig. 3 is that the photovoltaic parameter of the perovskite solar cell prepared by embodiment 1 in the present invention changes over time figure.
In figure：1, glass；2, FTO layers；3,TiO2Compacted zone；4,TiO2Mesoporous layer；5,ZrO2Mesoporous layer；6, perovskite is lived
Property layer；7, carbon electrode layer.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
The every other embodiment that logical technical staff is obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention can be combined with each other.
As shown in Figure 1 to Figure 3, the specific embodiment of the invention provides a kind of perovskite solar-electricity of inexpensive high stability
Pond, perovskite solar cell includes successively from the bottom to top：Conducting base, TiO2Compacted zone 3, TiO2Mesoporous layer 4, ZrO2It is mesoporous
Layer 5, perovskite active layer 6 and conductive carbon electrode layer 7.
Perovskite active layer in the present invention is to prepare perovskite active layer using the spin-coating method of a step, perovskite activity
Layer 6 is by Br-The mixing perovskite CH of doping3NH3Pb(I1-xBrx)3Composition, wherein x are amount of substance score.Preferably, calcium mixture titanium
Mine CH3NH3Pb(I1-xBrx)3In x be 0.05~0.35 (such as 0.06,0.08,0.1,0.12,0.14,0.16,0.18,
0.2、0.22、0.24、0.26、0.28、0.30、0.31、0.33、0.34)。
In the present invention, the infiltration of perovskite active layer 6 is filled into TiO2Mesoporous layer 4 and ZrO2In mesoporous layer 5, and cover
ZrO2The surface of mesoporous layer 5.
In the present invention, conducting base is FTO electro-conductive glass (being specifically to be made of glass 1 and FTO layers 2)；Preferably,
TiO2The thickness of compacted zone 3 be 10~60nm (such as 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm,
30nm,35nm,40nm,45nm,50nm,52nm,58nm)；TiO2The thickness of mesoporous layer 4 be 100~300nm (such as 120nm,
140nm,160nm,180nm,200nm,220nm,240nm,260nm,280nm,290nm)；ZrO2The thickness of mesoporous layer 5 is 100
~300nm (such as 110nm, 130nm, 150nm, 170nm, 180nm, 200nm, 240nm, 260nm, 280nm, 290nm)；Calcium titanium
The thickness of mine active layer 6 be 300~700nm (such as 330nm, 350m, 370nm, 400nm, 420nm, 450nm, 470nm,
500nm,530nm,550nm,570nm,590nm,600nm,650nm,690nm)；The thickness of conductive carbon electrode layer 7 is 5~30 μm
(such as 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 29 μm).
In addition, the present invention also provides a kind of preparation method of perovskite solar cell, which includes as follows
Step：
1) FTO electro-conductive glass/TiO2The preparation of compacted zone membrane electrode
The spin coating TiO in the non-etched portions of FTO electro-conductive glass2After colloidal sol, first preheated processing, then through TiCl4At solution
Reason, is then placed on warm table and calcines, and forms TiO2Compacted zone, to obtain FTO electro-conductive glass/TiO2Compacted zone membrane electrode.
In this step 1), the spin coating TiO in the non-etched portions of FTO electro-conductive glass2After colloidal sol, through 100-150 DEG C of (example
Such as 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 148 DEG C, 149 DEG C) the pre-heat treatment
5-20min (such as 7min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min,
After 19min), natural cooling；Again through TiCl4Solution treatment 10-40min (such as 12min, 14min, 16min, 18min,
20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 39min), it is placed in warm table
It is upper and 450-550 DEG C (such as 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C, 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 535 DEG C, 540
DEG C, 545 DEG C) calcining 10-40min (such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min,
28min, 30min, 32min, 34min, 36min, 38min, 39min), natural cooling forms TiO2Compacted zone obtains FTO and leads
Electric glass/TiO2Compacted zone electrode.
It is further preferred that through TiCl4To use deionized water and washes of absolute alcohol, drying after solution treatment respectively again
It is placed on warm table and calcines again afterwards.
It is further preferred that the spin coating TiO in the non-etched portions of FTO electro-conductive glass2Before colloidal sol, first clean
One end of the non-etched portions of FTO electro-conductive glass pastes one section of high temperature gummed tape or deposition protective film is protected, reserved and external circuit
The electrode of connection；Preferably, the high temperature gummed tape of stickup or deposit the length of protective film, width be respectively 1-5mm (such as 1.3mm,
1.5mm、1.8mm、2mm、2.3mm、2.5mm、2.7mm、3mm、3.3mm、3.5mm、3.7mm、4mm、4.3mm、4.5mm、
4.7mm, 4.9mm) and 2-240mm (such as 2mm, 4mm, 8mm, 10mm, 50mm, 70mm, 100mm, 120mm, 140mm, 160mm,
180mm、200mm、220mm、230mm、235mm、239mm)。
2) FTO electro-conductive glass/TiO2Compacted zone/TiO2The preparation of mesoporous layer film electrode
In FTO electro-conductive glass/TiO prepared by step 1)2Spin coating TiO on compacted zone membrane electrode2Slurry after dry, is placed
In on warm table, temperature programmed control be heated to 450-550 DEG C (such as 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C, 500 DEG C, 510 DEG C,
520 DEG C, 530 DEG C, 535 DEG C, 540 DEG C, 545 DEG C), heat preservation 10-30min (such as 12min, 14min, 16min, 18min,
20min, 22min, 24min, 26min, 28min, 29min) after, natural cooling, to obtain FTO electro-conductive glass/TiO2It is fine and close
Layer/TiO2Mesoporous layer film electrode.
3) FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2The preparation of mesoporous layer film electrode
In FTO electro-conductive glass/TiO prepared by step 2)2Compacted zone/TiO2Mesoporous layer film electrode spin coating ZrO2Slurry is done
After dry, be positioned on warm table, temperature programmed control be heated to 450-600 DEG C (such as 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C, 500
℃、510℃、520℃、530℃、535℃、540℃、545℃、550℃、560℃、570℃、575℃、580℃、585℃、
590 DEG C, 595 DEG C), heat preservation 10-30min (such as 12min, 14min, 16min, 18min, 20min, 22min, 24min,
26min, 28min, 29min) after, natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2It is situated between
Aperture layer membrane electrode.
4) FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2The preparation of mesoporous layer/perovskite thin film electrode
In FTO electro-conductive glass/TiO prepared by step 3)2Compacted zone/TiO2Mesoporous layer/ZrO2It is revolved on mesoporous layer film electrode
Apply perovskite CH3NH3Pb(I1-xBrx)3Precursor liquid is positioned on warm table, be heated to 80-110 DEG C (such as 82 DEG C, 84 DEG C, 86
DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C, 98 DEG C, 100 DEG C, 102 DEG C, 104 DEG C, 105 DEG C, 106 DEG C, 108 DEG C, 109 DEG C),
Keep the temperature crystallization 10-50min (such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min,
29min, 30min, 32min, 34min, 36min, 38min, 40min, 42min, 44min, 46min, 48min, 49min), to
Obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film electrode.
It is further preferred that perovskite CH3NH3Pb(I1-xBrx)3Precursor liquid be using n,N-Dimethylformamide as solvent,
CH3NH3I、PbI2And PbBr2Obtained by three kinds of solution mixing systems are standby.Preferably, perovskite CH3NH3Pb(I1-xBrx)3In precursor liquid
X be amount of substance score, x be 0.05~0.35 (such as 0.055,0.07,0.09,0.11,0.13,0.15,0.17,0.19,
0.21、0.23、0.25、0.27、0.29、0.30、0.32、0.33、0.35、0.45)。
5) perovskite solar cell is obtained
In FTO electro-conductive glass/TiO prepared by step 4)2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film
On electrode scratch conductive carbon paste after, and 80-120 DEG C (such as 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 96
℃、98℃、100℃、102℃、104℃、105℃、106℃、108℃、109℃、110℃、112℃、114℃、116℃、117
DEG C, 118 DEG C, 119 DEG C) solidification 5-30min (such as 7min, 9min, 10min, 11min, 12min, 13min, 14min, 15min,
16min, 17min, 18min, 19min, 20min, 21min, 22min, 24min, 26min, 27min, 28min, 29min), it prepares
Carbon electrode, to obtain stable perovskite solar cell.
In the present invention, the non-etched portions of FTO electro-conductive glass specifically refer to the conductive layer (FTO one piece of electro-conductive glass
Layer) one is etched away, the part of etching is non-conductive；What is do not etched is partially electronically conductive, spin coating preparation light anode on the part；If
If not etching, galvanic anode and cathode can not detach, and direct short-circuit causes final battery idle.
In the present invention, TiO2Colloidal sol：Grain size is less than the TiO of 100nm2In a liquid, the intuitive observation of naked eyes is transparent for dispersion
Liquid, concentration is relatively low, wherein TiO2It is unformed.
TiO2Slurry：Average grain diameter is that 20nm mix with the ethyl cellulose certain ratio of 2 kinds of viscositys, with note product alcohol with
The suspension of absolute ethyl alcohol in the mixed solvent dispersion, the intuitive observation of naked eyes is emulsion, opaque, higher concentration, wherein
TiO2It is Detitanium-ore-type TiO2Crystal and rutile TiO2Crystal composition, Detitanium-ore-type TiO2Crystalline content 75%.In this hair
In bright, the preparation process of perovskite solar cell is the completion carried out under the conditions of humidity is less than 50% natural air, no
Glove box is needed, other special safeguard measures are not needed.Each functional layer is successively prepared using whole soln method.Whole soln method
It specifically refers to：It is entirely solwution method operation (spin coating or blade coating etc.) successively to prepare plural layers and obtain the process of battery.In this hair
In bright, the infiltration of perovskite active layer is filled into TiO2Mesoporous layer and ZrO2In mesoporous layer, and cover ZrO2The surface of mesoporous layer is specific
Operation is prepared using spin-coating method：TiO2Mesoporous layer and ZrO2It is about 55% that mesoporous layer, which has certain gap, porosity,；When
When its surface is added dropwise in above-mentioned perovskite precursor liquid, perovskite precursor liquid is penetrated into automatically in the gap of mesoporous layer, and when rotation is more
Remaining solution, which is got rid of, to be removed, and by the volatilization of solvent, perovskite material material crystallizes on the gap and surface of mesoporous layer and forms calcium titanium
Mine active layer.
In the present invention, perovskite solar cell process is being prepared, rotation speed when spin coating slurry, colloidal sol or precursor liquid
Rate be 3000-4000rpm (such as 3100rpm, 3150rpm, 3200rpm, 3250rpm, 3300rpm, 3350rpm, 3400rpm,
3450rpm、3500rpm、3550rpm、3600rpm、3650rpm、3700rpm、3750rpm、3800rpm、3850rpm、
3900rpm, 3950rpm), spin-coating time be 10-30s (such as 12s, 14s, 16s, 18s, 20s, 22s, 23s, 25s, 26s,
27s、28s、29s)。
In the step 2) and step 3) of the preparation method of the perovskite solar cell of the present invention, the heating of temperature programmed control
Program is：Under the conditions of moving air, with 5-20 DEG C/min (6 DEG C/min, 8 DEG C/min, 10 DEG C/min, 11 DEG C/min, 12 DEG C/
Min, 13 DEG C/min, 14 DEG C/min, 15 DEG C/min, 16 DEG C/min, 17 DEG C/min, 18 DEG C/min, 19 DEG C/min) rate heating,
Temperature reach 280-360 DEG C (such as 285 DEG C, 290 DEG C, 295 DEG C, 300 DEG C, 305 DEG C, 310 DEG C, 315 DEG C, 320 DEG C, 325 DEG C,
330 DEG C, 335 DEG C, 340 DEG C, 345 DEG C, 350 DEG C, 355 DEG C) when, heat preservation 5-20min (such as 7min, 9min, 10min, 11min,
12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min), continue with 5-20 DEG C/min (6 DEG C/min, 8
℃/min、10℃/min、11℃/min、12℃/min、13℃/min、14℃/min、15℃/min、16℃/min、17℃/
Min, 18 DEG C/min, 19 DEG C/min) rate be heated to 450-550 DEG C (such as 460 DEG C, 465 DEG C, 470 DEG C, 475 DEG C, 480 DEG C,
485℃、490℃、495℃、500℃、510℃、515℃、520℃、530℃、540℃、545℃)。
Embodiment 1
Under the conditions of humidity is less than 50% natural air, the calcium of high stability is successively prepared using simple whole soln method
Titanium ore solar cell, is as follows：
(1) the FTO electro-conductive glass of 1 piece of partial etching is taken, (being formed see Fig. 1 glass 1 and the FTO not etched layers 2), cleaning,
It is (reserved to connect with external circuit that the high temperature gummed tape that one small width is 3mm is pasted after drying, in the non-etched portions of FTO electro-conductive glass
The electrode connect) protection after, spin coating TiO2Colloidal sol, in 130 DEG C of the pre-heat treatments, natural cooling, in TiCl470 DEG C of processing in aqueous solution
After 15min, deionized water and washes of absolute alcohol is used to be positioned on warm table after dry respectively, 500 DEG C of calcining 30min, from
It is so cooling, form TiO2Compacted zone obtains FTO electro-conductive glass/TiO2Compacted zone electrode.
(2) spin coating TiO on above-mentioned membrane electrode2Slurry, speed of rotation 3000rpm, spin-coating time 20s, 100 DEG C dry
It after dry 10min, is placed on warm table, 300 DEG C is being heated to 10 DEG C/min rates, after keeping the temperature 10min, with 10 DEG C/min speed
Rate is being heated to 500 DEG C, keeps the temperature 15min, and natural cooling forms TiO2Mesoporous layer obtains FTO electro-conductive glass/TiO2Compacted zone/
TiO2Mesoporous layer electrode.
(3) spin coating ZrO on above-mentioned membrane electrode2Slurry, speed of rotation 4000rpm, spin-coating time 20s, 100 DEG C dry
It after dry 10min, is placed on warm table, 300 DEG C is being heated to 10 DEG C/min rates, after keeping the temperature 10min, with 10 DEG C/min speed
Rate is being heated to 500 DEG C, keeps the temperature 15min, natural cooling, and natural cooling forms ZrO2Mesoporous layer, acquisition FTO electro-conductive glass/
TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer electrode.
(4) spin coating mixing perovskite CH on above-mentioned membrane electrode3NH3Pb(I1-xBrx)3Precursor liquid.CH3NH3Pb(I1-xBrx)3
Precursor liquid is the CH for solvent with n,N-Dimethylformamide (DMF)3NH3I、PbI2And PbBr2Certain ratio is pressed Deng solution in 3
It is mixed with, wherein amount of substance score x is 0.25.The speed of rotation is 3000rpm, and spin-coating time 20s is placed on warm table
On be heated to 90 DEG C, after heat preservation crystallization 30min, natural cooling forms mixing calcium titanium ore bed (see Fig. 1 mixing perovskites active layer 6
Infiltration is in TiO2Mesoporous layer 4 and ZrO2Mesoporous layer 5, and cover its surface), obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2It is situated between
Aperture layer/ZrO2Mesoporous layer/mixing perovskite membrane electrode.
(5) it after scratching conductive carbon paste on above-mentioned membrane electrode, is placed on warm table, is heated at 100 DEG C, heat preservation solidification
15min, natural cooling form carbon electrode layer, obtain stable perovskite solar cell.
By perovskite solar cell manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) the lower test J-V indicatrixes of irradiation, have rated photovoltaic parameter.J-V indicatrixes test result is with Fig. 2 tables
Show.The solar cell has measured short-circuit current density (Jsc) it is 20.93mA/cm2, open-circuit voltage (Vcc) it is 0.967V, filling
The factor (FF) is 0.49 and power conversion efficiency (PCE) is 9.92%.
Perovskite solar cell manufactured in the present embodiment is stored under field conditions (factors), no any encapsulation and protection are arranged
It applies, every 1 week, in AM1.5G standards sunlight (the intensity 100mW/cm of solar simulator2) the lower test J-V of irradiation
Indicatrix has rated photovoltaic parameter and changes over time relationship, and test result is indicated with Fig. 3.The result shows that the solar cell
It stores, is slowly improved with the extension open-circuit voltage of time under field conditions (factors)；Short-circuit current density slightly fluctuates, and reduces by one
A bit, but reduction amplitude is little.The extension at any time of fill factor and power conversion efficiency and be slowly increased, be the 3rd week when the time
When reach maximum value, then extend the time, decrease；Change less after spending the 6th week, tends towards stability.After 8 weeks, power turns
Efficiency has still maintained initial value 93% or more is changed, demonstrating the solar cell has very high stability.
Embodiment 2
Under the conditions of humidity is less than 50% natural air, the calcium titanium of high stable is successively prepared using simple whole soln method
Mine solar cell, is as follows：
(1)~(3) same operation of step (1)~(3) and embodiment 1 in the present embodiment, acquisition FTO electro-conductive glass/
TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer electrode.
(4) spin coating mixing perovskite CH on above-mentioned membrane electrode3NH3Pb(I1-xBrx)3Precursor liquid.CH3NH3Pb(I1-xBrx)3
Precursor liquid is DMF with the mixed solution for preparing of solvent, and wherein amount of substance score x is 0.30.The speed of rotation is 3000rpm, rotation
The painting time is 20s, is placed on warm table and is heated to 90 DEG C, and after keeping the temperature crystallization 30min, natural cooling forms mixing perovskite
Layer obtains FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/mixing perovskite membrane electrode.
(5) it after scratching conductive carbon paste on above-mentioned membrane electrode, is placed on warm table, is heated at 100 DEG C, heat preservation solidification
15min, natural cooling form carbon electrode layer, obtain stable perovskite solar cell.
By perovskite solar cell manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) the lower test J-V indicatrixes of irradiation, have rated photovoltaic parameter.It is close that the solar cell has measured short circuit current
Degree is 21.16mA/cm2, open-circuit voltage 942mV, fill factor 0.45 and power conversion efficiency are 8.97%.
Embodiment 3
Under the conditions of humidity is less than 50% natural air, the calcium titanium of high stable is successively prepared using simple whole soln method
Mine solar cell, is as follows：
(1)~(3) same operation of step (1)~(3) and embodiment 1 in the present embodiment, acquisition FTO electro-conductive glass/
TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer electrode.
(4) spin coating mixing perovskite CH on above-mentioned membrane electrode3NH3Pb(I1-xBrx)3Precursor liquid.CH3NH3Pb(I1-xBrx)3
Precursor liquid is DMF with the mixed solution for preparing of solvent, and wherein amount of substance score x is 0.20.The speed of rotation is 3000rpm, rotation
The painting time is 20s, is placed on warm table and is heated to 90 DEG C, and after keeping the temperature crystallization 30min, natural cooling forms mixing perovskite
Layer obtains FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/mixing perovskite membrane electrode.
(5) it after scratching conductive carbon paste on above-mentioned membrane electrode, is placed on warm table, is heated at 100 DEG C, heat preservation solidification
15min, natural cooling form carbon electrode layer, obtain stable perovskite solar cell.
In the AM1.5G standards sunlight of solar simulator, (intensity is perovskite solar cell manufactured in the present embodiment
100mW/cm2) the lower test J-V indicatrixes of irradiation, have rated photovoltaic parameter.The solar cell has measured short-circuit current density
For 19.75mA/cm2, open-circuit voltage 928mV, fill factor 0.47 and power conversion efficiency are 8.61%.
Embodiment 4
Under the conditions of humidity is less than 50% natural air, the calcium titanium of high stable is successively prepared using simple whole soln method
Mine solar cell, is as follows：
(1)~(3) same operation of step (1)~(3) and embodiment 1 in the present embodiment, acquisition FTO electro-conductive glass/
TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer electrode.
(4) spin coating mixing perovskite CH on above-mentioned membrane electrode3NH3Pb(I1-xBrx)3Precursor liquid.CH3NH3Pb(I1-xBrx)3
Precursor liquid is DMF with the mixed solution for preparing of solvent, and wherein amount of substance score x is 0.15.The speed of rotation is 3000rpm, rotation
The painting time is 20s, is placed on warm table and is heated to 90 DEG C, and after keeping the temperature crystallization 30min, natural cooling forms mixing perovskite
Layer obtains FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/mixing perovskite membrane electrode.
(5) it after scratching conductive carbon paste on above-mentioned membrane electrode, is placed on warm table, is heated at 100 DEG C, heat preservation solidification
15min, natural cooling form carbon electrode layer, obtain stable perovskite solar cell.
In the AM1.5G standards sunlight of solar simulator, (intensity is perovskite solar cell manufactured in the present embodiment
100mW/cm2) the lower test J-V indicatrixes of irradiation, have rated photovoltaic parameter.The solar cell has measured short-circuit current density
For 19.35mA/cm2, open-circuit voltage 937mV, fill factor 0.46 and power conversion efficiency are 8.34%.
Comparative example
Under the conditions of humidity is less than 50% natural air, the calcium titanium of high stable is successively prepared using simple whole soln method
Mine solar cell, is as follows：
(1)~(2) same operation of step (1)~(2) and embodiment 1 in the comparative example, acquisition FTO electro-conductive glass/
TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer electrode.
(3) spin coating mixing perovskite CH on above-mentioned membrane electrode3NH3Pb(I1-xBrx)3Precursor liquid.CH3NH3Pb(I1-xBrx)3
Precursor liquid is DMF with the mixed solution for preparing of solvent, and wherein amount of substance score x is 0.25.The speed of rotation is 3000rpm, rotation
The painting time is 20s, is placed on warm table and is heated to 90 DEG C, and after keeping the temperature crystallization 30min, natural cooling forms mixing perovskite
Layer obtains FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/mixing perovskite membrane electrode.
(4) chlorobenzene solution that Spiro-MeOTAD bases hole passes material is added dropwise on above-mentioned membrane electrode, the speed of rotation is
4000rpm, spin-coating time 20s obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/calcium mixture
Titanium ore/Spiro-MeOTAD membrane electrodes.
(6) above-mentioned membrane electrode is placed on plated film and floods in the slot of plate downward, and plated film floods the plating that plate is fixed on vacuum coating equipment
In membrane cavity, plated film chamber door is shut.It is evacuated to plated film intracavitary pressure and reaches 4 × 10-2Pa, opens heater switch, and heating evaporation is high
Purity silver, deposits 80-150nm thickness Ag films.Stop heating, pressure release opens plated film chamber door, takes perovskite thin film solar-electricity
Pond.
(intensity is perovskite solar cell prepared by the comparative example in the AM1.5G standards sunlight of solar simulator
100mW/cm2) the lower test J-V indicatrixes of irradiation, have rated photovoltaic parameter.The solar cell has measured short-circuit current density
For 21.49mA/cm2, open-circuit voltage 781mV, fill factor 0.55 and power conversion efficiency are 9.23%.But it should
Battery is especially unstable, is placed in natural air item for 24 hours, and power conversion efficiency is reduced to 7.31%, and attenuation amplitude is initial
20.8%；After 72h, power conversion efficiency is reduced to 3.06%, and attenuation amplitude is 66.8% initially；By 168h
After (one week), electric current is not measured substantially, and device is scrapped.
Solar cell device structure prepared by the comparative example is FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/
Mix perovskite/Spiro-MeOTAD/Ag/.Device includes hole transmission layer Spiro-MeOTAD and noble metal electrode Ag.Mesh
Before, Spiro-MeOTAD prices are somewhat expensive, and purity is 1 gram 1500 yuan of 99.9%, then doping and solvent etc., contains 1 gram
Spiro-MeOTAD solution prices reach 2200 yuan.The preparation of gold or silver electrode needs vacuum evaporation process, and condition is harsh, operates
It is complicated.The device preparation manipulation step that the comparative example is prepared is complicated, solar cell stability of high cost, and obtaining
Difference, conversion ratio are low, cannot be promoted use well.
To sum up, by comparative example 1-4 and comparative example it is found that present invention offer perovskite solar cell has
Low cost, high power conversion efficiency and stability is strong and cheap preparation method.The solar cell of the present invention includes FTO successively
Electro-conductive glass, TiO2Compacted zone, TiO2Mesoporous layer, ZrO2It is mesoporous layer by layer, perovskite active layer and carbon electrode.From classical calcium titanium
Expensive hole transmission layer and noble metal electrode have been abandoned in mine solar battery structure, and have selected cheap hydrophobicity
Carbon electrode.With Br-The mixing perovskite CH of doping3NH3Pb(I1-xBrx)3For active material, under the conditions of natural air, using letter
Single whole soln method is successively prepared, and perovskite material permeates TiO2And ZrO2Double mesoporous layers, and its surface is covered, final blade coating is led
Electrical carbon is starched, and low-temperature setting obtains solar cell device.Perovskite solar cell prepared by this method has power conversion effect
Rate is high, steady in a long-term under the conditions of natural air, and the advantage that preparation process is simple and manufacturing cost is cheap, can meet big
The industrialization production requirements of scale.
In conclusion the present invention also has the following technical effect that：
(1) perovskite solar cell provided by the invention has high power conversion efficiency and stability, and the side of preparation
Method is simply and the features such as of low cost.The power conversion efficiency of perovskite solar cell prepared by the present invention reach 8.34% with
On.
(2) perovskite solar cell is prepared using whole solution process, preparation process is complete in natural air atmosphere
At not needing glove box, and do not need other special safeguard measures.
(3) do not include expensive hole mobile material and metal electrode in perovskite solar cell prepared by the present invention,
Manufacturing cost can be greatly lowered.
(4) technical solution provided by the invention selects carbon electrode instead of metal when preparing perovskite solar cell
Electrode.Carbon electrode has hydrophobicity, when perovskite solar cell works under field conditions (factors), improves device corrosion stability, makes it
Long-term stable operation.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and principle within, any modification, equivalent replacement, improvement and so on, accompanying claims protection domain of the present invention it
It is interior.
Claims (10)
1. it is a kind of low cost high stability perovskite solar cell, which is characterized in that the perovskite solar cell by
Under supreme include successively：Conducting base, TiO2Compacted zone, TiO2Mesoporous layer, ZrO2Mesoporous layer, perovskite active layer and conductive carbon
Electrode layer.
2. perovskite solar cell as described in claim 1, which is characterized in that the perovskite active layer is to use a step
Spin-coating method prepare perovskite active layer, the perovskite active layer is by Br-The mixing perovskite CH of doping3NH3Pb(I1-xBrx)3Group
At wherein x is amount of substance score；
Preferably, the mixing perovskite CH3NH3Pb(I1-xBrx)3In x be 0.05~0.35；
More preferably, the perovskite active layer infiltration is filled into TiO2Mesoporous layer and ZrO2In mesoporous layer, and cover ZrO2It is mesoporous
The surface of layer.
3. perovskite solar cell as described in claim 1, which is characterized in that the conducting base is FTO electro-conductive glass；
Preferably, the TiO2The thickness of compacted zone is 10~60nm；
The TiO2The thickness of mesoporous layer is 100~300nm；
The ZrO2The thickness of mesoporous layer is 100~300nm；
The thickness of the perovskite active layer is 300~700nm；
The thickness of the conductive carbon electrode layer is 5~30 μm.
4. a kind of preparation method of perovskite solar cell as described in any one of claims 1-3, which is characterized in that described
Preparation method includes the following steps：
1) FTO electro-conductive glass/TiO2The preparation of compacted zone membrane electrode
The spin coating TiO in the non-etched portions of FTO electro-conductive glass2After colloidal sol, first preheated processing, then through TiCl4Solution treatment,
Then it is placed on warm table and calcines, form TiO2Compacted zone, to obtain FTO electro-conductive glass/TiO2Compacted zone membrane electrode；
2) FTO electro-conductive glass/TiO2Compacted zone/TiO2The preparation of mesoporous layer film electrode
In FTO electro-conductive glass/TiO prepared by step 1)2Spin coating TiO on compacted zone membrane electrode2Slurry after dry, be positioned over and add
In thermal station, after temperature programmed control is heated and is kept the temperature, natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer
Membrane electrode；
3) FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2The preparation of mesoporous layer film electrode
In FTO electro-conductive glass/TiO prepared by step 2)2Compacted zone/TiO2Mesoporous layer film electrode spin coating ZrO2Slurry, it is dry
Afterwards, it is positioned on warm table, after temperature programmed control is heated and is kept the temperature, natural cooling, to obtain FTO electro-conductive glass/TiO2It is fine and close
Layer/TiO2Mesoporous layer/ZrO2Mesoporous layer film electrode；
4) FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2The preparation of mesoporous layer/perovskite thin film electrode
In FTO electro-conductive glass/TiO prepared by step 3)2Compacted zone/TiO2Mesoporous layer/ZrO2Spin coating calcium on mesoporous layer film electrode
Titanium ore CH3NH3Pb(I1-xBrx)3Precursor liquid is positioned on warm table, heats and keep the temperature crystallization, to obtain FTO electro-conductive glass/
TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film electrode；
5) perovskite solar cell is obtained
In FTO electro-conductive glass/TiO prepared by step 4)2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film electrode
After upper blade coating conductive carbon paste, solidification prepares carbon electrode, to obtain stable perovskite solar cell.
5. preparation method as claimed in claim 4, which is characterized in that in the step 1), in not etching for FTO electro-conductive glass
Spin coating TiO on part2After colloidal sol, after 100-150 DEG C of the pre-heat treatment 5-20min, natural cooling；Again through TiCl4Solution treatment
10-40min is placed on warm table and calcines 10-40min at 450-550 DEG C, and natural cooling forms TiO2Compacted zone obtains
FTO electro-conductive glass/TiO2Compacted zone electrode；
Preferably, through TiCl4To be added respectively with deionized water and washes of absolute alcohol, dry be placed in again later again after solution treatment
It is calcined in thermal station；
More preferably, the spin coating TiO in the non-etched portions of FTO electro-conductive glass2Before colloidal sol, do not etched in FTO electro-conductive glass first
Partial one end pastes one section of high temperature gummed tape or deposition protective film is protected, the reserved electrode being connect with external circuit；
Preferably, the length of the high temperature gummed tape of stickup or deposition protective film is 2-240mm.
6. preparation method as claimed in claim 4, which is characterized in that in the step 2), in FTO electro-conductive glass/TiO2It is fine and close
Spin coating TiO on layer film electrode2Slurry is positioned over after dry on warm table, and temperature programmed control is heated to 450-550 DEG C, heat preservation
After 10-30min, natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer film electrode.
7. preparation method as claimed in claim 4, which is characterized in that in the step 3), in FTO electro-conductive glass/TiO2It is fine and close
Layer/TiO2Mesoporous layer film electrode spin coating ZrO2Slurry is positioned on warm table, temperature programmed control is heated to 450-600 after dry
DEG C, after keeping the temperature 10-30min, natural cooling, to obtain FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2It is mesoporous
Layer film electrode.
8. preparation method as claimed in claim 4, which is characterized in that conductive in FTO prepared by step 3) in the step 4)
Glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Spin coating perovskite CH on mesoporous layer film electrode3NH3Pb(I1-xBrx)3Forerunner
Liquid is positioned on warm table, is heated to 80-110 DEG C, crystallization 10-50min is kept the temperature, to obtain FTO electro-conductive glass/TiO2It causes
Close layer/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite thin film electrode；
Preferably, the perovskite CH3NH3Pb(I1-xBrx)3Precursor liquid is the CH using n,N-Dimethylformamide as solvent3NH3I、
PbI2And PbBr2Obtained by three kinds of solution mixing systems are standby；
Preferably, the perovskite CH3NH3Pb(I1-xBrx)3X is amount of substance score in precursor liquid, and x is 0.05~0.35.
9. preparation method as claimed in claim 4, which is characterized in that the preparation process of the perovskite solar cell be
What humidity carried out under the conditions of the natural air less than 50%, each functional layer is successively prepared using whole soln method；
Preferably, in the step 5), in FTO electro-conductive glass/TiO2Compacted zone/TiO2Mesoporous layer/ZrO2Mesoporous layer/perovskite
After scratching conductive carbon paste on membrane electrode, and cure 5-30min at 80-120 DEG C, carbon electrode is prepared, to obtain stable calcium
Titanium ore solar cell.
10. preparation method as claimed in claims 6 or 7, which is characterized in that the heating schedule of described program temperature control is：It is flowing
It under dynamic air conditions, is heated with 5-20 DEG C/min rates, when temperature reaches 280-360 DEG C, keeps the temperature 5-20min, continue with 5-20
DEG C/min rates are heated to 450-550 DEG C.
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| JP2020088316A (en) * | 2018-11-30 | 2020-06-04 | 国立大学法人東京工業大学 | Laminate, solar cell, and method of manufacturing solar cell |
| CN113285029A (en) * | 2021-04-23 | 2021-08-20 | 北方民族大学 | Organic-inorganic hybrid perovskite solar cell |
| CN113571341A (en) * | 2021-07-09 | 2021-10-29 | 西安交通大学 | All-solid-state supercapacitor with photoelectric conversion function and preparation method thereof |
| CN117790045A (en) * | 2023-12-28 | 2024-03-29 | 桑若(厦门)光伏产业有限公司 | Mesoporous titanium dioxide slurry and application thereof in preparation of printable mesoscopic perovskite solar cell electron transport layer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020088316A (en) * | 2018-11-30 | 2020-06-04 | 国立大学法人東京工業大学 | Laminate, solar cell, and method of manufacturing solar cell |
| CN113285029A (en) * | 2021-04-23 | 2021-08-20 | 北方民族大学 | Organic-inorganic hybrid perovskite solar cell |
| CN113571341A (en) * | 2021-07-09 | 2021-10-29 | 西安交通大学 | All-solid-state supercapacitor with photoelectric conversion function and preparation method thereof |
| CN117790045A (en) * | 2023-12-28 | 2024-03-29 | 桑若(厦门)光伏产业有限公司 | Mesoporous titanium dioxide slurry and application thereof in preparation of printable mesoscopic perovskite solar cell electron transport layer |
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