CN108511610A - A kind of spraying perovskite preparation method of solar battery and device entirely - Google Patents
A kind of spraying perovskite preparation method of solar battery and device entirely Download PDFInfo
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- CN108511610A CN108511610A CN201810232410.7A CN201810232410A CN108511610A CN 108511610 A CN108511610 A CN 108511610A CN 201810232410 A CN201810232410 A CN 201810232410A CN 108511610 A CN108511610 A CN 108511610A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/08—Plant for applying liquids or other fluent materials to objects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/08—Plant for applying liquids or other fluent materials to objects
- B05B5/087—Arrangements of electrodes, e.g. of charging, shielding, collecting electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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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 invention discloses a kind of full spraying perovskite preparation method of solar battery, including sequentially carrying out the electrostatic spraying of electron transfer layer slurry and sintering, mesoporous layer slurry electrostatic spraying and sintering, the electrostatic spraying of wall slurry and sintering, the electrostatic spraying of carbon-coating slurry and sintering in conductive substrates, electron transfer layer, mesoporous layer, wall and carbon-coating are made successively；Then perovskite precursor liquid electrostatic spraying is carried out on carbon-coating, so that perovskite precursor liquid is penetrated into mesoporous layer and wall under electrostatic field and gravity, perovskite solar cell is obtained after drying.The invention also discloses a kind of full spraying perovskite solar cell preparation facilities, including electrostatic field generator, alternating electric field generator, atomizer and heating platform.The present invention has carried out carrying out subsequent processing using electrostatic field, alternating electric field after spraying each functional layer, and the uniformity of each functional layer is made to be obviously improved.
Description
Technical field
The present invention relates to a kind of full spraying perovskite preparation method of solar battery and devices, belong to photovoltaic technology field.
Background technology
The peak efficiency of perovskite solar cell by 2009 3.8% it is rapid be promoted to 2016 22.1%,
Efficiency has reached application requirement, but perovskite material, to moisture-sensitive, the unstable disadvantage of efficiency prevents its industrialization development.
Carbon-based structure battery is because having higher stability and lower manufacturing cost, and industrial prospect is preferable, and 2016 yearly efficiencies have reached
To 15.3%, however large area component (effective area：74cm2) efficiency only 10%, this mainly collects difficult and big face by electronics
Caused by crystallizing the factors such as poor in product, the large area of perovskite solution is crystallized without relative special-purpose equipment, calcium titanium ore bed at present
It prepares and is mainly carried out by spraying or drop coating perovskite precursor liquid mode.
Disclosed on December 11st, 2013 Chinese patent database one it is entitled " based on perovskite light absorbent
The patent application of mesoscopic solar cells and preparation method thereof ", application No. is：201310297115.7 specially disclosing：Make
Carbon-based PSC is prepared with all print mode, meso-porous nano crystal layer, wall and hole collection layer are prepared using mode of printing, sintering
Temperature is at 400-500 DEG C.Preparation method is complex；Secondly calcium titanium ore bed prepared using drop coating mode, perovskite crystalline by
The multifactor impacts such as the pore size of mesoporous layer, wall and carbon-coating, it is difficult to more excellent crystal is obtained, especially in large area preparation
This difficulty becomes apparent, and to obtain preferable calcium titanium ore bed crystal, the aperture of carbon-coating is larger, sacrifices partially electronically conductive property, shadow
The collection in hole is rung.
Invention content
It is an object of the invention to overcome deficiency in the prior art, a kind of full spraying perovskite solar cell system is provided
Preparation Method and device, solve in the prior art in perovskite solar cell calcium titanium ore bed in carbon-coating, wall and mesoporous layer
Uneven, the technical issues of being difficult to obtain more excellent crystal.
In order to solve the above technical problems, used by full spraying perovskite preparation method of solar battery provided by the invention
Technical solution is：Including horizontally disposed heating platform, perpendicular to heating platform setting electrostatic field, be parallel to heating platform
Alternating electric field；The preparation method includes the following steps：
Conductive substrates are placed on heating platform, the electrostatic field perpendicular to heating platform are opened, in conductive substrates upper surface
Sequentially carry out the electrostatic spraying of electron transfer layer slurry and sintering, mesoporous layer slurry electrostatic spraying and sintering, wall slurry electrostatic
Spraying and sintering, carbon-coating slurry electrostatic spraying and sintering, are sequentially prepared electron transfer layer, mesoporous layer, wall and carbon-coating；
Perovskite precursor liquid electrostatic spraying is carried out to conductive substrates obtained above, makes calcium under electrostatic field and gravity
Titanium ore precursor liquid penetrates into mesoporous layer and wall, obtains perovskite solar cell.
Further, it prepares electron transfer layer the specific method is as follows：
By the electron transfer layer slurry electrostatic spraying after atomization in conductive substrates；
The maximum intensity for two groups of alternating electric fields for being parallel to heating platform is adjusted to 20~500V/cm, frequency is adjusted to
50~400Hz is opened and is adjusted alternating electric field in place simultaneously to the mechanical shake of conductive substrates progress of spraying electron transfer layer slurry
Dynamic processing, is closed after keeping 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens and adjusts in place
Electrostatic field, the surface temperature for controlling heating platform are 300~500 DEG C, and the conductive substrates to spraying electron transfer layer slurry are sintered
30~120min.
Further, it needs to be handled as follows respectively after the mesoporous layer slurry of electrostatic spraying, wall slurry and carbon-coating slurry：
The maximum intensity for two groups of alternating electric fields for being parallel to heating platform is adjusted to 200~1000V/cm, frequency is adjusted
For 50~400Hz, opens and adjust alternating electric field in place simultaneously to the functional layer progress mechanical shock processing after spraying slurry, protect
It is closed after holding 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens and adjusts in place
Electrostatic field, the surface temperature for controlling heating platform are 200~600 DEG C, and 30~120min is sintered to the functional layer after spraying slurry.
Further, it needs to be handled as follows after spraying perovskite precursor liquid：
The maximum intensity for two groups of alternating electric fields for being parallel to heating platform is adjusted to 20~1000V/cm, frequency is adjusted to
50~100Hz opens the alternating electric field of adjusting in place and is carried out at mechanical shock to the conductive substrates after spraying perovskite precursor liquid
Reason is closed after keeping 10~60s；
Adjusting is 500~2000V/cm perpendicular to the electrostatic field intensity of heating platform, opens the electrostatic field adjusted in place, room
Temperature stands 10-20min, and the surface temperature for then controlling heating platform is 30~100 DEG C, to leading after spraying perovskite precursor liquid
Electric substrate is sintered 30~120min.
Further, it needs to pre-process conductive substrates before the electrostatic spraying of electron transfer layer slurry, specific method is：
The electron transfer layer slurry solid content is 0.5-3%, and bulk composition is titanium dioxide, zinc oxide, tin oxide, oxygen
It is 3-10% to change niobium, one or more mixtures in barium stannate, the mesoporous layer slurry solid content, and bulk composition is titanium dioxide
One or more mixtures in titanium, zinc oxide, tin oxide, niobium oxide, barium stannate；The wall slurry is solid content 3-
10%, bulk composition is one or more mixing in zirconium oxide, silica, aluminium oxide, indium oxide, gallium oxide, cadmium sulfide
Object；The carbon-coating slurry solid content is 3-10%, and bulk composition is carbon black, graphite, graphene, one kind in carbon nanotube or more
Kind mixture；The calcium titanium ore bed is with perovskite structure ABX3Crystal as main body, wherein A is CH3NH3 +, B Pb2 +, X is
I-、Br-Or Cl-In it is one or more, perovskite forerunner's fluid solid content be 5-30%.
The present invention also provides a kind of full spraying perovskite solar cell preparation facilities, including electrostatic field generator, friendship
Power transformation field generator, for by the atomizer of solution to be sprayed or slurry atomization and horizontally disposed heating platform, the mist
Change nozzle to be set to above heating platform；Two voltage output ends of the electrostatic field generator are separately connected upper flat plate electrode, lower flat
Plate electrode, the lower plate electrode are close to the upper working face setting of heating platform；There are two the alternating electric field generator settings,
Two voltage output ends of one of alternating electric field generator are separately connected left plate electrode and right plate electrode, another alternation electricity
Plate electrode and rear plate electrode before two voltage output ends of field generator are separately connected.
Further, the bottom of the heating platform is additionally provided with shaking device.
Further, the shaking device using can rapid starting/stopping vibrator, the vibrator uses linear motor.
Further, it is additionally provided with level(l)ing device on the heating platform.
Compared with prior art, the advantageous effect of the invention reached is：
Material is sprayed on electrically-conductive backing plate in the way of electrostatic spraying, by the electrostatic field, parallel for opening upper and lower directions
In two alternating electric fields and shaking device of table top, hence it is evident that improve the uniformity of each functional layer, can get more excellent interlayer
Interfacial contact is conducive to the transmission of electronics and hole；
By shaking device with the electrostatic field perpendicular to conductive substrates/heating platform direction, it can be achieved that perovskite precursor liquid
Quick fully penetrated in porous layer；
With drying course, the Gibbs free energy of material system can be changed in the presence of electrostatic field for sintering, is conducive to regulation and control knot
Crystalline state；The presence of electrostatic field makes compacted zone be contacted closely with mesoporous layer nano particle, realizes quick electron-transport；
Description of the drawings
Fig. 1 is the structural schematic diagram of full spraying perovskite solar cell preparation facilities provided by the invention；
Fig. 2 is heating platform and each plate electrode in full spraying perovskite solar cell preparation facilities provided by the invention
Location diagram；
In figure：1, shaking device；2, heating platform；31, upper flat plate electrode；32, lower plate electrode；33, upper and lower electrostatic field
Generator, 41, left plate electrode；42, right plate electrode；43, left and right directions alternating electric field generator；51, preceding plate electrode；
52, rear plate electrode；53, front-rear direction alternating electric field generator；6, atomizer.
Specific implementation mode
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention
Technical solution, and not intended to limit the protection scope of the present invention.
As shown in Figure 1 and Figure 2, it is full spraying perovskite solar cell preparation facilities provided by the invention, including electrostatic field
Generator, alternating electric field generator, for by the atomizer of solution to be sprayed or slurry atomization and horizontally disposed heated flat
Platform, atomizer are set to above heating platform.Two voltage output ends of electrostatic field generator are separately connected upper flat plate electrode, lower flat
Plate electrode, lower plate electrode are close to the upper working face setting of heating platform.The bottom of heating platform is additionally provided with shaking device, vibrations
Device using can rapid starting/stopping vibrator, vibrator use linear motor.There are two the settings of alternating electric field generator, wherein one
A is left and right directions alternating electric field generator, and two voltage output ends are separately connected left plate electrode and right plate electrode；It is another
A is front-rear direction alternating electric field generator, plate electrode and rear plate electrode before two voltage output ends are separately connected.
In order to ensure the lower plate electrode holding for being close to the upper working face setting of heating platform is horizontal, also set on heating platform
There is level(l)ing device.
Heating platform is using pre-oxidation nickel chromium triangle electrothermal alloy heater strip.It is arranged for ease of temperature monitoring, on heating platform more
A temperature sensor, to carry out multi-point Temperature Collection.
Electric field strength between each plate electrode can be by changing the distance between two plate electrodes and adjusting electric field
The output voltage of device is realized.
Each plate electrode is using the copper plate electrode Jing Guo polishing treatment.
The present invention also provides a kind of full spraying perovskite preparation method of solar battery, which can be used above-mentioned
Preparation facilities is realized, is specifically comprised the following steps：
Step 1：Conductive substrates are pre-processed：
Use deionized water, acetone, ethyl alcohol to be cleaned by ultrasonic conductive substrates successively, after nitrogen drying using UVO at
15min is managed, is positioned on heating platform；
Step 2：It is prepared by electron transfer layer：
The electric field strength that will be perpendicular to the electrostatic field of heating platform is adjusted to 2000-4000V/cm, opens and adjusts in place
Electrostatic field, by the electron transfer layer slurry electrostatic spraying after atomization in conductive substrates；
The maximum intensity for the alternating electric field for being parallel to heating platform is adjusted to 20~500V/cm, frequency is adjusted to 50~
400Hz is opened and is adjusted at conductive substrates progress mechanical shock of the alternating electric field in place simultaneously to spraying electron transfer layer slurry
Reason is closed after keeping 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens and adjusts in place
Electrostatic field, the surface temperature for controlling heating platform are 300~500 DEG C, and the conductive substrates to spraying electron transfer layer slurry are sintered
30~120min.
Electron transfer layer slurry solid content is 0.5-3%, and bulk composition is titanium dioxide, zinc oxide, tin oxide, oxidation
One or more mixtures in niobium, barium stannate and corresponding dopant.
Step 3：It is prepared by mesoporous layer：
The electric field strength that will be perpendicular to the electrostatic field of heating platform is adjusted to 2000-4000V/cm, opens and adjusts in place
Electrostatic field, by the mesoporous layer slurry electrostatic spraying after atomization on the electron transfer layer obtained by step 2；
The maximum intensity for the alternating electric field for being parallel to heating platform is adjusted to 200~1000V/cm, frequency is adjusted to 50
~400Hz opens the alternating electric field adjusted in place while being carried out at mechanical shock to the conductive base after the mesoporous layer slurry of spraying
Reason is closed after keeping 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens and adjusts in place
Electrostatic field, the surface temperature for controlling heating platform are 200~600 DEG C, to the conductive base sintering 30 after the mesoporous layer slurry of spraying
~120min.
The mesoporous layer slurry solid content be 3-10%, bulk composition be titanium dioxide, zinc oxide, tin oxide, niobium oxide,
One or more mixtures in barium stannate and corresponding dopant.
Step 4：It is prepared by wall：
The electric field strength that will be perpendicular to the electrostatic field of heating platform is adjusted to 2000-4000V/cm, opens and adjusts in place
Electrostatic field, by the wall slurry electrostatic spraying after atomization on the mesoporous layer obtained by step 3；
The maximum intensity for the alternating electric field for being parallel to heating platform is adjusted to 200~1000V/cm, frequency is adjusted to 50
~400Hz opens the alternating electric field adjusted in place while being carried out at mechanical shock to the conductive base after spraying wall slurry
Reason is closed after keeping 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens and adjusts in place
Electrostatic field, the surface temperature for controlling heating platform are 200~600 DEG C, to the conductive base sintering 30 after spraying wall slurry
~120min.
The wall slurry be solid content 3-10%, bulk composition be zirconium oxide, silica, aluminium oxide, indium oxide,
One or more mixtures in gallium oxide, cadmium sulfide and corresponding dopant.
Step 5：It is prepared by carbon-coating：
The electric field strength that will be perpendicular to the electrostatic field of heating platform is adjusted to 2000-4000V/cm, opens and adjusts in place
Electrostatic field, by the carbon-coating slurry electrostatic spraying after atomization on the wall obtained by step 4；
The maximum intensity for the alternating electric field for being parallel to heating platform is adjusted to 200~1000V/cm, frequency is adjusted to 50
~400Hz opens the alternating electric field adjusted in place while carrying out mechanical shock processing to the conductive base after spraying carbon-coating slurry,
It is closed after keeping 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens and adjusts in place
Electrostatic field, control heating platform surface temperature be 200~600 DEG C, to spraying carbon-coating slurry after conductive base sintering 30~
120min。
The carbon-coating slurry solid content is 3-10%, and bulk composition is carbon black, graphite, graphene, carbon nanotube and corresponding
Dopant in one or more mixtures..
Step 6：Spray perovskite precursor liquid：
The electric field strength that will be perpendicular to the electrostatic field of heating platform is adjusted to 2000-4000V/cm, opens and adjusts in place
Electrostatic field, by the perovskite precursor liquid electrostatic spraying after atomization on the carbon-coating obtained by step 5；
The maximum intensity for the alternating electric field for being parallel to heating platform is adjusted to 20~1000V/cm, frequency is adjusted to 50~
100Hz is opened and is adjusted alternating electric field in place to the conductive substrates progress mechanical shock processing after spraying perovskite precursor liquid, protects
It is closed after holding 10~60s；
Adjusting is 500~2000V/cm perpendicular to the electrostatic field intensity of heating platform, opens the electrostatic field adjusted in place, room
Temperature stands 10-20min, and the surface temperature for then controlling heating platform is 30~100 DEG C, to leading after spraying perovskite precursor liquid
Electric substrate is sintered 30~120min.
The calcium titanium ore bed is with perovskite structure ABX3Crystal as main body, wherein A is CH3NH3 +, B Pb2 +, X is
I-、Br-Or Cl-In it is one or more, perovskite forerunner's fluid solid content be 5-30%.
Full spraying perovskite preparation method of solar battery provided by the invention is done into one with reference to specific embodiment
Step is described in detail.
Embodiment one：
1. conductive substrates pre-process
Conductive substrates are used successively deionized water, acetone, ethyl alcohol are cleaned by ultrasonic 15min respectively, is used after nitrogen drying
UVO handles 15min, is positioned on heating platform.Conductive substrates use FTO substrates.
2. prepared by electron transfer layer
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 2500V/cm, by 0.5% TiO2It causes
Close layer solution electrostatic spraying opens shaking device 1 on FTO substrates, adjusts setting left plate electrode 41 and right plate electrode 42
Between alternating electric field frequency be 100Hz, maximum intensity 30V/cm, adjust setting before handed between plate electrode 51 and rear plate electrode 52
Power transformation field frequencies range is 100Hz, maximum intensity 30V/cm, while opening shaking device 1, is closed after keeping 10s；Adjust 31 and 32
Between electrostatic field intensity be 300V/cm, be warming up to 450 DEG C sintering 30min.
3. prepared by mesoporous layer
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 3500V/cm, by solid content 3%TiO2
Mesoporous layer slurry is sprayed on 2. obtained electron transfer layer, opens shaking device 1, adjust setting left plate electrode 41 with it is right
42 alternating electric field frequencies of plate electrode are 100Hz, maximum intensity 500V/cm, and plate electrode 51 is put down with rear before adjusting setting
52 alternating electric field frequencies of plate electrode are 100Hz, maximum intensity 500V/cm, while opening shaking device 1, are closed after keeping 10s
It closes；It is 300V/cm to adjust electrostatic field intensity between upper flat plate electrode 31 and lower plate electrode 32, and 30min is kept the temperature at 450 DEG C.
4. prepared by wall
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 4500V/cm, by solid content 3%ZrO2
Mesoporous layer slurry is sprayed on 3. obtained mesoporous layer, opens shaking device 1, adjusts setting left plate electrode 41 and right tablet
42 alternating electric field frequencies of electrode are 200Hz, maximum intensity 500V/cm, adjust plate electrode 51 and rear plate electricity before setting
The alternating electric field frequency of pole 52 is 200Hz, maximum intensity 500V/cm, while opening shaking device 1, is closed after keeping 10s；
It is 300V/cm to adjust electrostatic field intensity between upper flat plate electrode 31 and lower plate electrode 32, and 30min is kept the temperature at 400 DEG C.
5. prepared by carbon-coating
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 800V/cm, by the carbon-coating of solid content 3%
Slurry electrostatic spraying opens shaking device 1 on 4. obtained wall, adjusts setting left plate electrode 41 and right tablet electricity
The alternating electric field frequency of pole 42 is 60Hz, maximum intensity 500V/cm, adjusts plate electrode 51 and rear plate electrode 52 before setting
Between alternating electric field frequency be 60Hz, maximum intensity 500V/cm, while opening shaking device 1, closed after keeping 10s；In adjusting
Electrostatic field intensity is 300V/cm between plate electrode 31 and lower plate electrode 32, and 30min is kept the temperature at 400 DEG C.
6. spraying perovskite precursor liquid
It is 500V/cm to adjust and open upper and lower directions electrostatic field intensity, by 10% perovskite precursor liquid electrostatic spraying in temperature
Degree is adjusted on 30 DEG C of 5. obtained carbon-coating, to open shaking device 1 between setting left plate electrode 41 and right plate electrode 42
Alternating electric field frequency is 100Hz, maximum intensity 800V/cm, is handed between plate electrode 51 and rear plate electrode 52 before adjusting setting
Power transformation field frequencies range is 100Hz, maximum intensity 800V/cm, while opening shaking device 1, is closed after keeping 30s；It is put down in adjusting
Electrostatic field intensity is 1500V/cm between plate electrode 31 and lower plate electrode 32, is stored at room temperature 20min, 30min is dried at 50 DEG C.
Embodiment two：
1. conductive substrates pre-process
Conductive substrates are used successively deionized water, acetone, ethyl alcohol are cleaned by ultrasonic 15min respectively, is used after nitrogen drying
UVO handles 15min, is positioned on heating platform.Conductive substrates use FTO substrates.
2. prepared by electron transfer layer
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 2500V/cm, by 3% SnO2It is fine and close
Layer solution electrostatic spraying opens shaking device 1 on FTO substrates, adjusts between setting left plate electrode 41 and right plate electrode 42
Alternating electric field frequency is 100Hz, maximum intensity 300V/cm, is handed between plate electrode 51 and rear plate electrode 52 before adjusting setting
Power transformation field frequencies range is 100Hz, maximum intensity 300V/cm, while opening shaking device 1, is closed after keeping 10s；Adjust 31 with
32 electrostatic field intensities are 300V/cm, are warming up to 500 DEG C of sintering 30min.
3. prepared by mesoporous layer
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 3500V/cm, by solid content 3%TiO2
Mesoporous layer slurry is sprayed on 2. obtained electron transfer layer, opens shaking device 1, adjust setting left plate electrode 41 with it is right
42 alternating electric field frequencies of plate electrode are 100Hz, maximum intensity 300V/cm, and plate electrode 51 is put down with rear before adjusting setting
52 alternating electric field frequencies of plate electrode are 100Hz, maximum intensity 300V/cm, while opening shaking device 1, are closed after keeping 10s
It closes；It is 300V/cm to adjust electrostatic field intensity between upper flat plate electrode 31 and lower plate electrode 32, and 30min is kept the temperature at 450 DEG C.
4. prepared by wall
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 4500V/cm, by solid content 3%Al2O3
Mesoporous layer slurry is sprayed on 3. obtained mesoporous layer, opens shaking device 1, adjusts setting left plate electrode 41 and right tablet
42 alternating electric field frequencies of electrode are 200Hz, maximum intensity 300V/cm, adjust plate electrode 51 and rear plate electricity before setting
The alternating electric field frequency of pole 52 is 200Hz, maximum intensity 300V/cm, while opening shaking device 1, is closed after keeping 10s；
It is 300V/cm to adjust electrostatic field intensity between upper flat plate electrode 31 and lower plate electrode 32, and 30min is kept the temperature at 400 DEG C.
5. prepared by carbon-coating
Set between upper flat plate electrode 31 and lower plate electrode 32 that electrostatic field intensity is 800V/cm, by the carbon-coating of solid content 3%
Slurry electrostatic spraying opens shaking device 1 on 4. obtained wall, adjusts setting left plate electrode 41 and right tablet electricity
The alternating electric field frequency of pole 42 is 60Hz, maximum intensity 500V/cm, adjusts plate electrode 51 and rear plate electrode 52 before setting
Between alternating electric field frequency be 60Hz, maximum intensity 500V/cm, while opening shaking device 1, closed after keeping 10s；In adjusting
Electrostatic field intensity is 300V/cm between plate electrode 31 and lower plate electrode 32, and 30min is kept the temperature at 400 DEG C.
6. spraying perovskite precursor liquid
It is 500V/cm to adjust and open upper and lower directions electrostatic field intensity, by 10% perovskite precursor liquid electrostatic spraying in temperature
Degree is adjusted on 30 DEG C of 5. obtained carbon-coating, to open shaking device 1 between setting left plate electrode 41 and right plate electrode 42
Alternating electric field frequency is 100Hz, maximum intensity 800V/cm, is handed between plate electrode 51 and rear plate electrode 52 before adjusting setting
Power transformation field frequencies range is 100Hz, maximum intensity 800V/cm, while opening shaking device 1, is closed after keeping 50s；It is put down in adjusting
Electrostatic field intensity is 2000V/cm between plate electrode 31 and lower plate electrode 32, is stored at room temperature 20min, 50min is dried at 50 DEG C.
The present invention replaces mode of printing to realize that in carbon-based perovskite battery prepared by each layer using spraying method, shaking device with
Two alternating electric fields of horizontal direction may make the slurry after spraying more smooth uniform, and the electrostatic field of upper and lower directions may make spray
Slurry after painting realizes outstanding interfacial contact with lower layer, and in addition the electrostatic field of upper and lower directions can not only realize perovskite precursor liquid
Fully penetrated, the Gibbs free energy of also changeable perovskite precursor liquid system is easy to realize crystallization control over a large area.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of full spraying perovskite preparation method of solar battery, including horizontally disposed heating platform, perpendicular to heated flat
The electrostatic field of platform setting, the alternating electric field for being parallel to heating platform；It is characterized in that, the preparation method includes the following steps：
Conductive substrates are placed on heating platform, open perpendicular to heating platform electrostatic field, conductive substrates upper surface sequentially
Carry out the electrostatic spraying of electron transfer layer slurry and sintering, mesoporous layer slurry electrostatic spraying and sintering, wall slurry electrostatic spraying
And sintering, the electrostatic spraying of carbon-coating slurry and sintering, it is sequentially prepared electron transfer layer, mesoporous layer, wall and carbon-coating；
Perovskite precursor liquid electrostatic spraying is carried out to conductive substrates obtained above, makes perovskite under electrostatic field and gravity
Precursor liquid penetrates into mesoporous layer and wall, obtains perovskite solar cell.
2. full spraying perovskite preparation method of solar battery according to claim 1, which is characterized in that prepare electronics biography
The specific method is as follows for defeated layer：
By the electron transfer layer slurry electrostatic spraying after atomization in conductive substrates；
The maximum intensity for two groups of alternating electric fields for being parallel to heating platform is adjusted to 20~500V/cm, frequency is adjusted to 50~
400Hz is opened and is adjusted at conductive substrates progress mechanical shock of the alternating electric field in place simultaneously to spraying electron transfer layer slurry
Reason is closed after keeping 10~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens the electrostatic adjusted in place
, control heating platform surface temperature be 300~500 DEG C, to spray electron transfer layer slurry conductive substrates sintering 30~
120min。
3. full spraying perovskite preparation method of solar battery according to claim 1 or 2, which is characterized in that electrostatic
It needs to be handled as follows respectively after applying mesoporous layer slurry, wall slurry and carbon-coating slurry：
The maximum intensity for two groups of alternating electric fields for being parallel to heating platform is adjusted to 200~1000V/cm, frequency is adjusted to 50
~400Hz opens and adjusts alternating electric field in place simultaneously to the functional layer progress mechanical shock processing after spraying slurry, keeps 10
It is closed after~60s；
The maximum intensity that will be perpendicular to the electrostatic field of heating platform is adjusted to 300~1000V/cm, opens the electrostatic adjusted in place
, the surface temperature for controlling heating platform is 200~600 DEG C, and 30~120min is sintered to the functional layer after spraying slurry.
4. full spraying perovskite preparation method of solar battery according to claim 3, which is characterized in that spraying perovskite
It needs to be handled as follows after precursor liquid：
The maximum intensity for two groups of alternating electric fields for being parallel to heating platform is adjusted to 20~1000V/cm, frequency is adjusted to 50~
100Hz is opened and is adjusted alternating electric field in place to the conductive substrates progress mechanical shock processing after spraying perovskite precursor liquid, protects
It is closed after holding 10~60s；
Adjusting is 500~2000V/cm perpendicular to the electrostatic field intensity of heating platform, opens the electrostatic field adjusted in place, and room temperature is quiet
10-20min is set, the surface temperature for then controlling heating platform is 30~100 DEG C, to the conductive base after spraying perovskite precursor liquid
Bottom is sintered 30~120min.
5. full spraying perovskite preparation method of solar battery according to claim 3, which is characterized in that electron transfer layer
It needs to pre-process conductive substrates before slurry electrostatic spraying, specific method is：
It is cleaned by ultrasonic using deionized water, acetone, ethyl alcohol, UVO processing is carried out after being dried up using nitrogen.
6. full spraying perovskite preparation method of solar battery according to claim 3, which is characterized in that the electronics passes
Defeated layer slurry solid content is 0.5-3%, and bulk composition is one in titanium dioxide, zinc oxide, tin oxide, niobium oxide, barium stannate
Kind or a variety of mixtures, the mesoporous layer slurry solid content be 3-10%, bulk composition be titanium dioxide, zinc oxide, tin oxide,
One or more mixtures in niobium oxide, barium stannate；The wall slurry is solid content 3-10%, and bulk composition is oxidation
One or more mixtures in zirconium, silica, aluminium oxide, indium oxide, gallium oxide, cadmium sulfide；The carbon-coating slurry contains admittedly
Amount is 3-10%, and bulk composition is one or more mixtures in carbon black, graphite, graphene, carbon nanotube；The perovskite
Layer is with perovskite structure ABX3Crystal as main body, wherein A is CH3NH3 +, B Pb2 +, X I-、Br-Or Cl-In one kind or
A variety of, perovskite forerunner's fluid solid content is 5-30%.
7. a kind of full spraying perovskite solar cell preparation facilities, which is characterized in that including electrostatic field generator, alternating electric field
Generator, for by the atomizer of solution to be sprayed or slurry atomization and horizontally disposed heating platform, the atomizer
Above heating platform；Two voltage output ends of the electrostatic field generator are separately connected upper flat plate electrode, lower plate electrode,
The lower plate electrode is close to the upper working face setting of heating platform；There are two the alternating electric field generator settings, wherein one
Two voltage output ends of a alternating electric field generator are separately connected left plate electrode and right plate electrode, and another alternating electric field occurs
Plate electrode and rear plate electrode before two voltage output ends of device are separately connected.
8. full spraying perovskite solar cell preparation facilities according to claim 7, which is characterized in that the heated flat
The bottom of platform is additionally provided with shaking device.
9. full spraying perovskite solar cell preparation facilities according to claim 8, which is characterized in that the vibrations dress
Set using can rapid starting/stopping vibrator, the vibrator use linear motor.
10. the full spraying perovskite solar cell preparation facilities according to claim 7 or 8 or 9, which is characterized in that institute
It states and is additionally provided with level(l)ing device on heating platform.
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