CN108511610B - Preparation method and device of full-spraying perovskite solar cell - Google Patents

Preparation method and device of full-spraying perovskite solar cell Download PDF

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CN108511610B
CN108511610B CN201810232410.7A CN201810232410A CN108511610B CN 108511610 B CN108511610 B CN 108511610B CN 201810232410 A CN201810232410 A CN 201810232410A CN 108511610 B CN108511610 B CN 108511610B
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heating platform
plate electrode
spraying
adjusting
slurry
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CN108511610A (en
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朱同波
文贵华
张继远
叶金花
刘建国
吴聪萍
邹志刚
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KUNSHAN SUNLAITE NEW ENERGY CO Ltd
Kunshan Innovation Institute of Nanjing University
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KUNSHAN SUNLAITE NEW ENERGY CO Ltd
Kunshan Innovation Institute of Nanjing University
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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
    • 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
    • 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
    • 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
    • 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
    • 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 preparation method of a full-spraying perovskite solar cell, which comprises the steps of sequentially carrying out electrostatic spraying and sintering of electron transport layer slurry, electrostatic spraying and sintering of mesoporous layer slurry, electrostatic spraying and sintering of spacer layer slurry and electrostatic spraying and sintering of carbon layer slurry on a conductive substrate to sequentially prepare an electron transport layer, a mesoporous layer, a spacer layer and a carbon layer; and then carrying out electrostatic spraying on the perovskite precursor solution on the carbon layer, enabling the perovskite precursor solution to permeate into the mesoporous layer and the spacing layer under the action of an electrostatic field and gravity, and drying to obtain the perovskite solar cell. The invention also discloses a device for preparing the full-spraying perovskite solar cell, which comprises an electrostatic field generator, an alternating field generator, an atomizing nozzle and a heating platform. After the functional layers are sprayed, the subsequent treatment is carried out by adopting an electrostatic field and an alternating electric field, so that the uniformity of the functional layers is obviously improved.

Description

Preparation method and device of full-spraying perovskite solar cell
Technical Field
The invention relates to a preparation method and a device of a full-spraying perovskite solar cell, and belongs to the technical field of photovoltaics.
Background
The maximum efficiency of the perovskite solar cell is rapidly increased from 3.8% in 2009 to 22.1% in 2016, and the efficiency reaches the application requirement, but the defects that the perovskite material is sensitive to moisture and unstable in efficiency prevent the industrial development of the perovskite material. The carbon-based structure battery has high stability and low preparation cost, the industrialization prospect is good, the efficiency in 2016 reaches 15.3%, but the efficiency of a large-area assembly (effective area: 74cm2) is only 10%, which is mainly caused by factors such as difficulty in collecting electrons and poor crystallization on a large area, at present, large-area crystallization of perovskite solution has no relevant special equipment, and perovskite layer preparation is mainly carried out by spraying or dripping perovskite precursor liquid.
A patent application named as a mesoscopic solar cell based on perovskite light absorption materials and a preparation method thereof is disclosed in a patent database of China 12 months and 11 days in 2013, and the application numbers are as follows: 201310297115.7, specifically discloses: the carbon-based PSC is prepared by a full printing mode, the mesoporous nanocrystalline layer, the spacing layer and the hole collecting layer are prepared by a printing mode, and the sintering temperature is 400-500 ℃. The preparation method is more complex; secondly, the perovskite layer is prepared in a dripping mode, perovskite crystals are influenced by multiple factors such as the pore sizes of the mesoporous layer, the spacing layer and the carbon layer, better crystals are difficult to obtain, the difficulty is more obvious particularly in large-area preparation, and in order to obtain better perovskite layer crystals, the pore sizes of the carbon layer are larger, partial conductivity is sacrificed, and the collection of cavities is influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a preparation method and a device of a full-spraying perovskite solar cell, and solves the technical problems that in the perovskite solar cell in the prior art, a perovskite layer is uneven in a carbon layer, a spacing layer and a mesoporous layer, and a better crystal is difficult to obtain.
In order to solve the technical problem, the invention provides a preparation method of a full-spraying perovskite solar cell, which comprises a heating platform, an electrostatic field, an alternating electric field and a vibration device, wherein the heating platform is horizontally arranged, the electrostatic field is vertical to the heating platform, the alternating electric field is parallel to the heating platform, and the vibration device is arranged at the bottom of the heating platform; the preparation method comprises the following steps:
placing a conductive substrate on a heating platform, starting an electrostatic field vertical to the heating platform, and sequentially performing electrostatic spraying and sintering of electron transport layer slurry, electrostatic spraying and sintering of mesoporous layer slurry, electrostatic spraying and sintering of spacer layer slurry and electrostatic spraying and sintering of carbon layer slurry on the upper surface of the conductive substrate to sequentially prepare an electron transport layer, a mesoporous layer, a spacer layer and a carbon layer;
performing electrostatic spraying of the perovskite precursor solution on the conductive substrate, and enabling the perovskite precursor solution to permeate into the mesoporous layer and the spacing layer under the action of an electrostatic field and gravity to obtain the perovskite solar cell;
the preparation method further comprises the following steps: and simultaneously starting an alternating electric field and a vibration device which are parallel to the heating platform after each slurry is electrostatically sprayed and before sintering.
Further, the specific method for preparing the electron transport layer is as follows:
electrostatically spraying the atomized electron transport layer slurry on a conductive substrate;
adjusting the highest intensity of two groups of alternating electric fields parallel to the heating platform to be 20-500V/cm, adjusting the frequency to be 50-400 Hz, starting the alternating electric fields which are adjusted in place, simultaneously carrying out mechanical vibration treatment on the conductive substrate sprayed with the electronic transmission layer slurry, and closing the conductive substrate after keeping the time of 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 300-500 ℃, and sintering the conductive substrate sprayed with the electronic transmission layer slurry for 30-120 min.
Further, after the dielectric layer slurry, the spacer layer slurry and the carbon layer slurry are electrostatically sprayed, the following treatments are respectively required:
adjusting the highest intensity of two groups of alternating electric fields parallel to the heating platform to be 200-1000V/cm, adjusting the frequency to be 50-400 Hz, starting the alternating electric fields which are adjusted in place, simultaneously carrying out mechanical vibration treatment on the functional layer after slurry spraying, and closing after keeping for 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 200-600 ℃, and sintering the functional layer after slurry spraying for 30-120 min.
Further, after spraying the perovskite precursor liquid, the following treatment is required:
adjusting the highest intensity of two groups of alternating electric fields parallel to the heating platform to be 20-1000V/cm, adjusting the frequency to be 50-100 Hz, starting the alternating electric fields adjusted in place to mechanically vibrate the conductive substrate sprayed with the perovskite precursor liquid, and closing the conductive substrate after keeping the temperature for 10-60 s;
adjusting the intensity of an electrostatic field vertical to the heating platform to be 500-2000V/cm, starting the electrostatic field adjusted in place, standing at room temperature for 10-20min, controlling the surface temperature of the heating platform to be 30-100 ℃, and sintering the conductive substrate sprayed with the perovskite precursor liquid for 30-120 min.
Further, the conductive substrate needs to be pretreated before the electrostatic spraying of the slurry of the electron transport layer, and the specific method comprises the following steps:
the solid content of the electron transport layer slurry is 0.5-3%, the main component is one or more of titanium dioxide, zinc oxide, tin oxide, niobium oxide and barium stannate, the solid content of the mesoporous layer slurry is 3-10%, and the main component is one or more of titanium dioxide, zinc oxide, tin oxide, niobium oxide and barium stannate; the spacer layer slurry has a solid content of 3-10%, and the main component is one or more of zirconia, silicon dioxide, alumina, indium oxide, gallium oxide and cadmium sulfide; the solid content of the carbon layer slurry is 3-10%, and the main component is one or a mixture of carbon black, graphite, graphene and carbon nanotubes; the perovskite is in a perovskite structure ABX3Wherein A is CH3NH3 +B is Pb2 +X is I-、Br-Or Cl-The solid content of the perovskite precursor liquid is 5-30%.
The invention also provides a preparation device of the full-spraying perovskite solar cell, which comprises an electrostatic field generator, an alternating field generator, an atomizing nozzle for atomizing the solution or slurry to be sprayed and a horizontally arranged heating platform, wherein the atomizing nozzle is arranged above the heating platform; two voltage output ends of the electrostatic field generator are respectively connected with an upper flat plate electrode and a lower flat plate electrode, and the lower flat plate electrode is arranged close to the upper working surface of the heating platform; the alternating field generators are provided with two, two voltage output ends of one alternating field generator are respectively connected with the left flat plate electrode and the right flat plate electrode, and two voltage output ends of the other alternating field generator are respectively connected with the front flat plate electrode and the rear flat plate electrode.
Furthermore, the bottom of the heating platform is also provided with a vibration device.
Further, the vibration device adopts a vibrator capable of being started and stopped quickly, and the vibrator adopts a linear motor.
Furthermore, a horizontal adjusting device is further arranged on the heating platform.
Compared with the prior art, the invention has the following beneficial effects:
the material is sprayed on the conductive substrate by an electrostatic spraying mode, the uniformity of each functional layer is obviously improved by opening up and down electrostatic fields and two alternating electric fields and a vibration device which are parallel to the table top, more excellent interlayer interface contact can be obtained, and the transmission of electrons and holes is facilitated;
the perovskite precursor liquid can be quickly and fully permeated in the porous layer through the vibration device and the electrostatic field vertical to the direction of the conductive substrate/the heating platform;
in the sintering and drying processes, the existence of the electrostatic field can change the Gibbs free energy of a material system, and the crystallization state can be favorably regulated and controlled; the existence of the electrostatic field leads the compact layer to be closely contacted with the mesoporous layer nano particles, thereby realizing rapid electron transmission;
drawings
FIG. 1 is a schematic structural diagram of a device for preparing a full-spray perovskite solar cell provided by the invention;
FIG. 2 is a diagram showing the positional relationship between a heating platform and each flat plate electrode in the apparatus for manufacturing a fully-sprayed perovskite solar cell according to the present invention;
in the figure: 1. a vibration device; 2. a heating platform; 31. an upper plate electrode; 32. a lower plate electrode; 33. an upper and lower electrostatic field generator 41, a left plate electrode; 42. a right plate electrode; 43. a left-right direction alternating electric field generator; 51. a front plate electrode; 52. a rear plate electrode; 53. a front-back direction alternating electric field generator; 6. an atomizing nozzle.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
As shown in fig. 1 and 2, the device for preparing a fully-sprayed perovskite solar cell provided by the invention comprises an electrostatic field generator, an alternating field generator, an atomizing nozzle for atomizing a solution or slurry to be sprayed, and a horizontally arranged heating platform, wherein the atomizing nozzle is arranged above the heating platform. Two voltage output ends of the electrostatic field generator are respectively connected with an upper flat plate electrode and a lower flat plate electrode, and the lower flat plate electrode is arranged to be clung to the upper working surface of the heating platform. The bottom of the heating platform is also provided with a vibration device, the vibration device adopts a vibrator capable of being started and stopped quickly, and the vibrator adopts a linear motor. The alternating field generator is provided with two alternating field generators, one of the alternating field generators is a left-right alternating field generator, and two voltage output ends of the alternating field generator are respectively connected with the left flat plate electrode and the right flat plate electrode; the other is a front-back direction alternating electric field generator, and two voltage output ends of the front-back direction alternating electric field generator are respectively connected with a front flat plate electrode and a back flat plate electrode.
In order to ensure that the lower flat plate electrode arranged close to the upper working surface of the heating platform is kept horizontal, the heating platform is also provided with a horizontal adjusting device.
The heating platform adopts a pre-oxidized nickel-chromium electrothermal alloy heating wire. In order to facilitate temperature monitoring, a plurality of temperature sensors are arranged on the heating platform to acquire multipoint temperatures.
The electric field intensity between the plate electrodes can be realized by changing the distance between the two plate electrodes and adjusting the output voltage of the electric field generator.
Each flat plate electrode adopts a copper flat plate electrode which is subjected to polishing treatment.
The invention also provides a preparation method of the full-spraying perovskite solar cell, which can be realized by adopting the preparation device and specifically comprises the following steps:
the method comprises the following steps: pretreating the conductive substrate:
sequentially adopting deionized water, acetone and ethanol to carry out ultrasonic cleaning on the conductive substrate, drying the conductive substrate with nitrogen, treating the conductive substrate with UVO for 15min, and placing the conductive substrate on a heating platform;
step two: preparing an electron transport layer:
adjusting the electric field intensity of an electrostatic field vertical to the heating platform to 2000-4000V/cm, starting the electrostatic field adjusted in place, and electrostatically spraying the atomized slurry of the electron transport layer on the conductive substrate;
adjusting the highest intensity of an alternating electric field parallel to the heating platform to be 20-500V/cm, adjusting the frequency to be 50-400 Hz, starting the properly adjusted alternating electric field, simultaneously carrying out mechanical vibration treatment on the conductive substrate sprayed with the electronic transmission layer slurry, and closing the conductive substrate after keeping the temperature for 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 300-500 ℃, and sintering the conductive substrate sprayed with the electronic transmission layer slurry for 30-120 min.
The solid content of the electron transport layer slurry is 0.5-3%, and the main component is at least one of titanium dioxide, zinc oxide, tin oxide, niobium oxide, barium stannate and corresponding doping substances.
Step three: preparing a mesoporous layer:
adjusting the electric field intensity of the electrostatic field vertical to the heating platform to 2000-4000V/cm, starting the electrostatic field adjusted in place, and electrostatically spraying the atomized mesoporous layer slurry on the electron transport layer prepared in the step two;
adjusting the highest intensity of an alternating electric field parallel to the heating platform to be 200-1000V/cm, adjusting the frequency to be 50-400 Hz, starting the properly adjusted alternating electric field, simultaneously performing mechanical vibration treatment on the conductive base sprayed with the mesoporous layer slurry, and closing the conductive base after keeping the state for 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 200-600 ℃, and sintering the conductive base sprayed with the mesoporous layer slurry for 30-120 min.
The solid content of the mesoporous layer slurry is 3-10%, and the main component is at least one of titanium dioxide, zinc oxide, tin oxide, niobium oxide, barium stannate and corresponding doping substances.
Step four: preparing a spacing layer:
adjusting the electric field intensity of the electrostatic field vertical to the heating platform to 2000-4000V/cm, starting the electrostatic field adjusted in place, and electrostatically spraying the atomized spacer layer slurry on the dielectric layer prepared in the third step;
adjusting the highest intensity of an alternating electric field parallel to the heating platform to be 200-1000V/cm, adjusting the frequency to be 50-400 Hz, starting the alternating electric field which is adjusted in place, simultaneously carrying out mechanical vibration treatment on the conductive base after spraying the spacer layer slurry, and closing the conductive base after keeping the period of 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 200-600 ℃, and sintering the conductive base sprayed with the spacer layer slurry for 30-120 min.
The spacer layer slurry has a solid content of 3-10%, and the main component is at least one of zirconia, silica, alumina, indium oxide, gallium oxide, cadmium sulfide and corresponding doping substances.
Step five: preparation of a carbon layer:
adjusting the electric field intensity of the electrostatic field vertical to the heating platform to 2000-4000V/cm, starting the electrostatic field adjusted in place, and electrostatically spraying the atomized carbon layer slurry on the spacing layer prepared in the fourth step;
adjusting the highest intensity of an alternating electric field parallel to the heating platform to be 200-1000V/cm, adjusting the frequency to be 50-400 Hz, starting the properly adjusted alternating electric field, simultaneously performing mechanical vibration treatment on the conductive base sprayed with the carbon layer slurry, and closing the conductive base after keeping the temperature for 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 200-600 ℃, and sintering the conductive base sprayed with the carbon layer slurry for 30-120 min.
The carbon layer slurry has a solid content of 3-10%, and the main component is at least one of carbon black, graphite, graphene, carbon nanotubes and corresponding doping substances.
Step six: spraying perovskite precursor liquid:
adjusting the electric field intensity of the electrostatic field vertical to the heating platform to 2000-4000V/cm, starting the electrostatic field adjusted in place, and electrostatically spraying the atomized perovskite precursor liquid on the carbon layer prepared in the fifth step;
adjusting the highest intensity of an alternating electric field parallel to the heating platform to be 20-1000V/cm, adjusting the frequency to be 50-100 Hz, starting the alternating electric field which is adjusted in place to perform mechanical vibration treatment on the conductive substrate which is sprayed with the perovskite precursor liquid, and closing the conductive substrate after keeping the period of 10-60 s;
adjusting the intensity of an electrostatic field vertical to the heating platform to be 500-2000V/cm, starting the electrostatic field adjusted in place, standing at room temperature for 10-20min, controlling the surface temperature of the heating platform to be 30-100 ℃, and sintering the conductive substrate sprayed with the perovskite precursor liquid for 30-120 min.
The perovskite layer is in a perovskite structure ABX3Wherein A is CH3NH3 +B is Pb2 +X is I-、Br-Or Cl-The solid content of the perovskite precursor liquid is 5-30%.
The method for preparing the full-spray perovskite solar cell provided by the invention is further described in detail by combining specific embodiments.
The first embodiment is as follows:
pretreatment of conductive substrate
The conductive substrate is sequentially ultrasonically cleaned for 15min by using deionized water, acetone and ethanol, is subjected to UVO treatment for 15min after being dried by nitrogen, and is placed on a heating platform. The conductive substrate adopts an FTO substrate.
Preparation of electron transport layer
The electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 was set to 2500V/cm, and 0.5% TiO was added2Electrostatic spraying of the dense layer solution on an FTO substrate, starting a vibration device 1, adjusting and setting the frequency of an alternating electric field between a left plate electrode 41 and a right plate electrode 42 to be 100Hz and the highest intensity to be 30V/cm, adjusting and setting the frequency of the alternating electric field between a front plate electrode 51 and a rear plate electrode 52 to be 100Hz and the highest intensity to be 30V/cm, and simultaneously starting the vibration device 1, keeping the state for 10s and then closing; adjusting the intensity of the electrostatic field between 31 and 32 to 300V/cm, and heating to 450 ℃ for sintering for 30 min.
Preparation of mesoporous layer
The electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 was set to 3500V/cm, and TiO 3% solid content was added2Spraying the mesoporous layer slurry on the prepared electronic transmission layer, starting the vibration device 1, adjusting and setting the frequency of an alternating electric field between the left flat plate electrode 41 and the right flat plate electrode 42 to be 100Hz and the highest intensity to be 500V/cm, adjusting and setting the frequency of the alternating electric field between the front flat plate electrode 51 and the rear flat plate electrode 52 to be 100Hz and the highest intensity to be 500V/cm, simultaneously starting the vibration device 1, keeping the state for 10s, and then closing the vibration device; adjusting the electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 to 300V/cm, and keeping the temperature at 450 ℃ for 30 min.
Preparation of spacer layer
The electrostatic field strength between the upper plate electrode 31 and the lower plate electrode 32 was set to 4500V/cm, and ZrO was added at a solid content of 3%2Spraying the mesoporous layer slurry on the mesoporous layer prepared in the third step, starting the vibration device 1, adjusting and setting the frequency of an alternating electric field between the left flat plate electrode 41 and the right flat plate electrode 42 to be 200Hz and the highest intensity to be 500V/cm, adjusting and setting the frequency of the alternating electric field between the front flat plate electrode 51 and the rear flat plate electrode 52 to be 200Hz and the highest intensity to be 500V/cm, and simultaneously starting the vibration device 1 to keep the vibration device closed after 10 s; adjusting the electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 to 300V/cm, and keeping the temperature at 400 ℃ for 30 min.
Preparation of carbon layer
Setting the electrostatic field intensity between the upper flat plate electrode 31 and the lower flat plate electrode 32 to be 800V/cm, electrostatically spraying carbon layer slurry with the solid content of 3% on the spacer layer prepared by the fourth step, starting the vibrating device 1, adjusting and setting the alternating electric field frequency between the left flat plate electrode 41 and the right flat plate electrode 42 to be 60Hz and the highest intensity to be 500V/cm, adjusting and setting the alternating electric field frequency between the front flat plate electrode 51 and the rear flat plate electrode 52 to be 60Hz and the highest intensity to be 500V/cm, simultaneously starting the vibrating device 1, keeping the state for 10s and then closing; adjusting the electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 to 300V/cm, and keeping the temperature at 400 ℃ for 30 min.
Spray perovskite precursor liquid
Adjusting and starting up and down electrostatic field intensity to be 500V/cm, electrostatically spraying 10% perovskite precursor liquid on the carbon layer prepared at the temperature of 30 ℃, starting the vibration device 1, adjusting and setting the frequency of an alternating electric field between the left plate electrode 41 and the right plate electrode 42 to be 100Hz and the highest intensity to be 800V/cm, adjusting and setting the frequency of an alternating electric field between the front plate electrode 51 and the rear plate electrode 52 to be 100Hz and the highest intensity to be 800V/cm, simultaneously starting the vibration device 1, keeping the vibration device closed after 30 s; adjusting the electrostatic field strength between the upper plate electrode 31 and the lower plate electrode 32 to 1500V/cm, standing at room temperature for 20min, and oven drying at 50 deg.C for 30 min.
Example two:
pretreatment of conductive substrate
The conductive substrate is sequentially ultrasonically cleaned for 15min by using deionized water, acetone and ethanol, is subjected to UVO treatment for 15min after being dried by nitrogen, and is placed on a heating platform. The conductive substrate adopts an FTO substrate.
Preparation of electron transport layer
Setting the electrostatic field strength between the upper plate electrode 31 and the lower plate electrode 32 to 2500V/cm, and adding 3% SnO2Electrostatic spraying of the dense layer solution on an FTO substrate, starting a vibration device 1, adjusting and setting the frequency of an alternating electric field between a left plate electrode 41 and a right plate electrode 42 to be 100Hz and the highest intensity to be 300V/cm, adjusting and setting the frequency of the alternating electric field between a front plate electrode 51 and a rear plate electrode 52 to be 100Hz and the highest intensity to be 300V/cm, and simultaneously starting the vibration device 1, keeping the state for 10s and then closing; adjusting the intensity of the electrostatic field between 31 and 32 to 300V/cm, and heating to 500 ℃ for sintering for 30 min.
Preparation of mesoporous layer
The electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 was set to 3500V/cm, and TiO 3% solid content was added2Spraying the mesoporous layer slurry on the prepared electronic transmission layer, starting the vibration device 1, adjusting and setting the frequency of an alternating electric field between the left flat plate electrode 41 and the right flat plate electrode 42 to be 100Hz and the highest intensity to be 300V/cm, adjusting and setting the frequency of the alternating electric field between the front flat plate electrode 51 and the rear flat plate electrode 52 to be 100Hz and the highest intensity to be 300V/cm, simultaneously starting the vibration device 1, keeping the state for 10s, and then closing the vibration device; adjusting the electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 to 300V/cm, and keeping the temperature at 450 ℃ for 30 min.
Preparation of spacer layer
The electrostatic field strength between the upper plate electrode 31 and the lower plate electrode 32 was set to 4500V/cm, and the solid content was adjusted to 3% Al2O3Spraying the mesoporous layer slurry on the mesoporous layer prepared in the third step, starting the vibration device 1, adjusting and setting the frequency of an alternating electric field between the left flat plate electrode 41 and the right flat plate electrode 42 to be 200Hz and the highest intensity to be 300V/cm, adjusting and setting the frequency of the alternating electric field between the front flat plate electrode 51 and the rear flat plate electrode 52 to be 200Hz and the highest intensity to be 300V/cm, and simultaneously starting the vibration device 1 to keep the vibration device closed after 10 s; adjusting the electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 to 300V/cm, and keeping the temperature at 400 ℃ for 30 min.
Preparation of carbon layer
Setting the electrostatic field intensity between the upper flat plate electrode 31 and the lower flat plate electrode 32 to be 800V/cm, electrostatically spraying carbon layer slurry with the solid content of 3% on the spacer layer prepared by the fourth step, starting the vibrating device 1, adjusting and setting the alternating electric field frequency between the left flat plate electrode 41 and the right flat plate electrode 42 to be 60Hz and the highest intensity to be 500V/cm, adjusting and setting the alternating electric field frequency between the front flat plate electrode 51 and the rear flat plate electrode 52 to be 60Hz and the highest intensity to be 500V/cm, simultaneously starting the vibrating device 1, keeping the state for 10s and then closing; adjusting the electrostatic field intensity between the upper plate electrode 31 and the lower plate electrode 32 to 300V/cm, and keeping the temperature at 400 ℃ for 30 min.
Spray perovskite precursor liquid
Adjusting and starting up and down electrostatic field intensity to be 500V/cm, electrostatically spraying 10% perovskite precursor liquid on the carbon layer prepared at the temperature of 30 ℃, starting the vibration device 1, adjusting and setting the frequency of an alternating electric field between the left plate electrode 41 and the right plate electrode 42 to be 100Hz and the highest intensity to be 800V/cm, adjusting and setting the frequency of an alternating electric field between the front plate electrode 51 and the rear plate electrode 52 to be 100Hz and the highest intensity to be 800V/cm, simultaneously starting the vibration device 1, keeping 50s and then closing; adjusting the electrostatic field strength between the upper plate electrode 31 and the lower plate electrode 32 to 2000V/cm, standing at room temperature for 20min, and drying at 50 deg.C for 50 min.
According to the invention, a spraying mode is used for replacing a printing mode to realize preparation of each layer in the carbon-based perovskite battery, the vibration device and two alternating electric fields in the horizontal direction can enable the sprayed slurry to be relatively flat and uniform, the electrostatic fields in the vertical direction can enable the sprayed slurry to be in excellent interface contact with a lower layer, in addition, the electrostatic fields in the vertical direction can realize full permeation of perovskite precursor liquid, the Gibbs free energy of a perovskite precursor liquid system can be changed, and crystallization regulation and control can be easily realized on a large area.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a full-spraying perovskite solar cell comprises a heating platform arranged horizontally, an electrostatic field arranged perpendicular to the heating platform, an alternating electric field parallel to the heating platform and a vibration device arranged at the bottom of the heating platform; the preparation method is characterized by comprising the following steps:
placing a conductive substrate on a heating platform, starting an electrostatic field vertical to the heating platform, and sequentially performing electrostatic spraying and sintering of electron transport layer slurry, electrostatic spraying and sintering of mesoporous layer slurry, electrostatic spraying and sintering of spacer layer slurry and electrostatic spraying and sintering of carbon layer slurry on the upper surface of the conductive substrate to sequentially prepare an electron transport layer, a mesoporous layer, a spacer layer and a carbon layer;
performing electrostatic spraying of the perovskite precursor solution on the conductive substrate, and enabling the perovskite precursor solution to permeate into the mesoporous layer and the spacing layer under the action of an electrostatic field and gravity to obtain the perovskite solar cell;
the preparation method further comprises the following steps: and simultaneously starting an alternating electric field and a vibration device which are parallel to the heating platform after each slurry is electrostatically sprayed and before sintering.
2. The method for preparing the full-spray perovskite solar cell according to claim 1, wherein the specific method for preparing the electron transport layer is as follows:
electrostatically spraying the atomized electron transport layer slurry on a conductive substrate;
adjusting the highest intensity of two groups of alternating electric fields parallel to the heating platform to be 20-500V/cm, adjusting the frequency to be 50-400 Hz, starting the alternating electric fields which are adjusted in place, simultaneously carrying out mechanical vibration treatment on the conductive substrate sprayed with the electronic transmission layer slurry, and closing the conductive substrate after keeping the time of 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 300-500 ℃, and sintering the conductive substrate sprayed with the electronic transmission layer slurry for 30-120 min.
3. The method for preparing a full-spray perovskite solar cell according to claim 1 or 2, wherein the dielectric layer slurry, the spacer layer slurry and the carbon layer slurry are subjected to electrostatic spraying and then respectively treated as follows:
adjusting the highest intensity of two groups of alternating electric fields parallel to the heating platform to be 200-1000V/cm, adjusting the frequency to be 50-400 Hz, starting the alternating electric fields which are adjusted in place, simultaneously carrying out mechanical vibration treatment on the functional layer after slurry spraying, and closing after keeping for 10-60 s;
adjusting the highest intensity of an electrostatic field vertical to the heating platform to 300-1000V/cm, starting the electrostatic field adjusted in place, controlling the surface temperature of the heating platform to be 200-600 ℃, and sintering the functional layer after slurry spraying for 30-120 min.
4. The method for preparing the full-spray perovskite solar cell as claimed in claim 3, wherein the perovskite precursor liquid is sprayed and then treated as follows:
adjusting the highest intensity of two groups of alternating electric fields parallel to the heating platform to be 20-1000V/cm, adjusting the frequency to be 50-100 Hz, starting the alternating electric fields adjusted in place to mechanically vibrate the conductive substrate sprayed with the perovskite precursor liquid, and closing the conductive substrate after keeping the temperature for 10-60 s;
adjusting the intensity of an electrostatic field vertical to the heating platform to be 500-2000V/cm, starting the electrostatic field adjusted in place, standing at room temperature for 10-20min, controlling the surface temperature of the heating platform to be 30-100 ℃, and sintering the conductive substrate sprayed with the perovskite precursor liquid for 30-120 min.
5. The preparation method of the full-spray perovskite solar cell according to claim 3, wherein the conductive substrate is required to be pretreated before the electron transport layer slurry is electrostatically sprayed, and the specific method comprises the following steps:
ultrasonic cleaning is carried out by adopting deionized water, acetone and ethanol, and UVO treatment is carried out after nitrogen is used for drying.
6. The preparation method of the full-spray perovskite solar cell as claimed in claim 3, wherein the solid content of the electron transport layer slurry is 0.5-3%, the main component is one or more of titanium dioxide, zinc oxide, tin oxide, niobium oxide and barium stannate, the solid content of the mesoporous layer slurry is 3-10%, and the main component is one or more of titanium dioxide, zinc oxide, tin oxide, niobium oxide and barium stannate; the spacer layer slurry has a solid content of 3-10%, and the main component is one or more of zirconia, silicon dioxide, alumina, indium oxide, gallium oxide and cadmium sulfide; the solid content of the carbon layer slurry is 3-10%, and the main component is one or a mixture of carbon black, graphite, graphene and carbon nanotubes; the perovskite is in a perovskite structure ABX3Wherein A is CH3NH3 +B is Pb2 +X is I-、Br-Or Cl-The solid content of the perovskite precursor liquid is 5-30%.
7. The device for preparing the full-spraying perovskite solar cell is characterized by comprising an electrostatic field generator, an alternating field generator, an atomizing nozzle for atomizing a solution or slurry to be sprayed and a heating platform which is horizontally arranged, wherein the atomizing nozzle is arranged above the heating platform; two voltage output ends of the electrostatic field generator are respectively connected with an upper flat plate electrode and a lower flat plate electrode, and the lower flat plate electrode is arranged close to the upper working surface of the heating platform; the alternating field generators are provided with two, two voltage output ends of one alternating field generator are respectively connected with the left flat plate electrode and the right flat plate electrode, and two voltage output ends of the other alternating field generator are respectively connected with the front flat plate electrode and the rear flat plate electrode.
8. The apparatus according to claim 7, wherein the bottom of the heating platform is further provided with a vibration device.
9. The apparatus according to claim 8, wherein the vibration device is a vibrator capable of being started and stopped rapidly, and the vibrator is a linear motor.
10. The apparatus according to claim 7, 8 or 9, wherein a level adjustment device is further disposed on the heating platform.
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