CN108987581A - A kind of automatically cleaning perovskite solar battery and preparation method thereof - Google Patents

A kind of automatically cleaning perovskite solar battery and preparation method thereof Download PDF

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Publication number
CN108987581A
CN108987581A CN201810825715.9A CN201810825715A CN108987581A CN 108987581 A CN108987581 A CN 108987581A CN 201810825715 A CN201810825715 A CN 201810825715A CN 108987581 A CN108987581 A CN 108987581A
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layer
cleaning
preparation
precursor liquid
perovskite
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罗伟
任辉彩
庞茂印
李雁鸿
胡臻玉
曹原
张江峰
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Valiant Co Ltd
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Valiant Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4213Comprising organic semiconductor-inorganic semiconductor hetero-junctions
    • H01L51/422Majority carrier devices using sensitisation of widebandgap semiconductors, e.g. TiO2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/44Details of devices
    • H01L51/448Passivation, containers, encapsulations
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Abstract

The present invention discloses a kind of automatically cleaning perovskite solar battery and preparation method thereof, the perovskite solar battery includes the glass substrate being cascading from top to bottom, preceding electrode, hole transmission layer, perovskite absorbed layer, electron transfer layer, buffer layer, metal electrode layer, unlike the prior art, self-cleaning layer is set in the glass substrate upper surface, the self-cleaning layer is TiO2Film layer or doped with Yb3+、Er3+、Ho3+Or Tm3+The TiO of upper conversion ions2Film layer.Self-cleaning layer has photocatalytic and photic Superhydrophilic, and photocatalytic can degrade the organic pollutant of solar cell surface, and photic Superhydrophilic can make solar battery wash away the dust on surface using natural rain.

Description

A kind of automatically cleaning perovskite solar battery and preparation method thereof
Technical field
The invention belongs to photovoltaic material fields, and in particular to a kind of automatically cleaning perovskite solar battery and its preparation side Method.
Background technique
Solar battery has many advantages, such as that environmentally protective, energy storage is abundant, is known as most promising green energy resource.In recent years Coming, the development of hybrid inorganic-organic perovskite solar battery is very rapid, and photoelectric conversion efficiency has reached 22% or so, and Perovskite solar battery raw material sources are abundant, and simple process, cost is relatively low, can be prepared into flexible battery, has obtained academia With the extensive attention of industrial circle.
The Chinese invention patent of Publication No. CN10710891A disclose a kind of wide spectrum perovskite solar battery and its Preparation method, the wide spectrum perovskite solar battery include the FTO glass substrate being cascading, TiO2Compacted zone, TiO2 Porous luminescent layer, perovskite light-absorption layer, hole transmission layer and metal electrode, the TiO2In porous luminescent layer containing doping from Son, the Doped ions include Yb3+With other ions, other described ions include IIo3+、Er3+、 Mn2+. Tm3+In at least It is a kind of.The invention by using doping TiO2Porous luminescent layer utilizes the TiO with the characteristics of luminescence2Nano particle is more to prepare Aperture layer, while adulterating Yb3+ 、IIo3+、Er3+、 Mn2+Or Tm3+Ion can effectively be inhaled as electron transfer layer and light conversion layer The infrared light and ultraviolet light that cannot be absorbed by perovskite material are received, visible light is converted into, to be absorbed by perovskite material, mentions The photoelectric current and transfer efficiency of high battery.The absorption spectrum of perovskite solar battery can be effectively widened, the perovskite sun is improved It can cell light electric current and transfer efficiency.
But solar battery in use process, inevitably covers dust or organic pollutant, causes to penetrate outdoors Rate reduces, and reduces the generating efficiency of solar battery, and non-uniform pollutant will cause hot spot effect, and battery is caused to be scrapped.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of automatically cleaning perovskite solar battery preparation method letters It is single, the photoelectric properties of solar battery can be effectively improved, industrial demand is suitable for.
The technical scheme to solve the above technical problems is that a kind of automatically cleaning perovskite solar battery, including The glass substrate that is cascading from top to bottom, preceding electrode, hole transmission layer, perovskite absorbed layer, electron transfer layer, buffering Automatically cleaning is arranged in the glass substrate upper surface unlike the prior art in layer, metal electrode layer, film and/or backboard Layer, the self-cleaning layer are TiO2Film layer or doped with Yb3+、Er3+、Ho3+Or Tm3+The TiO of upper conversion ions2Film layer.
Further, further include film and backboard under the metal electrode layer, the self-cleaning layer with a thickness of 20- 300nm。
Further, the glass substrate is flexible and transparent material substitution.
Titanium dioxide (TiO2) there is photocatalytic and photic Superhydrophilic, photocatalytic can degrade solar battery table The organic pollutant in face, and photic Superhydrophilic can make solar battery wash away the dust on surface using natural rain.Simultaneously Upper conversion particles are adulterated in titanium dioxide, solar battery nonabsorbable infrared light in part can be converted to it is absorbable can It is light-exposed, improve the photoelectric conversion efficiency of battery.The present invention also provides the preparation method of this automatically cleaning perovskite solar battery, The following steps are included:
A, the processing of conductive substrates: the glass of electrode or flexible organic transparent substrates start the cleaning processing for use before being integrated with;
B, the preparation of self-cleaning layer: acetylacetone,2,4-pentanedione and butyl titanate are added drop-wise in the alcohol under magnetic agitation, dense nitre is then added dropwise Acid-conditioning solution pH to 2-5 is aged 0.5-10h after stirring, obtains TiO2Solution, as the first precursor liquid;Step A is obtained Glass or flexible and transparent material substrate deviate from the side of preceding electrode layer upward, are coated with first precursor liquid, and coating finishes, into The processing of row heating anneal, cooled to room temperature obtain the glass or flexible and transparent material lining of the film layer coated with self-cleaning layer Bottom;
C, the preparation of hole transmission layer: by NiOxUltrasonic disperse in solvent is added in nano particle, is configured to NiOxSuspension, as Second precursor liquid;It is again that oneself of the glass of the obtained film layer coated with self-cleaning layer of step B or flexible and transparent material substrate is clear Clean layer is coated with second precursor liquid downward, in another side, and coating finishes, progress heating anneal processing, cooled to room temperature, Hole transmission layer is formed in the another side of glass or flexible and transparent material substrate;
D, the preparation of perovskite absorbed layer: lead halide and halogenated methyl amine are dissolved in organic solvent, are configured to third precursor liquid, And stirring and dissolving, perovskite precursor liquid is obtained, perovskite precursor liquid is coated on the hole transmission layer of step C formation, and Perovskite absorbed layer is obtained after making annealing treatment in heating plate;Wherein, lead halide is PbCl2 、PbBr2Or PbI2One of or Two kinds;Halogenated methyl amine is CH3NH3Cl、CH3NH3Br or CH3NH3One of I;
E, the preparation of electron transfer layer: fullerene derivate is dissolved in chlorobenzene, and heating stirring dissolves to obtain the 4th precursor liquid, The 4th obtained precursor liquid is coated on the perovskite absorbed layer that step D is obtained, and is obtained after making annealing treatment on hot plate Electron transfer layer;
F, the preparation of buffer layer: BCP is added in methanol, obtains supersaturated solution, and be applied to the electron-transport that step E is obtained On layer, buffer layer is obtained after then making annealing treatment on hot plate;
G, the preparation of metal electrode layer: buffering made from step F is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 Au, Ag or Al is deposited in Pa or more on buffer-layer surface, forms metal electrode layer;
H, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, packaging plastic is successively spread Piece repaves upper backboard, heat lamination when having backboard.
As further preferred, in stepb, by ytterbium nitrate Yb(NO3)3With erbium nitrate Er(NO3)3, ytterbium nitrate Yb (NO3)3With holmium nitrate Ho(NO3)3Or ytterbium nitrate Yb(NO3)3With thulium nitrate Tm(NO3)3The TiO is added2It is stirred in solution molten Solution, obtains doped with ytterbium ion Yb3+With erbium ion Er3+、Yb3+With holmium ion Ho3+Or Yb3+With thulium ion Tm3+TiO2Solution, As the first precursor liquid, foreign atom number Yb:Ti=15-25:100, Er:Ti=2-5:100, Ho:Ti=2-5:100, Tm:Ti =2-5:100。
As further preferred, in stepb, acetylacetone,2,4-pentanedione and butyl titanate volume ratio are 1:2-5, and the alcohol is second The volume ratio of the mixture of one or more of alcohol, isopropanol, n-butanol, the butyl titanate and alcohol is 5-20:100;Institute The temperature for stating heating anneal processing is 400-600 DEG C.
As further preferred,
In step, cleaning method is to be cleaned by ultrasonic 10-30min with glass cleaning agent solution respectively, and deionized water ultrasound is clear It washes twice, each 10-30min, ethyl alcohol cleans twice, each 10-30min, and acetone ultrasonic cleaning is primary, 10-30min, nitrogen Drying;
In step C, the solvent is deionized water, ethyl alcohol or n-butanol;Heating anneal temperature is 100-200 DEG C, and the time is 10-30min;
In step D, the organic solvent is the mixed solution of DMF, DMSO or both;Lead ion in the third precursor liquid Molar concentration is 0.5-2 mol/L;In the perovskite precursor liquid, CH3NH3X and PbX2Molar ratio be 1:1-3:1;Heating plate At 100-120 DEG C, annealing time is controlled in 10-30min for temperature control;
In step E, the solution temperature control is at 40-50 DEG C, and at 60-80 DEG C, annealing time is controlled for temperature of heating plate control In 10-30min;The fullerene derivate is PC61BM、PC71BM, ICBA or bis-PC61BM;The fullerene derivate exists Mass-volume concentration in 4th precursor liquid is 10-20 mg/mL;
In step F, at 60-80 DEG C, annealing time is controlled in 10-30min for the temperature of heating plate control;
In steph, encapsulation film is EVA or PVB, backboard PET, PET composite material or glass;The hot lamination temperature is 80-120 DEG C, the heat lamination time is 10-40min.
As further preferred,
In stepb, the thicknesses of layers of the self-cleaning layer is controlled in 20-300nm;
In step C, the thicknesses of layers of the hole transmission layer is controlled in 5-30nm;
In step D, the thicknesses of layers of the perovskite absorbed layer is controlled in 400-500nm;
In step E, the thicknesses of layers of the electron transfer layer is controlled in 50-80nm;
In step F, the thicknesses of layers of the buffer layer is controlled in 10-15nm;
In step G, the thicknesses of layers of the metal electrode layer is controlled in 70-200nm.
The beneficial effects of the present invention are:
The present invention increases titanium dioxide TiO in perovskite solar cell surface2Self-cleaning layer, titanium dioxide TiO2It is urged with light The property changed and photic Superhydrophilic, photocatalytic can degrade the organic pollutant of solar cell surface, and photic Superhydrophilic Solar battery can be made to wash away the dust on surface using natural rain.The light absorption of perovskite solar battery can be effectively improved Rate improves photoelectric conversion efficiency, and reduces hot spot effect odds.Simultaneously in titanium dioxide TiO2Conversion in middle doping Grain, can be converted to absorbable visible light for the nonabsorbable infrared light of part solar battery, improve the photoelectric conversion of battery Efficiency.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.
Embodiment one
A kind of perovskite solar battery, including successively transparent flexible organic or glass substrate 1, TiO2Self-cleaning layer, 2, soft The organic or glass substrate of property, 3, preceding electrode, 4, hole transmission layer, 5, perovskite absorbed layer, 6, electron transfer layer, 7, buffer layer, 8, metal electrode, 9, film, 10, backboard.Its specific preparation step is as follows:
A, the processing of conductive substrates: substrate selects flexible RF magnetron sputtering (PEI, PEN, PET, PI flexible plexiglass) or common glass Glass substrate, the sheet resistance of preceding electrode layer (FTO or ITO) are 5-40 Ω, transmitance 75-90%.Conductive substrates clean glass cleaner Solution is cleaned by ultrasonic 10-30min, and twice, 10-30min is each for cleaning ultrasonic cleaning, and ethyl alcohol cleans twice, and 10-30min is each, Acetone is cleaned by ultrasonic 10-30min, is dried with nitrogen;
B、TiO2The preparation of layer: 5mL acetylacetone,2,4-pentanedione and 10mL butyl titanate are added drop-wise in the 100mL ethyl alcohol under magnetic agitation, Then concentrated nitric acid is added dropwise and adjusts PH to 3, sealing and standing is aged 6h after stirring 3h, obtains TiO2Colloidal sol is as the first precursor liquid.It will Electrode is placed in down on spin coating machine table top before the above-mentioned conductive substrates handled well, and the first precursor liquid is added dropwise and carries out spin coating, speed 3000rpm, time 30s are spent, then 300-500 DEG C of annealing 2h, obtains TiO2Layer;
C, the preparation of hole transmission layer: ultrasonic disperse in 1ml deionized water is added in nickel oxide nanoparticle 3mg and for 24 hours, is configured to Uniform suspension is as the second precursor liquid.Electrode before the above-mentioned conductive substrates handled well is placed in spin coating machine table top up On, the second precursor liquid is added dropwise and carries out spin coating, speed 2000rpm, time 30s, then 100-200 DEG C of annealing 10-20min, obtains Fine and close NiOxHole transmission layer;
D, perovskite absorbed layer (CH3NH3PbX, X=Cl, Br, I) preparation: by molar ratio be 1:1-3:1 CH3NH3X and PbX2It is dissolved in the mixed solution of DMF or DMSO or both, is configured to the third precursor liquid that molar concentration is 0.5-2 mol/L, Then 4 h of stirring and dissolving forms perovskite precursor liquid.Above-mentioned third precursor liquid is spin-coated on NiOxOn hole transmission layer, spin coating Speed is 6000rpm, time 30s, and then anneal at 80-100 DEG C 10-30 min, and the perovskite for forming 400-500 nm is inhaled Receive layer;
E, the preparation of electron transfer layer: by PC61BM is dissolved in anhydrous chlorobenzene, is configured to the 4th precursor liquid of 10-20 mg/mL, Stirring and dissolving 3-4 h at 40-50 DEG C.By above-mentioned PC61The chlorobenzene solution of BM is spin-coated on perovskite absorbed layer, and spin speed is 1500rpm, time 30s, 70 DEG C of 10 min of annealing form the PC of 50-80 nm thickness61BM electron transfer layer;
F, the preparation of BCP buffer layer: on the electron transport layer by the methanol saturated solution spin coating of BCP, 70 DEG C of 10 min of annealing, shape Film forming layer with a thickness of 10-15 nm BCP buffer layer;
G, the preparation of metal electrode: the above-mentioned substrate prepared is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 Pa More than, 100 nm Ag are deposited, forms Ag electrode, completes the preparation of entire perovskite solar battery;
H, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, PVB glue is successively spread Piece and PET backboard, 90 DEG C of lamination 30min.
Embodiment two
A kind of perovskite solar battery, including successively transparent flexible organic or glass substrate 1, TiO2Self-cleaning layer, 2, soft The organic or glass substrate of property, 3, preceding electrode, 4, hole transmission layer, 5, perovskite absorbed layer, 6, electron transfer layer, 7, buffer layer, 8, metal electrode, 9, film, 10, backboard.Its specific preparation step is as follows:
A, the processing of conductive substrates: substrate selects flexible RF magnetron sputtering (PEI, PEN, PET, PI flexible glass) or simple glass lining Bottom, the sheet resistance of preceding electrode layer (FTO or ITO) are 5-40 Ω, transmitance 75-90%.Conductive substrates clean glass cleaning agent solution It is cleaned by ultrasonic 10-30min, twice, 10-30min is each, and ethyl alcohol is washed twice, and 10-30min is each for cleaning ultrasonic cleaning, and third Ketone is cleaned by ultrasonic 10-30min, is dried with nitrogen;
B、TiO2The preparation of layer: 5mL acetylacetone,2,4-pentanedione and 10mL butyl titanate are added drop-wise in the 100mL ethyl alcohol under magnetic agitation, Then concentrated nitric acid is added dropwise and adjusts PH to 3, by a certain amount of ytterbium nitrate Yb(NO3)3With erbium nitrate Er(NO3)3TiO is added2In solution Stirring and dissolving, wherein Yb:Ti=20:100, Er:Ti=3:100, sealing and standing is aged 6h after stirring 3h, obtain doped with ytterbium from Sub- Yb3+With erbium ion Er3+TiO2Solution is as the first precursor liquid.Electrode before the above-mentioned conductive substrates handled well is put down It is placed on spin coating machine table top, the above TiO is added dropwise2Colloidal sol carries out spin coating, then speed 3000rpm, time 30s are moved back for 300-500 DEG C Fiery 2h, obtains TiO2Layer;
C, the preparation of hole transmission layer: ultrasonic disperse in 1ml deionized water is added in nickel oxide nanoparticle 3mg and for 24 hours, is configured to Uniform suspension is as the second precursor liquid.Electrode before the above-mentioned conductive substrates handled well is placed in spin coating machine table top up On, above second precursor liquid is added dropwise and carries out spin coating, speed 2000rpm, time 30s, then 100-200 DEG C of annealing 10-20min, Obtain fine and close NiOxHole transmission layer;
D, perovskite absorbed layer (CH3NH3PbX, X=Cl, Br, I) preparation: by molar ratio be 1:1-3:1 CH3NH3X and PbX2It is dissolved in the mixed solution of DMF or DMSO or both, is configured to the third precursor liquid that molar concentration is 0.5-2 mol/L, Then 4 h of stirring and dissolving forms perovskite precursor liquid.Above-mentioned third precursor liquid is spin-coated on NiOxOn hole transmission layer, spin coating Speed is 6000rpm, time 30s, and then anneal at 80-100 DEG C 10-30 min, and the perovskite for forming 400-500 nm is inhaled Receive layer;
E, the preparation of electron transfer layer: by PC61BM is dissolved in anhydrous chlorobenzene, is configured to the 4th precursor liquid of 10-20 mg/mL, Stirring and dissolving 3-4 h at 40-50 DEG C.By above-mentioned PC61The chlorobenzene solution of BM is spin-coated on perovskite absorbed layer, and spin speed is 1500rpm, time 30s, 70 DEG C of 10 min of annealing form the PC of 50-80 nm thickness61BM electron transfer layer;
F, the preparation of BCP buffer layer: on the electron transport layer by the methanol saturated solution spin coating of BCP, 70 DEG C of 10 min of annealing, shape Film forming layer with a thickness of 10-15 nm BCP buffer layer;
G, the preparation of metal electrode: the above-mentioned substrate prepared is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 Pa More than, 100 nm Ag are deposited, forms Ag electrode, completes the preparation of entire perovskite solar battery;
H, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, PVB glue is successively spread Piece and PET backboard, 90 DEG C of lamination 30min.
Embodiment three
A kind of perovskite solar battery, including successively transparent flexibility or glass substrate 1, TiO2Self-cleaning layer, 2, flexibility has Machine or glass substrate, 3, preceding electrode, 4, hole transmission layer, 5, perovskite absorbed layer, 6, electron transfer layer, 7, buffer layer, 8, gold Belong to electrode, 9, film, 10, backboard.Its specific preparation step is as follows:
A, the processing of conductive substrates: substrate selects flexible RF magnetron sputtering (PEI, PEN, PET, PI flexible glass) or simple glass lining Bottom, the sheet resistance of preceding electrode layer (FTO or ITO) are 5-40 Ω, transmitance 75-90%.Conductive substrates clean glass cleaning agent solution It is cleaned by ultrasonic 10-30min, twice, 10-30min is each, and ethyl alcohol is washed twice, and 10-30min is each for cleaning ultrasonic cleaning, and third Ketone is cleaned by ultrasonic 10-30min, is dried with nitrogen;
B、TiO2The preparation of layer: 5mL acetylacetone,2,4-pentanedione and 10mL butyl titanate are added drop-wise in the 100mL ethyl alcohol under magnetic agitation, Then concentrated nitric acid is added dropwise and adjusts PH to 3, by a certain amount of ytterbium nitrate Yb(NO3)3With holmium nitrate IONS OF H o(NO3)3TiO is added2It is molten Stirring and dissolving in liquid, wherein Yb:Ti=25:100, Ho:Ti=5:100, sealing and standing is aged 6h after stirring 3h, obtain doped with Ytterbium ion Yb3+With erbium ion Ho3+TiO2Solution is as the first precursor liquid.By electrode surface court before the above-mentioned conductive substrates handled well Under be placed on spin coater table top, above first precursor liquid is added dropwise and carries out spin coating, speed 3000rpm, time 30s, then 300- 500 DEG C of annealing 2h, obtain TiO2Layer;
C, the preparation of hole transmission layer: ultrasonic disperse in 1ml deionized water is added in nickel oxide nanoparticle 3mg and for 24 hours, is configured to Uniform suspension is as the second precursor liquid.Electrode before the above-mentioned conductive substrates handled well is placed in spin coating machine table top up On, above second precursor liquid is added dropwise and carries out spin coating, speed 2000rpm, time 30s, then 100-200 DEG C of annealing 10-20min, Obtain fine and close NiOxHole transmission layer;
D, perovskite absorbed layer (CH3NH3PbX, X=Cl, Br, I) preparation: by molar ratio be 1:1-3:1 CH3NH3X and PbX2It is dissolved in the mixed solution of DMF or DMSO or both, is configured to the solution that molar concentration is 0.5-2 mol/L.Then it stirs 4 h of dissolution are mixed, the perovskite precursor liquid of formation is as third precursor liquid.Above-mentioned third precursor liquid is spin-coated on NiOxHole transport On layer, spin speed 6000rpm, time 30s, then anneal at 80-100 DEG C 10-30 min, forms 400-500 nm's Perovskite absorbed layer;
E, the preparation of electron transfer layer: by PC61BM is dissolved in anhydrous chlorobenzene, is configured to the 4th precursor liquid of 10-20 mg/mL, Stirring and dissolving 3-4 h at 40-50 DEG C.By above-mentioned PC61The chlorobenzene solution of BM is spin-coated on perovskite absorbed layer, and spin speed is 1500rpm, time 30s, 70 DEG C of 10 min of annealing form the PC of 50-80 nm thickness61BM electron transfer layer;
F, the preparation of BCP buffer layer: on the electron transport layer by the methanol saturated solution spin coating of BCP, 70 DEG C of 10 min of annealing, shape Film forming layer with a thickness of 10-15 nm BCP buffer layer;
G, the preparation of metal electrode: the above-mentioned substrate prepared is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 Pa More than, 100 nm Ag are deposited, forms Ag electrode, completes the preparation of entire perovskite solar battery;
H, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, PVB glue is successively spread Piece and PET backboard, 90 DEG C of lamination 30min.
Example IV
A kind of perovskite solar battery, including successively transparent flexible organic or glass substrate 1, TiO2Self-cleaning layer, 2, soft The organic or glass substrate of property, 3, preceding electrode, 4, hole transmission layer, 5, perovskite absorbed layer, 6, electron transfer layer, 7, buffer layer, 8, metal electrode, 9, film, 10, backboard.Its specific preparation step is as follows:
A, the processing of conductive substrates: substrate selects flexible RF magnetron sputtering (PEI, PEN, PET, PI flexible glass) or simple glass lining Bottom, the sheet resistance of preceding electrode layer (FTO or ITO) are 5-40 Ω, transmitance 75-90%.Conductive substrates clean glass cleaning agent solution It is cleaned by ultrasonic 10-30min, twice, 10-30min is each, and ethyl alcohol is washed twice, and 10-30min is each for cleaning ultrasonic cleaning, and third Ketone is cleaned by ultrasonic 10-30min, is dried with nitrogen;
B、TiO2The preparation of layer: 5mL acetylacetone,2,4-pentanedione and 10mL butyl titanate are added drop-wise in the 100mL ethyl alcohol under magnetic agitation, Then concentrated nitric acid is added dropwise and adjusts PH to 3, by a certain amount of ytterbium nitrate Yb(NO3)3With nitric acid thulium ion Tm(NO3)3TiO is added2It is molten Stirring and dissolving in liquid, wherein Tm:Ti=15:100, Ho:Ti=2:100, sealing and standing is aged 6h after stirring 3h, obtain doped with Ytterbium ion Yb3+With thulium ion Tm3+TiO2Solution is as the first precursor liquid.By electrode surface court before the above-mentioned conductive substrates handled well Under be placed on spin coater table top, above first precursor liquid is added dropwise and carries out spin coating, speed 3000rpm, time 30s, then 300- 500 DEG C of annealing 2h, obtain TiO2Layer;
C, the preparation of hole transmission layer: ultrasonic disperse in 1ml deionized water is added in nickel oxide nanoparticle 3mg and for 24 hours, is configured to Uniform suspension is as the second precursor liquid.Electrode before the above-mentioned conductive substrates handled well is placed in spin coating machine table top up On, above second precursor liquid is added dropwise and carries out spin coating, speed 2000rpm, time 30s, then 100-200 DEG C of annealing 10-20min, Obtain fine and close NiOxHole transmission layer;
D, perovskite absorbed layer (CH3NH3PbX, X=Cl, Br, I) preparation: by molar ratio be 1:1-3:1 CH3NH3X and PbX2It is dissolved in the mixed solution of DMF or DMSO or both, is configured to the third precursor liquid that molar concentration is 0.5-2 mol/L, Then 4 h of stirring and dissolving forms perovskite precursor liquid.Above-mentioned perovskite precursor liquid is spin-coated on NiOxOn hole transmission layer, rotation Painting speed is 6000rpm, time 30s, and then anneal at 80-100 DEG C 10-30 min, forms the perovskite of 400-500 nm Absorbed layer;
E, the preparation of electron transfer layer: by PC61BM is dissolved in anhydrous chlorobenzene, is configured to the 4th precursor liquid of 10-20 mg/mL, Stirring and dissolving 3-4 h at 40-50 DEG C.By above-mentioned PC61The chlorobenzene solution of BM is spin-coated on perovskite absorbed layer, and spin speed is 1500rpm, time 30s, 70 DEG C of 10 min of annealing form the PC of 50-80 nm thickness61BM electron transfer layer;
F, the preparation of BCP buffer layer: on the electron transport layer by the methanol saturated solution spin coating of BCP, 70 DEG C of 10 min of annealing, shape Film forming layer with a thickness of 10-15 nm BCP buffer layer;
G, the preparation of metal electrode: the above-mentioned substrate prepared is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 Pa More than, 100 nm Ag are deposited, forms Ag electrode, completes the preparation of entire perovskite solar battery;
H, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, PVB glue is successively spread Piece and PET backboard, 90 DEG C of lamination 30min.
Embodiment five (no self-cleaning layer perovskite solar battery)
A kind of perovskite solar battery, including successively 1, flexible organic or glass substrate, 2, preceding electrode, 3, hole transmission layer, 4, perovskite absorbed layer, 5, electron transfer layer, 6, buffer layer, 7, metal electrode, 8, film, 9, backboard, Conducting Glass choosing For FTO electro-conductive glass, its specific preparation step is as follows:
A, the processing of FTO Conducting Glass: the sheet resistance of the FTO in FTO Conducting Glass is 14 Ω, transmitance 90%, lining It is spare after the cleaning of bottom;
B, the preparation of hole transmission layer: ultrasonic disperse in 1ml deionized water is added in nickel oxide nanoparticle 3mg and for 24 hours, is configured to Uniform suspension is as the first precursor liquid.Electrode before the above-mentioned conductive substrates handled well is placed in spin coating machine table top up On, the above suspension is added dropwise and carries out spin coating, speed 2000rpm, time 30s, then 100-200 DEG C of annealing 10-20min, obtains Fine and close NiOxHole transmission layer 3;
C, the preparation of perovskite absorbed layer: the CH for being 0.95:1 by molar ratio3NH3I and PbI2It is dissolved in DMF solution, stirring and dissolving 4h is configured to the second precursor liquid, wherein PbI2Concentration in the second precursor liquid is 1.8mol/L, and the second precursor liquid is spin-coated on NiOxOn hole transmission layer, spin speed 6000rpm, time 30s, then anneal at 105 DEG C 10 min, obtains perovskite Absorbed layer 4, with a thickness of 495nm;
D, the preparation of electron transfer layer: by PC61BM is dissolved in anhydrous chlorobenzene, is configured to the third precursor liquid of 20 mg/mL, and 45 DEG C Lower stirring and dissolving 4h.By above-mentioned PC61The chlorobenzene solution of BM is spin-coated on perovskite absorbed layer, spin speed 1500rpm, the time 30s, 70 DEG C of 10 min of annealing form PC61BM electron transfer layer 5;
E, the preparation of BCP buffer layer: by the addition 10ml methanol of 30mg BCP, it is prepared into supersaturated solution, supernatant is taken to revolve It applies on the electron transport layer, 70 DEG C of 10 min of annealing form BCP buffer layer 6, with a thickness of 8nm;
F, the preparation of metal electrode layer: the above-mentioned substrate prepared is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 100 nm Ag are deposited in Pa or more, form Ag electrode layer 7;
G, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, PVB glue is successively spread Piece and PET backboard, 90 DEG C of lamination 30min.
Implementation result: carrying out electrical testing after device is placed in open air one month, during this period without taking device progress Artificial cleaning.Solar simulator is opened, irradiation level is set between 0.9990-1.0010, solar battery is placed on hot spot Central area, connection solar battery are tested with IC tester.Electrical data is obtained as shown in following table one:
Table one
As can be seen from the table, the open-circuit voltage (Voc) of perovskite solar battery prepared by four embodiments, short circuit current (Jsc) and fill factor (FF) is all higher, especially short circuit current (Jsc), significantly larger than battery prepared by conventional method Short circuit current (Jsc) increases titanium dioxide TiO in perovskite solar cell surface2Self-cleaning layer, photocatalytic can drop The organic pollutant of solar cell surface is solved, and photic Superhydrophilic can make solar battery wash away table using natural rain The dust in face.The absorptivity of perovskite solar battery can be effectively improved, photoelectric conversion efficiency is improved.Simultaneously in titanium dioxide TiO2Solar battery nonabsorbable infrared light in part can be converted to absorbable visible light by conversion particles in middle doping, Improve the photoelectric conversion efficiency of battery.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of automatically cleaning perovskite solar battery, including be cascading from top to bottom glass substrate, preceding electrode, it is empty Cave transport layer, perovskite absorbed layer, electron transfer layer, buffer layer, metal electrode layer, which is characterized in that in the glass substrate Self-cleaning layer is arranged in upper surface, and the self-cleaning layer is TiO2Film layer or in TiO2In doped with Yb3+And Er3+、Yb3+And Ho3+Or Yb3+And Tm3+The film layer of ion.
2. a kind of automatically cleaning perovskite solar battery according to claim 1, which is characterized in that the metal electrode layer Under further include film and/or backboard, the self-cleaning layer with a thickness of 20-300nm.
3. a kind of automatically cleaning perovskite solar battery according to claim 1, which is characterized in that the glass substrate is Flexible organic transparent substitution.
4. a kind of preparation method of automatically cleaning perovskite solar battery, which comprises the following steps:
A, the processing of conductive substrates: the glass of electrode or flexible organic transparent substrates start the cleaning processing for use before being integrated with;
B, the preparation of self-cleaning layer: acetylacetone,2,4-pentanedione and butyl titanate are added drop-wise in the alcohol under magnetic agitation, dense nitre is then added dropwise Acid-conditioning solution pH to 2-5 is aged 0.5-10h after stirring, obtains TiO2Solution, as the first precursor liquid;Step A is obtained The side that glass or flexible organic transparent substrates deviate from preceding electrode layer upward, is coated with first precursor liquid, and coating finishes, into The processing of row heating anneal, cooled to room temperature obtain the glass or flexible organic transparent lining of the film layer coated with self-cleaning layer Bottom;
C, the preparation of hole transmission layer: by NiOxUltrasonic disperse in solvent is added in nano particle, is configured to NiOxSuspension, as Second precursor liquid;It is again that oneself of the glass of the obtained film layer coated with self-cleaning layer of step B or flexible organic transparent substrates is clear Clean layer is coated with second precursor liquid downward, in another side, and coating finishes, progress heating anneal processing, cooled to room temperature, Hole transmission layer is formed in the another side of glass or flexible organic transparent substrates;
D, the preparation of perovskite absorbed layer: lead halide and halogenated methyl amine are dissolved in organic solvent, are configured to third precursor liquid, And stirring and dissolving, perovskite precursor liquid is obtained, perovskite precursor liquid is coated on the hole transmission layer of step C formation, and Perovskite absorbed layer is obtained after making annealing treatment in heating plate;Wherein, lead halide is PbCl2 、PbBr2Or PbI2One of or Two kinds;Halogenated methyl amine is CH3NH3Cl、CH3NH3Br or CH3NH3One of I;
E, the preparation of electron transfer layer: fullerene derivate is dissolved in chlorobenzene, and heating stirring dissolves to obtain the 4th precursor liquid, The 4th obtained precursor liquid is coated on the perovskite absorbed layer that step D is obtained, and is obtained after making annealing treatment on hot plate Electron transfer layer;
F, the preparation of buffer layer: BCP is added in methanol, obtains supersaturated solution, and be applied to the electron-transport that step E is obtained On layer, buffer layer is obtained after then making annealing treatment on hot plate;
G, the preparation of metal electrode layer: buffering made from step F is placed in vacuum evaporation room, vacuum degree reaches 1 × 10-4 Au, Ag or Al is deposited in Pa or more on buffer-layer surface, forms metal electrode layer;
H, the encapsulation of device: the device electrode layer that step G is obtained is placed into upward on lamination machine table top, packaging plastic is successively spread Piece repaves upper backboard, heat lamination when having backboard.
5. a kind of preparation method of automatically cleaning perovskite solar battery according to claim 4, which is characterized in that in step In B, by ytterbium nitrate Yb(NO3)3With erbium nitrate Er(NO3)3, ytterbium nitrate Yb(NO3)3With holmium nitrate Ho(NO3)3Or ytterbium nitrate Yb (NO3)3With thulium nitrate Tm(NO3)3The TiO is added2Stirring and dissolving in solution is obtained doped with ytterbium ion Yb3+And erbium ion Er3+、Yb3+With holmium ion Ho3+Or Yb3+With thulium ion Tm3+TiO2Solution, as the first precursor liquid, foreign atom number Yb:Ti= 15-25:100, Er:Ti=2-5:100, Ho:Ti=2-5:100, Tm:Ti=2-5:100.
6. a kind of preparation method of automatically cleaning perovskite solar battery according to claim 4, which is characterized in that in step In B, acetylacetone,2,4-pentanedione and butyl titanate volume ratio are 1:2-5, and the alcohol is one of ethyl alcohol, isopropanol, n-butanol or several The volume ratio of the mixture of kind, the butyl titanate and alcohol is 5-20:100;The temperature of the heating anneal processing is 400-600 ℃。
7. a kind of preparation method of automatically cleaning perovskite solar battery according to claim 4, which is characterized in that
In step, cleaning method is to be cleaned by ultrasonic 10-30min with glass cleaning agent solution respectively, and deionized water ultrasound is clear It washes twice, each 10-30min, ethyl alcohol cleans twice, each 10-30min, and acetone ultrasonic cleaning is primary, 10-30min, nitrogen Drying;
In step C, the solvent is deionized water, ethyl alcohol or n-butanol;Heating anneal temperature is 100-200 DEG C, and the time is 10-30min;
In step D, the organic solvent is the mixed solution of DMF, DMSO or both;Lead ion in the third precursor liquid Molar concentration is 0.5-2 mol/L;In the perovskite precursor liquid, CH3NH3X and PbX2Molar ratio be 1:1-3:1;Heating plate At 100-120 DEG C, annealing time is controlled in 10-30min for temperature control;
In step E, the solution temperature control is at 40-50 DEG C, and at 60-80 DEG C, annealing time is controlled for temperature of heating plate control In 10-30min;The fullerene derivate is PC61BM、PC71BM, ICBA or bis-PC61BM;The fullerene derivate exists Mass-volume concentration in 4th precursor liquid is 10-20 mg/mL;
In step F, at 60-80 DEG C, annealing time is controlled in 10-30min for the temperature of heating plate control;
In steph, encapsulation film is EVA or PVB, backboard PET, PET composite material or glass;The hot lamination temperature is 80-120 DEG C, the heat lamination time is 10-40min.
8. a kind of preparation method of automatically cleaning perovskite solar battery according to claim 4, which is characterized in that
In stepb, the thicknesses of layers of the self-cleaning layer is controlled in 20-300nm;
In step C, the thicknesses of layers of the hole transmission layer is controlled in 5-30nm;
In step D, the thicknesses of layers of the perovskite absorbed layer is controlled in 400-500nm;
In step E, the thicknesses of layers of the electron transfer layer is controlled in 50-80nm;
In step F, the thicknesses of layers of the buffer layer is controlled in 10-15nm;
In step G, the thicknesses of layers of the metal electrode layer is controlled in 70-200nm.
CN201810825715.9A 2018-07-25 2018-07-25 A kind of automatically cleaning perovskite solar battery and preparation method thereof Pending CN108987581A (en)

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