CN109326721A - A kind of the perovskite solar battery and its liquid phase preparation process of high stability - Google Patents
A kind of the perovskite solar battery and its liquid phase preparation process of high stability Download PDFInfo
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- CN109326721A CN109326721A CN201811189629.XA CN201811189629A CN109326721A CN 109326721 A CN109326721 A CN 109326721A CN 201811189629 A CN201811189629 A CN 201811189629A CN 109326721 A CN109326721 A CN 109326721A
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- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
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- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 9
- IVUHDTWRNCXVCD-UHFFFAOYSA-N methylazanium;iodate Chemical compound [NH3+]C.[O-]I(=O)=O IVUHDTWRNCXVCD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006748 scratching Methods 0.000 claims description 9
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- 230000000694 effects Effects 0.000 claims description 3
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- 238000001816 cooling Methods 0.000 description 5
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 206010054949 Metaplasia Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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Classifications
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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
- 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
- H10K30/81—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- 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
Abstract
The present invention provides the perovskite solar battery and its liquid phase preparation process of a kind of high stability, and solar battery includes: transparent conducting glass, electron transfer layer, mesoporous layer, insulating support layer, perovskite active layer and carbon electrode layer；The solar battery is to be prepared in natural air atmosphere using liquid phase method, prepares precursor liquid first, then using transparent conducting glass as substrate, is put into TiCl4It is calcined after aqueous solution processing, electron transfer layer is made, then as substrate, successively spin coating TiO2Slurry and ZrO2Slurry, in due course dry and heat treatment, is made mesoporous layer and insulating support layer；It instills precursor liquid in this substrate and heats and perovskite active layer is made, scratch conductive carbon paste on this substrate, so that the perovskite solar battery of high stability be made；Solar battery power conversion efficiency prepared by the present invention is high, and Long-Term Properties are stablized, and preparation process is simple, manufacturing cost is cheap, can satisfy large-scale industrialization production requirements.
Description
Technical field
The present invention relates to technical field of solar batteries, and in particular to it is a kind of low cost, high power conversion efficiency based on
The high stability perovskite solar battery and its simple liquid phase preparation process of carbon electrode.
Background technique
It enters after 21 century, as industry and rapid development of economy energy crisis have protruded and shown.Therefore, it develops
Clean renewable energy is imperative.Pillar industry of the photovoltaic power generation as renewable energy of new generation, possesses cleaning, without dirt
The advantages that contaminating, be low in cost.In recent years, the breakthrough of photovoltaic technology is created using perovskite as the novel solar battery of light-absorption layer
Property progress.Since perovskite material absorptivity is high, band gap is controllable, bipolarity (can transmit electronics but also transporting holes), expands
The advantages that scattered length is longer and carrier mobility is high, makes perovskite material possess preferable photoelectric properties, perovskite solar energy
High power conversion efficiency may be implemented in battery.But power converts high perovskite solar battery in high-purity at present
It is prepared in glove box, and using expensive hole transmission layer and noble metal electrode, the problems such as preparation cost is high, stability is poor is not
Conducive to industrialization large-scale production.
Chinese patent CN105870335A discloses a kind of simple perovskite solar battery of preparation process, with mesoporous branch
Based on frame structure devices, device architecture is simplified, the expensive noble metal electrode of carbon electrode replacement changes in certain degree
It has been apt to the performance of perovskite solar battery.But mesoporous shelf layer and carbon electrode will successively pass through silk-screen printing, calcining preparation
It after porous film electrode, is put into glove box, perovskite precursor liquid is added dropwise, after penetrating into mesoporous layer, solvent flashing, crystallization,
Complete preparation.Later stage of preparation uses glove box, and preparation process is not all of to be completed under natural air.
Chinese patent CN106601833A disclose a kind of inexpensive high stability solar battery suitable for production and its
Preparation method.Although perovskite solar battery power conversion efficiency has been more than 16% or more, vacuum thermal evaporation, spray are used
The methods of apply, deposit, last vacuum evaporation metal electrode, there are device preparation cost height and preparation process condition to require high, behaviour
Make the problems such as complicated.Although foregoing invention patent gradually constantly promotes perovskite solar battery to industrialization, calcium titanium
Mine solar battery is to oxygen, moisture sensitivity, and defect is easier to be formed, and causes perovskite solar cell stability poor.It seeks
Looking for stable perovskite preparation method of solar battery is the target of the field concerted effort.
Chinese patent CN106328813A discloses a kind of high stability and mixes caesium Ca-Ti ore type solar battery and its preparation
Method.The patent application improves device stability by the doping of cation to a certain extent, but introduces expensive 2,
2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell two fluorenes (Spiro-MeOTAD) base hole transmission layer.It causes
It is high to make device cost, and stability is still very low.
It can be seen that its crystallinity and stabilization can be enhanced, while adjusting calcium by perovskite material cation doping
Titanium ore material forbidden bandwidth, may finally improve perovskite solar battery power conversion efficiency and stability, therefore, for upper
The deficiencies in the prior art are stated, the present invention provides one kind under natural air, the high stability perovskite sun based on carbon electrode
It can battery and its simple liquid phase preparation process at low cost.
Summary of the invention
It is an object of the invention to overcome perovskite solar battery preparation aspect the deficiencies in the prior art, device is proposed
Structure optimization does not use expensive material, using the perovskite of simple liquid phase method preparation high stability under the conditions of natural air
The scheme of solar battery.Perovskite solar battery prepared by the present invention has power conversion efficiency high, in natural air item
It is steady in a long-term under part, and the advantage that preparation process is simple and manufacturing cost is cheap, it can satisfy large-scale industrial metaplasia
It produces and requires.
To achieve the goals above, the invention provides the following technical scheme:
A kind of perovskite solar battery of high stability, it is preferable that the perovskite solar battery includes: electrically conducting transparent
Glass, electron transfer layer, mesoporous layer, insulating support layer, perovskite active layer and carbon electrode layer；
The perovskite active layer is mixed-cation perovskite.
Perovskite solar battery as described above, it is preferable that the perovskite active layer is prepared using a step spin-coating method
Perovskite active layer, the perovskite active layer are mixed-cation perovskite (FA)x(MA)1-xPbI3, wherein x is the amount of substance
Score；
Preferably, the mixed-cation perovskite (FA)x(MA)1-xPbI3In x be 0.05~0.45；
More preferably, the mixed-cation perovskite (FA)x(MA)1-xPbI3Including first narrow cation and methylamine sun from
Son；
More preferably, the perovskite active layer infiltration is filled into mesoporous layer and insulating support layer, and covers insulation branch
The surface of rack-layer；
More preferably, the perovskite active layer with a thickness of 300~700nm.
Perovskite solar battery as described above, it is preferable that the transparent conducting glass is FTO electro-conductive glass；The electricity
Sub- transport layer is nano-TiO2Layer；The mesoporous layer is mesoporous TiO2Layer；The insulating support layer is porous ZrO2Layer；The carbon
Electrode layer is hydrophobicity carbon electrode.
Perovskite solar battery as described above, it is preferable that the electron transfer layer with a thickness of 10~40nm；It is given an account of
Aperture layer with a thickness of 150~300nm；The insulating support layer with a thickness of 150~300nm；The carbon electrode layer with a thickness of 8
~20 μm.
The liquid phase preparation process of described in any item perovskite solar batteries as above, it is preferable that the liquid phase preparation process
It is that all preparation process are completed using the liquid phase method of spin coating and blade coating in natural air atmosphere；The liquid phase preparation process packet
Include following steps:
1) mixed-cation perovskite precursor liquid is prepared
Mixed-cation perovskite (FA) is prepared according to the amount score of certain substancex(MA)1-xPbI3Precursor liquid, it is standby
With；
2) transparent conducting glass/electron transfer layer membrane electrode preparation
FTO electro-conductive glass is put into TiCl after ultrasonic cleaning and drying4Aqueous solution processing, is then placed on warm table and forges
It burns, forms TiO2Electron transfer layer, to obtain transparent conducting glass/electron transfer layer membrane electrode；
3) transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode preparation
The spin coating TiO on transparent conducting glass/electron transfer layer membrane electrode of step 2) preparation2Slurry is put after dry
It is placed on warm table after Low Temperature Heat Treatment, cooled to room temperature, then spin coating ZrO2Slurry is placed on warm table after dry
After calcining, cooled to room temperature, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electricity
Pole；
4) transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode system
It is standby
Transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode prepared by step 3) is placed in and is added
After being preheated in thermal station, it is added dropwise mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid is placed on warm table, is heated and is protected
Warm crystallization, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer thin-film electro
Pole；
5) perovskite solar battery is obtained
In transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer of step 4) preparation
After scratching conductive carbon paste on membrane electrode, solidification prepares carbon electrode, to obtain stable perovskite solar battery.
Liquid phase preparation process as described above, it is preferable that in step 1), the mixed-cation perovskite (FA)x(MA)1- xPbI3The preparation process of precursor liquid includes:
Lead iodide and iodate methylamine are put into anhydrous n,N-Dimethylformamide, ultrasound makes it completely dissolved, and obtains
MAPbI3DMF solution；Lead iodide and iodate carbonamidine are put into anhydrous n,N-Dimethylformamide, ultrasound keeps it completely molten
Solution obtains FAPbI3DMF solution；
By MAPbI3DMF solution and FAPbI3DMF solution mixed according to the amount score of certain substance, obtain
Mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid, wherein x is the amount score of substance, and x is 0.05~0.45.
Liquid phase preparation process as described above, it is preferable that in step 2), by FTO electro-conductive glass after ultrasonic cleaning and drying
It is put into the TiCl that concentration is 0.03~0.10mol/L450~80 DEG C of 20~50min of processing of aqueous solution, then spend respectively again from
After sub- water and washes of absolute alcohol, it is placed in 10~40min of calcining on 400~500 DEG C of warm tables, forms nano-TiO2Electron-transport
Layer, to obtain transparent conducting glass/electron transfer layer membrane electrode.
Liquid phase preparation process as described above, it is preferable that in step 3), in transparent conducting glass/electron transfer layer thin-film electro
Extremely upper spin coating TiO2Slurry after dry, be placed in after being heat-treated 8~12min on 150~250 DEG C of warm tables, naturally cool to room
Temperature；Spin coating ZrO again2Slurry after dry, be placed in after being heat-treated 25~35min on 450~600 DEG C of warm tables, naturally cool to
Room temperature, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode.
Liquid phase preparation process as described above, it is preferable that in step 4), by transparent conducting glass/electron transfer layer of preparation/
Mesoporous layer/insulating support layer film electrode is placed on warm table after preheating, is added dropwise mixed-cation perovskite (FA)x(MA)1- xPbI3Precursor liquid carries out spin coating, is placed on 80~110 DEG C of warm tables, heats and keep the temperature 10~70min of crystallization, mixed-cation
Perovskite (FA)x(MA)1-xPbI3Precursor liquid crystallizes on the gap and surface of mesoporous layer and insulating support layer, to obtain transparent
Electro-conductive glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode.
Liquid phase preparation process as described above, it is preferable that in step 5),
It is scraped on transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode
After applying conductive carbon paste, in 90~110 DEG C of 5~30min of solidification, hydrophobicity carbon electrode is formed, to obtain the perovskite of high stable
Solar battery.
Compared with the immediate prior art, technical solution provided by the invention is had the following beneficial effects:
(1) power conversion efficiency of perovskite solar battery provided by the invention is high, the sun prepared under optimal conditions
AM1.5G standard sunlight (intensity 100mW/cm of the energy battery in solar simulator2) irradiate lower measured power transfer efficiency
Up to 9.5% or more.
(2) perovskite solar battery provided by the invention has many advantages, such as moisture resistance by force and stablizes high.
(3) the perovskite solar battery technology scheme provided by the invention for preparing is under the conditions of natural air using liquid phase
Method preparation, does not need glove box, and do not need other special safeguard measures, has the features such as simple process, easy to operate.
(4) do not include expensive hole transmission layer in perovskite solar battery prepared by the present invention, and be not related to true
Sky vapor deposition noble metal electrode process, considerably reduces cost.
(5) technical solution provided by the invention selects carbon electrode instead of metal when preparing perovskite solar battery
Electrode.Carbon electrode has hydrophobicity, when perovskite solar battery works under field conditions (factors), improves device moisture resistance, makes it
Long-term stable operation, in particular to: the active layer that the present invention uses narrows (HC (NH for first2)2 +, FA+) and methylamine (CH3NH3 +, MA+)
The perovskite (FA) of cation mixingx(MA)1-xPbI3, select mixed-cation steady so as to improve the material of perovskite active layer
It is qualitative；Hydrophobicity carbon electrode resists erosion of the vapor to solar battery, further improves the stability of device.In high humidity
Attenuation test in degree air shows that solar battery power conversion efficiency has still maintained initial value after 2 months
90% or more, it is demonstrated by out long-time stability.
Detailed description of the invention
Fig. 1 is high stability perovskite solar battery structure figure provided by the invention；
Fig. 2 is the J-V indicatrix test chart of perovskite solar battery prepared by embodiment 1 in the present invention；
Fig. 3 is the carbon electrodes and water droplet contact angle of perovskite solar battery prepared by embodiment 1 in the present invention
Test chart；
Fig. 4 is the stability test figure of perovskite solar battery prepared by embodiment 1 in the present invention；
In figure: 1, transparent conducting glass；11, glass；12, FTO layers；3, electron transfer layer；4, mesoporous layer；5, insulating support
Layer；6, perovskite active layer；7, carbon electrode layer.
Specific embodiment
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 embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's every other embodiment 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 be can be combined with each other.
The perovskite solar battery and its liquid phase preparation process of a kind of high stability are provided in the present invention.The calcium titanium
Mine solar battery includes: transparent conducting glass 1, electron transfer layer 3, mesoporous layer 4, insulating support layer 5, perovskite active layer 6
With carbon electrode layer 7；Wherein, perovskite active layer 6 is mixed-cation perovskite.
Perovskite active layer 6 is to prepare perovskite active layer using the spin-coating method of a step, which is mixing
Cationic perovskite (FA)x(MA)1-xPbI3, wherein x be substance amount score, x be 0.05~0.45 (such as 0.06,0.08,
0.10、0.13、0.16、0.19、0.22、0.25、0.28、0.31、0.34、0.37、0.40、0.42、0.44)。
It is further preferred that mixed-cation perovskite (FA)x(MA)1-xPbI3It is that iodate first narrows (HC (NH2)2I, FAI)
With iodate methylamine (CH3NH3, MAI) and it is raw material preparation.
In a specific embodiment of the present invention, the infiltration of perovskite active layer 6 is filled into mesoporous layer 4 and insulating support layer 5,
And cover the surface of insulating support layer 5.
In a specific embodiment of the present invention, transparent conducting glass 1 is Fluorin doped stannic oxide (FTO) electro-conductive glass, i.e.,
FTO electro-conductive glass is in the upper surface of glass 11 to have one layer of FTO layer 12, immediately referred to as FTO electro-conductive glass；Electron transfer layer 3 is to receive
Rice TiO2Layer；Mesoporous layer 4 is mesoporous TiO2Layer；Insulating support layer 5 is porous ZrO2Layer；Carbon electrode layer 7 is hydrophobicity carbon electrode.
It is further preferred that electron transfer layer 3 with a thickness of 10~40nm (such as 12nm, 14nm, 16nm, 8nm, 20nm,
22nm,24nm,26nm,8nm,30nm,32nm,34nm,36nm,8nm,39nm)；Mesoporous layer 4 with a thickness of 150~300nm (example
As 152nm, 157nm, 160nm, 165nm, 170nm, 175nm, 80nm, 185nm, 190nm, 195nm, 200nm, 205nm,
210nm、215nm、220nm、225nm、230nm、235nm、240nm、248nm、256nm、262nm、268nm、275nm、
283nm,290nm,295nm,298nm)；Insulating support layer 5 with a thickness of 150~300nm (such as 152nm, 157nm, 160nm,
165nm、170nm、175nm、80nm、185nm、190nm、195nm、200nm、205nm、210nm、215nm、220nm、225nm、
230nm,235nm,240nm,248nm,256nm,262nm,268nm,275nm,283nm,290nm,295nm,298nm)；Carbon electricity
Pole layer 7 with a thickness of 8~20 μm of (such as 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μ
m)；Perovskite active layer 6 with a thickness of 300~700nm (such as 330nm, 370nm, 400nm, 450nm, 490nm, 530nm,
570nm、610nm、650nm、690nm)。
More preferably, insulating support layer 5 with a thickness of 200~300nm (such as 210nm, 220nm, 230nm, 240nm,
250nm、260nm、270nm、280nm、290nm)。
For the clearer structure composition for illustrating perovskite solar battery in the specific embodiment of the invention, the present invention is also
A kind of liquid phase preparation process of perovskite solar battery is provided, which used in natural air atmosphere
The liquid phase method of spin coating and blade coating completes all preparation process.The liquid phase preparation process includes the following steps:
1) mixed-cation perovskite precursor liquid is prepared
Mixed-cation perovskite (FA) is prepared according to the amount score of certain substancex(MA)1-xPbI3Precursor liquid, it is standby
With；
2) transparent conducting glass/electron transfer layer membrane electrode preparation
FTO electro-conductive glass is put into TiCl after ultrasonic cleaning and drying4Aqueous solution processing, is then placed on warm table and forges
It burns, forms TiO2Electron transfer layer, to obtain transparent conducting glass/electron transfer layer membrane electrode；
3) transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode preparation
The spin coating TiO on transparent conducting glass/electron transfer layer membrane electrode of step 2) preparation2Slurry is put after dry
It is placed on warm table after Low Temperature Heat Treatment, cooled to room temperature；Spin coating ZrO again2Slurry is placed on warm table after dry
After forged is burnt, cooled to room temperature, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film
Electrode；
4) transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode system
It is standby
Transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode prepared by step 3) is placed in and is added
After being preheated in thermal station, it is added dropwise mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid is placed on warm table, is heated and is protected
Warm crystallization, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer thin-film electro
Pole；
5) perovskite solar battery is obtained
In transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer of step 4) preparation
After scratching conductive carbon paste on membrane electrode, solidification prepares carbon electrode, to obtain stable perovskite solar battery.
In a specific embodiment of the present invention, in step 1), mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid
Preparation process include:
Lead iodide (the PbI for being 1:1 by molar ratio2) and iodate methylamine (AMI) be put into anhydrous N,N-dimethylformamide
(DMF) in, ultrasound is made it completely dissolved, and obtains MAPbI3DMF solution；Lead iodide (the PbI for being 1:1 by molar ratio2) and iodate
Carbonamidine (FMI) is put into anhydrous n,N-Dimethylformamide (DMF), and ultrasound makes it completely dissolved, and obtains FAPbI3DMF it is molten
Liquid；
By MAPbI3DMF solution and FAPbI3DMF solution mixed according to the amount score of certain substance, obtain
Mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid, wherein x be substance amount score, x be 0.05~0.45 (such as
0.06、0.08、0.10、0.13、0.16、0.19、0.22、0.25、0.28、0.31、0.34、0.37、0.40、0.42、0.44)。
In a specific embodiment of the present invention, in step 2), FTO electro-conductive glass is put into after ultrasonic cleaning and drying dense
Degree be 0.03~0.10mol/L (such as 0.035mol/L, 0.04mol/L, 0.045mol/L, 0.05mol/L, 0.055mol/L,
0.06mol/L、0.065mol/L、0.07mol/L、0.075mol/L、0.08mol/L、0.085mol/L、0.09mol/L、
TiCl 0.095mol/L)450~80 DEG C of aqueous solution (such as 53 DEG C, 55 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70 DEG C,
73 DEG C, 75 DEG C, 78 DEG C) processing 20~50min (such as 22min, 25min, 28min, 30min, 32min, 35min, 38min,
40min, 42min, 45min, 48min), after then being cleaned respectively with deionized water and washes of absolute alcohol again, it is placed in 400~
500 DEG C (such as 410 DEG C, 420 DEG C, 430 DEG C, 440 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C, 485 DEG C, 490 DEG C, 495 DEG C)
On warm table calcine 10~40min (such as 12min, 15min, 18min, 20min, 22min, 25min, 28min, 30min,
32min, 35min, 38min), form nano-TiO2Electron transfer layer, to obtain transparent conducting glass/electron-transport layer film
Electrode；
Preferably, after FTO electro-conductive glass is successively cleaned with tap water, distilled water, acetone and EtOH Sonicate containing dish washing liquid
It dries up again.
In a specific embodiment of the present invention, it in step 3), is revolved on transparent conducting glass/electron transfer layer membrane electrode
Apply TiO2Slurry, after dry, be placed in 150~250 DEG C (such as 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C,
185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C, 220 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C) heating
On platform be heat-treated 8~12min (such as 9min, 9.2min, 9.5min, 9.8min, 10min, 10.2min, 10.5min,
10.8min, 11min, 11.2min, 11.5min, 11.8min) after, cooled to room temperature；Spin coating ZrO again2Slurry, it is dry
Afterwards, it is placed on 450~600 DEG C of (such as 470 DEG C, 490 DEG C, 510 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 590 DEG C) warm tables hot
After handling 25~35min (such as 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min), from
It is so cooled to room temperature, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode.
More preferably, spin coating TiO2Slurry and spin coating ZrO2The speed of rotation of slurry be 3500~4500rpm (such as
3600rpm, 3700rpm, 3800rpm, 3900rpm, 4000rpm, 4100rpm, 4200rpm, 4300rpm, 4400rpm), spin coating
Time is 25~35s (such as 26s, 27s, 28s, 29s, 30s, 31s, 32s, 33s, 34s).
In a specific embodiment of the present invention, the spin coating TiO in step 3)2Mesoporous knot directly can not be just formed after slurry
Structure, this is because in spin coating TiO2Using Low Temperature Heat Treatment mode when slurry, Low Temperature Heat Treatment cannot completely remove bonding
The organic matters such as agent, also just do not form meso-hole structure also.It must be in spin coating TiO2Spin coating ZrO again after Low Temperature Heat Treatment after slurry2Slurry
Material, and high-temperature heat treatment is carried out, TiO can be thus obtained simultaneously2Meso-hole structure and ZrO2Structure (insulating support layer is mesoporous).
In a specific embodiment of the present invention, in step 4), by transparent conducting glass/electron transfer layer of preparation/mesoporous
Layer/insulating support layer film electrode is placed on warm table after preheating, is added dropwise mixed-cation perovskite (FA)x(MA)1-xPbI3Before
Liquid spin coating is driven, is (FA) of the spin coating with n,N-Dimethylformamide (DMF) for solvent on insulating support layerx(MA)1-xPbI3
Precursor liquid；Be placed in after spin coating 80~110 DEG C (such as 82 DEG C, 85 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C, 100 DEG C, 102 DEG C,
105 DEG C, 108 DEG C) on warm table, heat and keep the temperature 10~70min of crystallization (such as 12min, 15min, 20min, 25min,
30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 68min), solute is in mesoporous layer and insulating support
It is crystallized on the gap and surface of layer, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite
Active layer membrane electrode.
Preferably, transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode is placed on warm table
Preheating time is 7~15min (such as 8min, 9min, 10min, 11min, 12min, 13min, 14min), the mixing sun of dropwise addition
Ion perovskite (FA)x(MA)1-xPbI3The temperature of precursor liquid be 45~75 DEG C (such as 46 DEG C, 48 DEG C, 50 DEG C, 52 DEG C, 54 DEG C,
56℃,58℃,61℃,64℃,66℃,69℃,71℃,73℃,74℃)；
More preferably, mixed-cation perovskite (FA) is added dropwisex(MA)1-xPbI3First with the speed of rotation when precursor liquid spin coating
1700~1900rpm (such as 1710rpm, 1730rpm, 1750rpm, 1780rpm, 1800rpm, 1820rpm, 1840rpm,
1860rpm, 1880rpm, 1890rpm) 2~4s of spin coating (such as 2s, 2.2s, 2.4s, 2.5s, 2.7s, 2.9s, 3.0s, 3.2s,
3.5s, 3.8s, 3.9s, 4.0s), then again with 3500~3800rpm of the speed of rotation (such as 3510rpm, 3550rpm,
3580rpm, 3600rpm, 3630rpm, 3660rpm, 3690rpm, 3730rpm, 3760rpm, 3780rpm, 3790rpm) spin coating
25~35s (such as 26s, 27s, 28s, 29s, 30s, 31s, 32s, 33s, 34s).
In a specific embodiment of the present invention, in step 5), in transparent conducting glass/electron transfer layer/mesoporous layer/insulation
After scratching conductive carbon paste on shelf layer/perovskite active layer membrane electrode, in 90~110 DEG C of (such as 91 DEG C, 93 DEG C, 95 DEG C, 97
DEG C, 99 DEG C, 101 DEG C, 103 DEG C, 105 DEG C, 107 DEG C, 109 DEG C) solidification 5~30min (such as 6min, 8min, 10min, 12min,
14min, 16min, 18min, 20min, 22min, 25min, 28min, 29min), hydrophobicity carbon electrode is formed, to obtain height
Stable perovskite solar battery.
Hole transmission layer is not used in the device architecture of the perovskite solar battery of high stability provided by the invention, no
Use noble metal electrode.The perovskite solar battery is to improve the moisture resistance of device to electrode with hydrophobicity carbon electrode.
To sum up, the present invention provides the perovskite solar batteries and its simple preparation method of a kind of high stability.
The solar battery is by transparent conducting glass, electron transfer layer, mesoporous layer, insulating support layer, perovskite active layer and carbon electrode
Layer composition, preparation process do not have to glove box, carry out in natural air atmosphere.Active layer is that first narrows (HC (NH2)2 +, FA+) and first
Amine (CH3NH3 +, MA+) cation mixing perovskite (FA)x(MA)1-xPbI3.Mixed-cation is selected, it is living to improve perovskite
The stability of material of property layer；Hydrophobicity carbon electrode resists erosion of the vapor to solar battery, further improves device
Stability.Attenuation test in damp atmosphere shows that solar battery power conversion efficiency still maintains after 2 months
90% or more of initial value, is demonstrated by out long-time stability.High-cost hole transmission layer and your gold are abandoned in device architecture
Belong to electrode, selects the carbon electrode of low-temperature setting, significantly simplify preparation process, save the cost makes perovskite solar battery
Convenient for being mass produced and applying.
Embodiment 1
Under the conditions of natural air, using the perovskite solar battery of simple liquid phase method preparation high stability, specifically
Steps are as follows:
(1) lead iodide (PbI of 0.9353g is weighed2) and the iodate methylamine (AMI) of 0.3228g be put into the anhydrous N, N- of 2mL
In dimethylformamide (DMF), ultrasound is made it completely dissolved, and obtains MAPbI3DMF solution；Weigh 0.9167 PbI2With
The iodate carbonamidine (FMI) of 0.3420g is put into the anhydrous DMF of 2mL, and ultrasound makes it completely dissolved, and obtains FAPbI3DMF solution.
Above two perovskite solution is mixed by x=0.3, is obtained mixed-cation perovskite (FA)0.3(MA)0.7PbI3Forerunner
Liquid, it is spare.
(2) FTO electro-conductive glass is blown successively with the tap water containing dish washing liquid, distilled water, acetone and EtOH Sonicate cleaning
It is dry.Then above-mentioned substrate is put into the TiCl that concentration is 0.08mol/L4In aqueous solution, after keeping the temperature 40min under the conditions of 70 DEG C, take
Out, it is rinsed respectively with distilled water and ethyl alcohol, drying is placed on warm table, is heated to 450 DEG C, is heat-treated 30min, nanometer
TiO2Form electron transfer layer.
(3) spin coating nano-TiO on above-mentioned substrate2Slurry, speed of rotation 3800rpm, spin-coating time 30s, Zhi Hou
200 DEG C of heat treatment 10min, cooled to room temperature, then spin coating nanometer ZrO on warm table2Slurry, speed of rotation 4200rpm,
Spin-coating time is 30s, is finally placed on warm table and is heated to 500 DEG C, is heat-treated 30min, and cooled to room temperature forms and is situated between
Hole TiO2Layer and porous ZrO2Insulating support layer.
(4) after above-mentioned substrate preheats 10min on warm table, 50 DEG C of mixed-cation perovskite (FA) is added dropwise0.3
(MA)0.7PbI3Precursor liquid spin coating, after the rate spin coating 3s of 1800rpm, with the rate spin coating 30s of 3600rpm, later base
Piece is placed on 100 DEG C of warm table, is heated 50min, so that solvent is volatilized, solute is in mesoporous TiO2Layer and porous ZrO2Insulation branch
It is crystallized on the gap and surface of rack-layer, forms perovskite active layer.
(5) finally, scratching conductive carbon paste on above-mentioned substrate, 100 DEG C of solidification 15min form carbon electrode, and natural cooling obtains
To high stability perovskite solar battery as shown in Figure 1.
By perovskite solar battery manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) lower test Current density-voltage (J-V) indicatrix is irradiated, test result is indicated with Fig. 2.The solar-electricity
Pond obtained short-circuit current density (Jsc) it is 21.58mA/cm2, open-circuit voltage (V℃) it is 0.982V, fill factor (FF) is 0.452,
And power conversion efficiency (PCE) is 9.58%.
Contact angle, result are tested by water droplet is added dropwise in perovskite solar battery carbon electrodes manufactured in the present embodiment
Indicate that (figure when water droplet is added dropwise in the carbon electrodes of solar battery and is tested is black-and-white photograph figure, other are black using Fig. 3
White line figure cannot show the test effect, therefore providing here is black-and-white photograph figure).The result shows that water is at this
At spherical shape in carbon electrodes, extension drop shape at any time is constant, dimensionally stable, and the contact angle of carbon electrode and water is
123 °, show that the hydrophobicity of carbon electrode is high, moisture is unable to penetration carbon electrode layer, protects perovskite active layer well.
Perovskite solar battery manufactured in the present embodiment is not taken into any safeguard measure, is stored under field conditions (factors),
Every 1 week, in AM1.5G standard sunlight (the intensity 100mW/cm of solar simulator2) the lower test J-V spy of irradiation
Curve is levied, power conversion efficiency is had rated and changes with time relationship, as a result indicated with Fig. 4.The result shows that the solar battery
It stores under field conditions (factors), with the extension power conversion efficiency slow-decay of time, but rate of decay is especially slow, by 2
After month, power conversion efficiency has still maintained 90% of initial value or more, demonstrates the perovskite sun of straightforward procedure preparation
Energy battery has very high stability.
Embodiment 2
Under the conditions of natural air, using the perovskite solar battery of simple liquid phase method preparation high stability, specifically
Steps are as follows:
(1) PbI of 0.9353g is weighed2It is put into the AMI of 0.3228g in the DMF of anhydrous 2mL, ultrasound keeps it completely molten
Solution obtains perovskite MAPbI3Precursor liquid, it is spare.
(2) FTO electro-conductive glass is blown successively with the tap water containing dish washing liquid, distilled water, acetone and EtOH Sonicate cleaning
It is dry.Then above-mentioned substrate is put into the TiCl that concentration is 0.08mol/L4In aqueous solution, after keeping the temperature 40min under the conditions of 70 DEG C, take
Out, it is rinsed respectively with distilled water and ethyl alcohol, drying is placed on warm table, is heated to 450 DEG C, is heat-treated 30min, nanometer
TiO2Form electron transfer layer.
(3) spin coating nano-TiO on above-mentioned substrate2Slurry, speed of rotation 3800rpm, spin-coating time 30s, Zhi Hou
200 DEG C of heat treatment 10min, cooled to room temperature, then spin coating nanometer ZrO on warm table2Slurry, speed of rotation 4200rpm,
Spin-coating time is 30s, is finally placed on warm table and is heated to 500 DEG C, is heat-treated 30min, and cooled to room temperature forms and is situated between
Hole TiO2Layer and porous ZrO2Insulating support layer.
(4) after above-mentioned substrate preheats 10min on warm table, 50 DEG C of perovskite MAPbI is added dropwise3Precursor liquid spin coating, with
After the rate spin coating 3s of 1800rpm, with the rate spin coating 30s of 3600rpm, substrate is placed on later on 100 DEG C of warm table,
40min is heated, so that solvent is volatilized, solute is in mesoporous TiO2Layer and porous ZrO2It is crystallized on the gap and surface of insulating support layer,
Form perovskite active layer.
(5) finally, scratching conductive carbon paste on above-mentioned substrate, 100 DEG C of solidification 15min form carbon electrode, and natural cooling obtains
To high stability perovskite solar battery.
By perovskite solar battery manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) the lower test J-V indicatrix of irradiation, the short-circuit current density of the solar battery is 18.92mA/cm2, open circuit
Voltage is 0.928V, and fill factor 0.453 and power conversion efficiency are 7.95%；Other performance tests and 1 phase of embodiment
Together.
Embodiment 3
Under the conditions of natural air, using the perovskite solar battery of simple liquid phase method preparation high stability, specifically
Steps are as follows:
(1) lead iodide (PbI of 0.9353g is weighed2) and the iodate methylamine (AMI) of 0.3228g be put into the anhydrous N, N- of 2mL
In dimethylformamide (DMF), ultrasound is made it completely dissolved, and obtains MAPbI3DMF solution；Weigh 0.9167 PbI2With
The iodate carbonamidine (FMI) of 0.3420g is put into the anhydrous DMF of 2mL, and ultrasound makes it completely dissolved, and obtains FAPbI3DMF solution.
Above two perovskite solution is mixed by x=0.1, is obtained mixed-cation perovskite (FA)0.1(MA)0.9PbI3Forerunner
Liquid, it is spare.
(2) FTO electro-conductive glass is blown successively with the tap water containing dish washing liquid, distilled water, acetone and EtOH Sonicate cleaning
It is dry.Then above-mentioned substrate is put into the TiCl that concentration is 0.08mol/L4In aqueous solution, after keeping the temperature 40min under the conditions of 70 DEG C, take
Out, it is rinsed respectively with distilled water and ethyl alcohol, drying is placed on warm table, is heated to 450 DEG C, is heat-treated 30min, nanometer
TiO2Form electron transfer layer.
(3) spin coating nano-TiO on above-mentioned substrate2Slurry, speed of rotation 3800rpm, spin-coating time 30s, Zhi Hou
200 DEG C of heat treatment 10min, cooled to room temperature, then spin coating nanometer ZrO on warm table2Slurry, speed of rotation 4200rpm,
Spin-coating time is 30s, is finally placed on warm table and is heated to 500 DEG C, is heat-treated 30min, and cooled to room temperature forms and is situated between
Hole TiO2Layer and porous ZrO2Insulating support layer.
(4) after above-mentioned substrate preheats 10min on warm table, 50 DEG C of mixed-cation perovskite (FA) is added dropwise0.1
(MA)0.9PbI3Precursor liquid spin coating, after the rate spin coating 3s of 1800rpm, with the rate spin coating 30s of 3600rpm, later base
Piece is placed on 100 DEG C of warm table, is heated 50min, so that solvent is volatilized, solute is in mesoporous TiO2Layer and porous ZrO2Insulation branch
It is crystallized on the gap and surface of rack-layer, forms perovskite active layer.
(5) finally, scratching conductive carbon paste on above-mentioned substrate, 100 DEG C of solidification 15min form carbon electrode, and natural cooling obtains
To high stability perovskite solar battery.
By perovskite solar battery manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) the lower test J-V indicatrix of irradiation, the short-circuit current density of the solar battery is 17.32mA/cm2, open circuit
Voltage is 0.910V, and fill factor 0.452 and power conversion efficiency are 7.12%；Other performance tests and 1 phase of embodiment
Together.
Embodiment 4
Under the conditions of natural air, using the perovskite solar battery of simple liquid phase method preparation high stability, specifically
Steps are as follows:
(1) lead iodide (PbI of 0.9353g is weighed2) and the iodate methylamine (AMI) of 0.3228g be put into the anhydrous N, N- of 2mL
In dimethylformamide (DMF), ultrasound is made it completely dissolved, and obtains MAPbI3DMF solution；Weigh 0.9167 PbI2With
The iodate carbonamidine (FMI) of 0.3420g is put into the anhydrous DMF of 2mL, and ultrasound makes it completely dissolved, and obtains FAPbI3DMF solution.
Above two perovskite solution is mixed by x=0.2, is obtained mixed-cation perovskite (FA)0.2(MA)0.8PbI3Forerunner
Liquid, it is spare.
(2) FTO electro-conductive glass is blown successively with the tap water containing dish washing liquid, distilled water, acetone and EtOH Sonicate cleaning
It is dry.Then above-mentioned substrate is put into the TiCl that concentration is 0.08mol/L4In aqueous solution, after keeping the temperature 40min under the conditions of 70 DEG C, take
Out, it is rinsed respectively with distilled water and ethyl alcohol, drying is placed on warm table, is heated to 450 DEG C, is heat-treated 30min, nanometer
TiO2Form electron transfer layer.
(3) spin coating nano-TiO on above-mentioned substrate2Slurry, speed of rotation 3800rpm, spin-coating time 30s, Zhi Hou
200 DEG C of heat treatment 10min, cooled to room temperature, then spin coating nanometer ZrO on warm table2Slurry, speed of rotation 4200rpm,
Spin-coating time is 30s, is finally placed on warm table and is heated to 500 DEG C, is heat-treated 30min, and cooled to room temperature forms and is situated between
Hole TiO2Layer and porous ZrO2Insulating support layer.
(4) after above-mentioned substrate preheats 10min on warm table, 50 DEG C of mixed-cation perovskite (FA) is added dropwise0.2
(MA)0.8PbI3Precursor liquid spin coating, after the rate spin coating 3s of 1800rpm, with the rate spin coating 30s of 3600rpm, later base
Piece is placed on 100 DEG C of warm table, is heated 50min, so that solvent is volatilized, solute is in mesoporous TiO2Layer and porous ZrO2Insulation branch
It is crystallized on the gap and surface of rack-layer, forms perovskite active layer.
(5) finally, scratching conductive carbon paste on above-mentioned substrate, 100 DEG C of solidification 15min form carbon electrode, and natural cooling obtains
To high stability perovskite solar battery.
By perovskite solar battery manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) the lower test J-V indicatrix of irradiation, the short-circuit current density of the solar battery is 19.92mA/cm2, open circuit
Voltage is 0.933V, and fill factor 0.462 and power conversion efficiency are 8.59%；Other performance tests and 1 phase of embodiment
Together.
Embodiment 5
Under the conditions of natural air, using the perovskite solar battery of simple liquid phase method preparation high stability, specifically
Steps are as follows:
(1) lead iodide (PbI of 0.9353g is weighed2) and the iodate methylamine (AMI) of 0.3228g be put into the anhydrous N, N- of 2mL
In dimethylformamide (DMF), ultrasound is made it completely dissolved, and obtains MAPbI3DMF solution；Weigh 0.9167 PbI2With
The iodate carbonamidine (FMI) of 0.3420g is put into the anhydrous DMF of 2mL, and ultrasound makes it completely dissolved, and obtains FAPbI3DMF solution.
Above two perovskite solution is mixed by x=0.4, is obtained mixed-cation perovskite (FA)0.4(MA)0.6PbI3Forerunner
Liquid, it is spare.
(2) FTO electro-conductive glass is blown successively with the tap water containing dish washing liquid, distilled water, acetone and EtOH Sonicate cleaning
It is dry.Then above-mentioned substrate is put into the TiCl that concentration is 0.08mol/L4In aqueous solution, after keeping the temperature 40min under the conditions of 70 DEG C, take
Out, it is rinsed respectively with distilled water and ethyl alcohol, drying is placed on warm table, is heated to 450 DEG C, is heat-treated 30min, nanometer
TiO2Form electron transfer layer.
(3) spin coating nano-TiO on above-mentioned substrate2Slurry, speed of rotation 3800rpm, spin-coating time 30s, Zhi Hou
200 DEG C of heat treatment 10min, cooled to room temperature, then spin coating nanometer ZrO on warm table2Slurry, speed of rotation 4200rpm,
Spin-coating time is 30s, is finally placed on warm table and is heated to 500 DEG C, is heat-treated 30min, and cooled to room temperature forms and is situated between
Hole TiO2Layer and porous ZrO2Insulating support layer.
(4) after above-mentioned substrate preheats 10min on warm table, 50 DEG C of mixed-cation perovskite (FA) is added dropwise0.4
(MA)0.6PbI3Precursor liquid spin coating, after the rate spin coating 3s of 1800rpm, with the rate spin coating 30s of 3600rpm, later base
Piece is placed on 100 DEG C of warm table, is heated 50min, so that solvent is volatilized, solute is in mesoporous TiO2Layer and porous ZrO2Insulation branch
It is crystallized on the gap and surface of rack-layer, forms perovskite active layer.
(5) finally, scratching conductive carbon paste on above-mentioned substrate, 100 DEG C of solidification 15min form carbon electrode, and natural cooling obtains
To high stability perovskite solar battery.
By perovskite solar battery manufactured in the present embodiment solar simulator AM1.5G standard sunlight (intensity
For 100mW/cm2) the lower test J-V indicatrix of irradiation, the short-circuit current density of the solar battery is 19.65mA/cm2, open circuit
Voltage is 0.912V, and fill factor 0.454 and power conversion efficiency are 8.14%；Other performance tests and 1 phase of embodiment
Together.
Comparative example
(1) FTO electro-conductive glass is successively used into tap water containing dish washing liquid, distilled water, acetone and EtOH Sonicate cleaning, drying.
Then above-mentioned substrate is put into the TiCl that concentration is 0.08mol/L4In aqueous solution, after keeping the temperature 40min under the conditions of 70 DEG C, take out,
It is rinsed respectively with distilled water and ethyl alcohol, drying, is placed on warm table and is heat-treated 30 minutes for 450 DEG C, nano-TiO2Form electronics
Transport layer.
(2) spin coating nano-TiO on above-mentioned substrate2Slurry, speed of rotation 3800rpm, spin-coating time 30s, Zhi Hou
It is heated to 200 DEG C of heat preservation 10min on warm table, continues to be heated to 500 DEG C of heat preservation 30min, cooled to room temperature is formed mesoporous
TiO2Layer.
(3) lead iodide (PbI of 0.9353g is weighed2) and the iodate methylamine (AMI) of 0.3228g be put into the anhydrous N, N- of 2mL
In dimethylformamide (DMF), ultrasound is made it completely dissolved, and obtains MAPbI3DMF solution；Weigh 0.9167 PbI2With
The iodate carbonamidine (FMI) of 0.3420g is put into the anhydrous DMF of 2mL, and ultrasound makes it completely dissolved, and obtains FAPbI3DMF solution.
Above two perovskite solution is mixed by x=0.3, is obtained mixed-cation perovskite (FA)0.3(MA)0.7PbI3Forerunner
Liquid, it is spare.
(4) 1mL concentration is spiro-OMeTAD (2,2', 7,7'- tetra- [N, the N- bis- (4- methoxyphenyl) of 72.3mg/mL
Amino] two fluorenes of -9,9'- spiral shell) chlorobenzene solution and 19 μ L concentration be 520mg/mL double trifluoromethanesulfonimide lithiums acetonitrile
The 4- tert .-butylpyridine of solution and 29 μ L, which are uniformly mixed, obtains hole biography material precursor liquid, spare.
(5) substrate of above-mentioned steps (2) preparation is placed on warm table, is heated to 300 DEG C, keeps the temperature 10min, drives away residual
Absorption water after, on dislocation sol evenning machine, 50 DEG C of spin coating of mixing perovskite (FA)0.3(MA)0.7PbI3Precursor liquid, with 1800rpm
Rate spin coating 3s after, with the rate spin coating 30s of 3600rpm, substrate is placed on later on 100 DEG C of warm table, heat
40min makes solvent volatilize, and solute is in mesoporous TiO2It is crystallized on the gap and surface of layer, forms perovskite active layer.
(6) hole is added dropwise on above-mentioned substrate and passes material precursor liquid, speed of rotation 4000rpm, spin-coating time 20s, shape
At hole transmission layer.
Above-mentioned steps (3)~(6) are to operate to complete in glove box, and glove box atmosphere is high-purity nitrogen, H2O steam contains
Amount control is below 0.01%.
(7) above-mentioned substrate be fixed on vacuum coating equipment plated film it is intracavitary, be evacuated to the intracavitary pressure of plated film and reach 4 × 10- 4Pa, evaporation thickness are that 80nm gold obtains perovskite thin film solar battery.
In the AM1.5G standard sunlight of solar simulator, (intensity is the perovskite solar battery of comparative example preparation
100mW/cm2) the lower test J-V indicatrix of irradiation.The solar battery short-circuit current density is 21.89mA/cm2, open-circuit voltage
For 1.015V, fill factor 0.726 and power conversion efficiency are 16.13%.But the solar battery is especially unstable
It is fixed, it is placed 7 days in natural air item, power conversion efficiency is reduced to 11.56%, and attenuation amplitude is the 28.3% of initial value；
After 14 days, power conversion efficiency is reduced to 3.72%, and attenuation amplitude is the 76.9% of initial value；After 21, substantially
Electric current is not measured, device is scrapped.
Solar battery prepared by the comparative example is by FTO electro-conductive glass, TiO2Compacted zone, TiO2Mesoporous layer, mixing sun from
Sub- calcium titanium ore bed, Spiro-MeOTAD base hole transmission layer and gold form electrode layer.Currently, Spiro-MeOTAD is somewhat expensive, 1
It gram is 1800 yuan, then doping and solvent etc. reach 2400 yuan containing 1 gram of Spiro-MeOTAD solution price.Noble metal pair
The preparation of electrode needs vacuum evaporation process, and condition is harsh, complicated for operation.Although the perovskite solar-electricity of comparative example preparation
Pond power conversion efficiency is relatively high, but standby complicated for operation, at high cost, and obtained solar cell stability is poor, uses
It is worth low, cannot promote the use of.
To sum up, by comparative example 1~5 and comparative example it is found that the calcium of technical solution provided by the invention preparation
Titanium ore solar battery has low cost, high power conversion efficiency and stability is strong and cheap preparation method.The sun of the invention
Energy battery is made of transparent conducting glass, electron transfer layer, mesoporous layer, insulating support layer, perovskite active layer and carbon electrode layer.
Expensive hole transmission layer and noble metal electrode have been abandoned from efficient perovskite solar battery structure, and have selected valence
The cheap hydrophobicity carbon electrode of lattice.Under the conditions of natural air, prepared too using the simple liquid phase method such as spin coating and blade coating
Positive energy battery device.The perovskite solar battery of this method preparation has power conversion efficiency high, under the conditions of natural air
Feature steady in a long-term, and the advantage that preparation process is simple and manufacturing cost is cheap, can satisfy large-scale industrial metaplasia
It produces and requires.
In conclusion the present invention also has the following technical effect that
(1) power conversion efficiency of perovskite solar battery provided by the invention is high, the sun prepared under optimal conditions
AM1.5G standard sunlight (intensity 100mW/cm of the energy battery in solar simulator2) irradiate lower measured power transfer efficiency
Up to 9.5% or more.
(2) perovskite solar battery provided by the invention has many advantages, such as moisture resistance by force and stablizes high.
(3) the perovskite solar battery technology scheme provided by the invention for preparing is under the conditions of natural air using liquid phase
Not the features such as method preparation, does not need glove box, and does not need other special safeguard measures with simple process, easy to operate.
(4) do not include expensive hole transmission layer in perovskite solar battery prepared by the present invention, and be not related to true
Sky vapor deposition noble metal electrode process, considerably reduces cost.
(5) technical solution provided by the invention selects carbon electrode instead of metal when preparing perovskite solar battery
Electrode.Carbon electrode has hydrophobicity, when perovskite solar battery works under field conditions (factors), improves device moisture resistance, makes it
Long-term stable operation, in particular to: the active layer that the present invention uses narrows (HC (NH for first2)2 +, FA+) and methylamine (CH3NH3 +, MA+)
The perovskite (FA) of cation mixingx(MA)1-xPbI3, select mixed-cation steady so as to improve the material of perovskite active layer
It is qualitative；Hydrophobicity carbon electrode resists erosion of the vapor to solar battery, further improves the stability of device.In high humidity
Attenuation test in degree air shows that solar battery power conversion efficiency has still maintained initial value after 2 months
90% or more, it is demonstrated by out long-time stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Mind and principle within, any modification, equivalent replacement, improvement and so on, accompanying claims protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of perovskite solar battery of high stability, which is characterized in that the perovskite solar battery includes: transparent
Electro-conductive glass, electron transfer layer, mesoporous layer, insulating support layer, perovskite active layer and carbon electrode layer；
The perovskite active layer is mixed-cation perovskite.
2. perovskite solar battery as described in claim 1, which is characterized in that the perovskite active layer is using a step
Spin-coating method prepares perovskite active layer, and the perovskite active layer is mixed-cation perovskite (FA)x(MA)1-xPbI3, wherein x
For the amount score of substance；
Preferably, the mixed-cation perovskite (FA)x(MA)1-xPbI3In x be 0.05~0.45；
More preferably, the mixed-cation perovskite (FA)x(MA)1-xPbI3Cation and methylamine cation are narrowed including first；
More preferably, the perovskite active layer infiltration is filled into mesoporous layer and insulating support layer, and covers insulating support layer
Surface；
More preferably, the perovskite active layer with a thickness of 300~700nm.
3. perovskite solar battery as described in claim 1, which is characterized in that the transparent conducting glass is FTO conductive
Glass；The electron transfer layer is nano-TiO2Layer；The mesoporous layer is mesoporous TiO2Layer；The insulating support layer is porous
ZrO2Layer；The carbon electrode layer is hydrophobicity carbon electrode.
4. perovskite solar battery as claimed in claim 3, which is characterized in that the electron transfer layer with a thickness of 10~
40nm；The mesoporous layer with a thickness of 150~300nm；The insulating support layer with a thickness of 150~300nm；The carbon electrode
Layer with a thickness of 8~20 μm.
5. a kind of liquid phase preparation process of perovskite solar battery according to any one of claims 1-4, which is characterized in that
The liquid phase preparation process is to complete all preparation process using the liquid phase method of spin coating and blade coating in natural air atmosphere；Institute
Liquid phase preparation process is stated to include the following steps:
1) mixed-cation perovskite precursor liquid is prepared
Mixed-cation perovskite (FA) is prepared according to the amount score of certain substancex(MA)1-xPbI3Precursor liquid, it is spare；
2) transparent conducting glass/electron transfer layer membrane electrode preparation
FTO electro-conductive glass is put into TiCl after ultrasonic cleaning and drying4Aqueous solution processing, is then placed on warm table and calcines, shape
At TiO2Electron transfer layer, to obtain transparent conducting glass/electron transfer layer membrane electrode；
3) transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode preparation
The spin coating TiO on transparent conducting glass/electron transfer layer membrane electrode of step 2) preparation2Slurry is placed in after dry
On warm table after Low Temperature Heat Treatment, cooled to room temperature, then spin coating ZrO2Slurry is placed on warm table and calcines after dry
Afterwards, cooled to room temperature, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode；
4) transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode preparation
Transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode prepared by step 3) is placed in warm table
After upper preheating, it is added dropwise mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid is placed on warm table, is heated and is kept the temperature crystalline substance
Change, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode；
5) perovskite solar battery is obtained
In transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite activity layer film of step 4) preparation
After scratching conductive carbon paste on electrode, solidification prepares carbon electrode, to obtain stable perovskite solar battery.
6. liquid phase preparation process as claimed in claim 5, which is characterized in that in step 1), the mixed-cation perovskite
(FA)x(MA)1-xPbI3The preparation process of precursor liquid includes:
Lead iodide and iodate methylamine are put into anhydrous n,N-Dimethylformamide, ultrasound makes it completely dissolved, and obtains MAPbI3's
DMF solution；Lead iodide and iodate carbonamidine are put into anhydrous n,N-Dimethylformamide, ultrasound makes it completely dissolved, and obtains
FAPbI3DMF solution；
By MAPbI3DMF solution and FAPbI3DMF solution mixed according to the amount score of certain substance, mixed
Cationic perovskite (FA)x(MA)1-xPbI3Precursor liquid, wherein x is the amount score of substance, and x is 0.05~0.45.
7. liquid phase preparation process as claimed in claim 5, which is characterized in that in step 2), by FTO electro-conductive glass through ultrasonic clear
It washes and is put into the TiCl that concentration is 0.03~0.10mol/L after drying up450~80 DEG C of 20~50min of processing of aqueous solution, then again
Respectively with after deionized water and washes of absolute alcohol, it is placed in 10~40min of calcining on 400~500 DEG C of warm tables, forms nanometer
TiO2Electron transfer layer, to obtain transparent conducting glass/electron transfer layer membrane electrode.
8. liquid phase preparation process as claimed in claim 5, which is characterized in that in step 3), passed in transparent conducting glass/electronics
Spin coating TiO on defeated layer film electrode2Slurry after dry, is placed in after being heat-treated 8~12min on 150~250 DEG C of warm tables, from
So it is cooled to room temperature；Spin coating ZrO again2Slurry after dry, is placed in after being heat-treated 25~35min on 450~600 DEG C of warm tables,
Cooled to room temperature, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer film electrode.
9. the liquid phase preparation process as described in claim 5 or 8, which is characterized in that in step 4), by the electrically conducting transparent glass of preparation
Glass/electron transfer layer/mesoporous layer/insulating support layer film electrode is placed on warm table after preheating, and mixed-cation calcium titanium is added dropwise
Mine (FA)x(MA)1-xPbI3Precursor liquid carry out spin coating, be placed on 80~110 DEG C of warm tables, heat and keep the temperature crystallization 10~
70min, mixed-cation perovskite (FA)x(MA)1-xPbI3Precursor liquid is on the gap and surface of mesoporous layer and insulating support layer
Crystallization, to obtain transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode.
10. liquid phase preparation process as claimed in claim 5, which is characterized in that in step 5),
It scratches and leads on transparent conducting glass/electron transfer layer/mesoporous layer/insulating support layer/perovskite active layer membrane electrode
After electrical carbon slurry, in 90~110 DEG C of 5~30min of solidification, hydrophobicity carbon electrode is formed, to obtain the perovskite sun of high stable
It can battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112303A (en) * | 2019-04-09 | 2019-08-09 | 深圳市华星光电半导体显示技术有限公司 | Organic light emitting diode device |
| CN110867519A (en) * | 2019-11-26 | 2020-03-06 | 吉林大学 | Light emitting diode and preparation method thereof |
| CN111477747A (en) * | 2020-04-30 | 2020-07-31 | 兰州理工大学 | Perovskite solar cell with zirconium oxide passivated tin oxide as electron transport layer and method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150122314A1 (en) * | 2012-05-18 | 2015-05-07 | Isis Innovation Limited | Optoelectronic device comprising porous scaffold material and perovskites |
| CN106654020A (en) * | 2017-01-24 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Bulk-heterojunction perovskite thin film, production method thereof and solar cell |
| CN106784317A (en) * | 2016-11-29 | 2017-05-31 | 宁波大学 | The manufacture method of the perovskite solar cell of super-thin electronic transmission Rotating fields |
| US20170162811A1 (en) * | 2014-07-11 | 2017-06-08 | Ecole Polytechnique Federale De Lausanne (Epfl) | Template enhanced organic inorganic perovskite heterojunction photovoltaic device |
| US20170243699A1 (en) * | 2014-09-10 | 2017-08-24 | Oxford Photovoltaics Limited | Mixed organic-inorganic perovskite formulations |
| CN107464882A (en) * | 2017-06-26 | 2017-12-12 | 中国科学院广州能源研究所 | A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof |
| CN108269918A (en) * | 2016-12-31 | 2018-07-10 | 中国科学院上海硅酸盐研究所 | Porous perovskite thin film, carbon pastes and the solar cell based on carbon electrode |
| US20180218845A1 (en) * | 2017-01-30 | 2018-08-02 | Hairen TAN | Contact passivation for perovskite optoelectronics |
-
2018
- 2018-10-12 CN CN201811189629.XA patent/CN109326721B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150122314A1 (en) * | 2012-05-18 | 2015-05-07 | Isis Innovation Limited | Optoelectronic device comprising porous scaffold material and perovskites |
| US20170162811A1 (en) * | 2014-07-11 | 2017-06-08 | Ecole Polytechnique Federale De Lausanne (Epfl) | Template enhanced organic inorganic perovskite heterojunction photovoltaic device |
| US20170243699A1 (en) * | 2014-09-10 | 2017-08-24 | Oxford Photovoltaics Limited | Mixed organic-inorganic perovskite formulations |
| CN106784317A (en) * | 2016-11-29 | 2017-05-31 | 宁波大学 | The manufacture method of the perovskite solar cell of super-thin electronic transmission Rotating fields |
| CN108269918A (en) * | 2016-12-31 | 2018-07-10 | 中国科学院上海硅酸盐研究所 | Porous perovskite thin film, carbon pastes and the solar cell based on carbon electrode |
| CN106654020A (en) * | 2017-01-24 | 2017-05-10 | 中国科学院上海硅酸盐研究所 | Bulk-heterojunction perovskite thin film, production method thereof and solar cell |
| US20180218845A1 (en) * | 2017-01-30 | 2018-08-02 | Hairen TAN | Contact passivation for perovskite optoelectronics |
| CN107464882A (en) * | 2017-06-26 | 2017-12-12 | 中国科学院广州能源研究所 | A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LI Y , ZHAO L , WEI S , ET AL.: "Effect of ZrO2 film thickness on the photoelectric properties of mixed-cation perovskite solar cells", 《APPLIED SURFACE SCIENCE》 * |
| XIAO M , ZHAO L , WEI S , ET AL.: "Application of mixed-organic-cation for high performance hole-conductor-free perovskite solar cells", 《JOURNAL OF COLLOID & INTERFACE SCIENCE》 * |
| 魏寿彬: "FA1-xMAxPbI3钙钛矿在碳基无空穴传输层结构太阳能电池中的应用研究", 《中国优秀硕士论文全文库工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112303A (en) * | 2019-04-09 | 2019-08-09 | 深圳市华星光电半导体显示技术有限公司 | Organic light emitting diode device |
| CN110867519A (en) * | 2019-11-26 | 2020-03-06 | 吉林大学 | Light emitting diode and preparation method thereof |
| CN111477747A (en) * | 2020-04-30 | 2020-07-31 | 兰州理工大学 | Perovskite solar cell with zirconium oxide passivated tin oxide as electron transport layer and method |
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