CN114784197A - Preparation method of carbon electrode mesoscopic perovskite battery, assembly and power generation system - Google Patents
Preparation method of carbon electrode mesoscopic perovskite battery, assembly and power generation system Download PDFInfo
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- CN114784197A CN114784197A CN202210400161.4A CN202210400161A CN114784197A CN 114784197 A CN114784197 A CN 114784197A CN 202210400161 A CN202210400161 A CN 202210400161A CN 114784197 A CN114784197 A CN 114784197A
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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Abstract
The invention discloses a preparation method of a carbon electrode mesoscopic perovskite battery, the perovskite battery, a component and a power generation system, which comprise the following steps: step S1: selecting FTO conductive glass as a transparent conductive substrate or selecting a glass substrate, preparing a transparent conductive film on the glass substrate, and forming the transparent conductive substrate by the glass substrate and the transparent conductive film; step S2, preparing a compact electron transport layer on the transparent conductive film; step S3, preparing a mesoporous electron transport layer on the compact electron transport layer; step S4: preparing a ferroelectric interval insulating layer on the mesoporous electron transport layer by adopting inorganic ferroelectrics; step S5: preparing a carbon electrode on the ferroelectric spacer insulating layer; step S6, preparing a perovskite light absorption layer on the carbon electrode; step S7: applying a ferroelectric polarization field in a direction from the perovskite light absorption layer to the glass substrate 1 to the ferroelectric spacer insulating layer, wherein the intensity of the applied ferroelectric polarization field is greater than the ferroelectric coercive field of the ferroelectric spacer insulating layer; the invention improves the perovskite built-in field, and further improves the open-circuit voltage and the photoelectric conversion efficiency of the traditional perovskite battery.
Description
Technical Field
The invention relates to the technical field of perovskite batteries, in particular to a preparation method of a carbon electrode mesoscopic perovskite battery, the perovskite battery, a component and a power generation system.
Background
In the prior art, the preparation method of the electrode of the perovskite battery generally comprises the following steps:
step S1: preparing a transparent conductive film on a glass substrate;
step S2, preparing a compact electron transport layer on the transparent conductive film;
step S3, preparing a mesoporous electron transport layer on the compact electron transport layer;
step S4: preparing a ZrO insulating layer on the mesoporous electron transport layer by adopting ZrO;
step S5: preparing a carbon electrode on the ferroelectric spacer insulating layer;
step S6, preparing a perovskite light absorption layer on the carbon electrode;
according to the perovskite battery prepared by the method, the ZrO insulating layer can only prevent the carbon electrode from being in direct contact with the electron transport layer, so that electric leakage is prevented, and the recombination of photo-generated electron hole pairs is inhibited.
Therefore, how to increase the internal field of the perovskite and further increase the open-circuit voltage and the photoelectric conversion efficiency of the conventional perovskite battery becomes a difficult problem to be solved in the technical field of perovskite battery preparation.
Disclosure of Invention
The invention aims to enhance the perovskite built-in field and further improve the open-circuit voltage and the photoelectric conversion efficiency of the traditional perovskite battery, and provides a preparation method of a carbon electrode mesoscopic perovskite battery, the perovskite battery, a component and a power generation system.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the carbon electrode mesoscopic perovskite battery, the assembly and the power generation system are provided, and the preparation method comprises the following steps:
step S1: selecting FTO conductive glass as a transparent conductive substrate or selecting a glass substrate, preparing a transparent conductive film on the glass substrate, and forming the transparent conductive substrate by the glass substrate and the transparent conductive film;
step S2, preparing a compact electron transport layer on the transparent conductive film;
step S3, preparing a mesoporous electron transport layer on the compact electron transport layer;
step S4: preparing a ferroelectric interval insulating layer on the mesoporous electron transport layer by adopting inorganic ferroelectrics;
step S5: preparing a carbon electrode on the ferroelectric spacer insulating layer;
step S6, preparing a perovskite light absorption layer on the carbon electrode;
step S7: and applying a ferroelectric polarization field in a direction from the perovskite light absorption layer to the glass substrate to the ferroelectric spacer insulating layer, wherein the strength of the applied ferroelectric polarization field is greater than that of the ferroelectric coercive field of the ferroelectric spacer insulating layer.
Preferably, in step S4, PZT is used as the inorganic ferroelectric.
Preferably, the ferroelectric spacer insulating layer is prepared by the following steps:
step L1: grinding the PZT powder to obtain PZT nanocrystals;
step L2: adding PZT nanocrystalline into deionized water and stirring to obtain PZT hydrosol;
step L3: coating the PZT hydrosol on the mesoporous electron transmission layer, and annealing the PZT hydrosol coated on the mesoporous electron transmission layer to prepare the ferroelectric interval insulating layer.
Preferably, the transparent conductive film is made of one of ITO tin-doped indium oxide, FTO fluorine-doped tin oxide, IWO tungsten-doped indium oxide, and ICO cerium-doped indium oxide.
Preferably, the compact electron transport layer is made of at least one of PCBM, TiO2, ZnO, SnO2, H-PDI and F-PDI.
Preferably, the constituent material of the mesoporous electron transport layer is at least one of PCBM, TiO2, ZnO, SnO2, H-PDI and F-PDI.
Preferably, the perovskite light absorption layer is made of organic-inorganic hybrid perovskite with a general formula of ABX 3; wherein A is at least one of CH3NH3+ (MA +), CH (CH2)2+ (FA +), and Cs +, B is one of Pb2+, Sn2+, Ge2+, and X is at least one of Cl-, Br-and I-.
The invention also provides a perovskite battery which is prepared by applying the preparation method.
The invention also provides a perovskite battery component which is formed by electrically connecting a plurality of perovskite batteries prepared by the preparation method.
The invention also provides a solar power generation system comprising a plurality of electrically connected perovskite cell assemblies as described above.
The invention has the following beneficial effects:
preparing a ferroelectric interval insulating layer by adopting an inorganic ferroelectric, applying a ferroelectric polarization field to the ferroelectric interval insulating layer, and directionally arranging ferroelectric domains in the ferroelectric interval insulating layer so as to form a directional polarization electric field in the ferroelectric interval insulating layer, and performing field passivation on perovskite through ferroelectric polarization so as to enhance the perovskite built-in field;
the enhancement of the perovskite built-in field produces two beneficial effects:
1. on one hand: the split of quasi-Fermi energy levels of electrons and holes in a pin junction of the perovskite is aggravated by the enhanced built-in field of the perovskite material, so that the open-circuit voltage of the battery is further improved;
2. on the other hand: the enhanced built-in field of the perovskite material causes the energy band of a heterojunction interface formed by the perovskite light absorption layer 7 and the compact electron transmission layer 3 to bend, so that the separation and extraction rate of photon-generated carriers at the heterojunction interface is improved;
the improvement of the open-circuit voltage of the battery and the improvement of the separation and extraction rate of the current carrier are realized by the enhancement of the perovskite built-in field, and the problem of low photoelectric conversion efficiency of the perovskite battery prepared in the prior art is solved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic structural diagram of a carbon electrode mesoscopic perovskite battery prepared by the preparation method provided by the invention;
FIG. 2 is a schematic structural diagram of a large-area carbon electrode mesoscopic perovskite battery prepared by the preparation method provided by the invention;
FIG. 3 shows the ferroelectric spacer insulating layer selected from PZT, PbTiO3、BaTiO3、BiFeO3Or the experimental comparison data of the open-circuit voltage and the carrier separation and extraction rate of the carbon electrode mesoscopic perovskite battery when the zirconium oxide is prepared.
Reference numerals are as follows: 1.2, glass substrate, transparent conductive film; 3. a dense electron transport layer; 4. a mesoporous electron transport layer; 5. a ferroelectric spacer insulating layer; 6. a carbon electrode; 7. a perovskite light-absorbing layer; 8. and laser scribing the groove.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Wherein the showings are for the purpose of illustration only and not for the purpose of limiting the same, the same is shown by way of illustration only and not in the form of limitation; for a better explanation of the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if the terms "upper", "lower", "left", "right", "inner", "outer", etc. are used for indicating the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not indicated or implied that the referred device or element must have a specific orientation, be constructed in a specific orientation and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes and are not to be construed as limitations of the present patent, and the specific meanings of the terms may be understood by those skilled in the art according to specific situations.
In the description of the present invention, unless otherwise explicitly specified or limited, the term "connected" or the like, if appearing to indicate a connection relationship between the components, is to be understood broadly, for example, as being fixed or detachable or integral; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or may be connected through one or more other components or may be in an interactive relationship with one another. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
Example 1:
the embodiment of the invention provides a preparation method of a carbon electrode mesoscopic perovskite battery, the perovskite battery, a component and a power generation system, and as shown in figures 1 and 2, the preparation method comprises the following steps:
step S1: selecting a glass substrate 1, preparing a transparent conductive film 2 on the glass substrate 1, and forming a transparent conductive substrate on the glass substrate 1 and the transparent conductive film;
or directly adopting FTO conductive glass with high transmissivity as a transparent conductive substrate;
subsequently cleaning the transparent conductive substrateDipping the dust-free paper in ethanol to wipe the surface of the FTO substrate, sequentially ultrasonically cleaning the FTO substrate for 15-20 minutes by using a cleaning agent, deionized water, acetone and ethanol, drying the FTO substrate in a ventilation oven, and introducing O3And (5) performing UV treatment for 20 minutes, and cleaning the transparent conductive substrate.
Step S2, preparing a compact electron transport layer 3 on the transparent conductive film 2;
TiO2 is preferred as the raw material for the dense electron transport layer 3. Freezing a proper amount of deionized water into ice for later use, taking TiCl4 by using a liquid transfer gun under a fume hood, uniformly dripping the TiCl4 on the ice, quickly adding a small amount of deionized water, and stirring for 1h at 70 ℃ for later use. And (3) sticking a high-temperature adhesive tape on the treated FTO substrate, placing the FTO substrate in a watch glass, soaking the FTO substrate in the precursor solution, and reacting at 70 ℃ for 1h to complete the deposition of the TiO2 dense layer on the FTO. With N2Blowing TiO2And (3) drying the film at 70 ℃ for 1h to obtain the compact electron transport layer 3.
Step S3, preparing a mesoporous electron transport layer 4 on the compact electron transport layer 3;
preferably TiO2As the mesoporous electron transport layer 4 material. TiO to be purchased2Mixing the slurry with terpineol according to a certain proportion to obtain TiO2Mixing the slurry with TiO by screen printing2Printing the slurry mixture on the compact layer 3, standing for 30min until TiO2Drying the slurry mixture on a heating table at 70 ℃ after bubbles of the slurry mixture disappear; then placing the mesoporous electron transport layer on a high-temperature heating table, raising the temperature to 500 ℃, preserving the heat for 20min, and naturally cooling to room temperature to obtain a mesoporous electron transport layer 4;
step S4: preparing a ferroelectric interval insulating layer 5 on the mesoporous electron transport layer 4 by adopting inorganic ferroelectrics;
the inorganic ferroelectric is PZT, and because the PZT has high residual polarization strength, good ferroelectricity and low preparation cost, the PZT is preferably used for preparing the ferroelectric interval insulating layer 5;
step L1: synthesizing PZT powder by a hydrothermal method, and grinding the PZT powder into PZT nanocrystals by a ball mill;
step L2: adding the PZT nanocrystalline into deionized water and stirring for 2 hours to obtain PZT hydrosol;
step L3: coating PZT hydrosol on the mesoporous electron transmission layer 4 by slot-die slit coating method, and annealing at 350 ℃ to prepare the ferroelectric interval insulating layer 5.
Step S5: preparing a carbon electrode 6 on the ferroelectric spacer insulating layer 5;
printing carbon paste on the PZT ferroelectric interval insulating layer 5 by adopting a screen printing mode, standing for 10min, drying on a heating table at 70 ℃, then placing on a high-temperature heating table, programming to 400 ℃ for sintering, preserving heat for 30min, and naturally cooling to room temperature.
Step S6, preparing a perovskite light absorption layer 7 on the carbon electrode 6;
as the light absorbing layer of the perovskite solar cell, an MA + -free organic-inorganic hybrid perovskite material fa0.91cs0.09pbi3 is preferable. Firstly, preparing a FA0.91Cs0.09PbI3 precursor solution, and mixing PbI 2; FAI; CsI is added into a DMF/DMSO mixed solution with the volume ratio of 4.75:1 according to the chemical ratio of 1:0.91:0.09 until the solution concentration is 1.25mol/L, and then MaCl is added into the solution until the concentration is 23 mol% so as to stabilize perovskite phase formation. Then, filling the perovskite precursor liquid. And covering the non-filling area of the battery by using a high-temperature adhesive tape, filling the perovskite precursor liquid into the battery by using a liquid transfer gun, and annealing at 160 ℃ for 10-15 minutes to complete the preparation of the perovskite light absorption layer 7.
Step S7: polarizing the ferroelectric spacer insulating layer 5;
the polarization of the ferroelectric is realized by applying an electric field to the ferroelectric, and the method for applying the electric field by the constant current source is simple, high in speed and low in equipment cost, so that the electric field applied to the ferroelectric interval insulating layer adopts a mode of applying the electric field by the constant current source;
and applying a forward ferroelectric polarization field which is vertical to the surface of the perovskite battery and points to the transparent conductive substrate from the perovskite light absorption layer 7 by using a constant current voltage source to the ferroelectric spacing insulating layer 5, wherein the applied external electric field is larger than the ferroelectric coercive field of PZT, so that the ferroelectric spacing insulating layer 5 is polarized.
Example 2:
example 2 differs from example 1 in that PZT is used as the inorganic ferroelectric in step S4 in example 1, and PbTiO is used as the inorganic ferroelectric in S4 in example 23、BaTiO3Or BiFeO3Wherein BaTiO is3The ferroelectricity of the composite material is weaker, and the field passivation effect is not as good as that of PZT; BiFeO3Although possessing strong ferroelectric polarization, it is due to the preparation of pure phase BiFeO3Very difficult and therefore usually in BiFeO3The ferroelectric polarization measured in the ceramic is also weak, so BiFeO3The field passivation effect is also weak; PbTiO 23Compare with BaTiO3Or BiFeO3The ferroelectric property is stronger, and the field passivation effect is not much different from that of PZT; FIG. 3 shows the ferroelectric spacer insulating layer selected from PZT and PbTiO3、BaTiO3、BiFeO3Or the experimental comparison data of the open-circuit voltage and the carrier separation and extraction rate of the carbon electrode mesoscopic perovskite battery when the zirconium oxide is prepared.
Example 3:
step S7: polarizing the ferroelectric spacer insulating layer 5;
the method for polarizing the ferroelectrics is realized by applying an electric field to the ferroelectrics, and because the method for applying the electric field to the ferroelectrics by utilizing the PFM has better polarizing effect, but has long time consumption and large equipment investment, the process of applying the electric field to the ferroelectric interval insulating layer is carried out by utilizing the PFM under the condition of higher requirement on the polarizing effect;
and applying a forward ferroelectric polarization field which is vertical to the surface of the perovskite cell and is directed from the perovskite light absorption layer 7 to the transparent conductive substrate to the ferroelectric spacing insulating layer 5 by utilizing PFM, wherein the applied external electric field is larger than the ferroelectric coercive field of PZT, so that the ferroelectric spacing insulating layer 5 is polarized.
Example 4:
the method for polarizing the ferroelectrics is realized by applying an electric field to the ferroelectrics, and because the method for applying the electric field to the ferroelectrics by utilizing the PFM has better polarizing effect, but has long time consumption and large equipment investment, the process of applying the electric field to the ferroelectric interval insulating layer is carried out by utilizing the PFM under the condition of higher requirement on the polarizing effect;
and applying a forward ferroelectric polarization field which is vertical to the surface of the perovskite cell and is directed from the perovskite light absorption layer 7 to the transparent conductive substrate to the ferroelectric spacing insulating layer 5 by utilizing PFM, wherein the applied external electric field is larger than the ferroelectric coercive field of PZT, so that the ferroelectric spacing insulating layer 5 is polarized.
When the preparation of the large-area carbon electrode mesoscopic perovskite battery is required, any one of the examples 1, 2, 3 and 4 is selected, laser scribing and cutting are performed on the transparent conductive film 2 of the transparent conductive substrate after the step S1 in the example to form the laser scribing groove 8, then a plurality of carbon electrode mesoscopic perovskite battery cells isolated by the laser scribing groove 8 are obtained by sequentially performing the steps from S2 in the example, and the adjacent carbon electrode mesoscopic perovskite battery cells are connected in series through the carbon electrodes to form the large-area perovskite battery module.
The invention also provides a perovskite battery which is prepared by applying the preparation method.
The invention also provides a perovskite battery component which is characterized by being formed by electrically connecting a plurality of perovskite batteries prepared by the preparation method.
The invention also provides a solar power generation system comprising a plurality of electrically connected perovskite cell assemblies as described above.
It should be understood that the above-described embodiments are merely preferred embodiments of the invention and the technical principles applied thereto. Various modifications, equivalent substitutions, changes, etc., will also be apparent to those skilled in the art. However, such variations are within the scope of the invention as long as they do not depart from the spirit of the invention. In addition, certain terminology used in the description and claims of the present application is not limiting, but is used for convenience only.
Claims (10)
1. A preparation method of a carbon electrode mesoscopic perovskite battery is characterized by comprising the following steps:
step S1: selecting FTO conductive glass as a transparent conductive substrate or selecting a glass substrate 1, preparing a transparent conductive film 2 on the glass substrate 1, and forming the transparent conductive substrate by the glass substrate 1 and the transparent conductive film 2;
step S2, preparing a compact electron transport layer 3 on the transparent conductive film 2;
step S3, preparing a mesoporous electron transport layer 4 on the compact electron transport layer 3;
step S4: preparing a ferroelectric interval insulating layer 5 on the mesoporous electron transport layer 4 by adopting inorganic ferroelectrics;
step S5: preparing a carbon electrode 6 on the ferroelectric spacer insulating layer 5;
step S6, preparing a perovskite light absorption layer 7 on the carbon electrode 6;
step S7: a ferroelectric polarization field directed from the perovskite light absorption layer 7 toward the glass substrate 1 is applied to the ferroelectric spacer insulating layer 5, and the strength of the applied ferroelectric polarization field is larger than the ferroelectric coercive field of the ferroelectric spacer insulating layer 5.
2. The method for preparing a carbon electrode mesoscopic perovskite battery as claimed in claim 1, wherein in step S4, PZT is used as the inorganic ferroelectric.
3. The method for preparing a carbon electrode mesoscopic perovskite battery as claimed in claim 2, wherein the ferroelectric spacer insulating layer 5 is prepared by the steps of:
step L1: grinding the PZT powder to obtain PZT nanocrystals;
step L2: adding PZT nanocrystalline into deionized water and stirring to obtain PZT hydrosol;
step L3: and coating the PZT hydrosol on the mesoporous electron transmission layer 4, and annealing the PZT hydrosol coated on the mesoporous electron transmission layer 4 to prepare the ferroelectric spacer insulating layer 5.
4. The method for preparing a carbon electrode mesoscopic perovskite cell as defined in claim 1, wherein the transparent conductive thin film 2 is made of one of ITO tin-doped indium oxide, FTO fluorine-doped tin oxide, IWO tungsten-doped indium oxide, and ICO cerium-doped indium oxide.
5. The method for preparing the carbon electrode mesoscopic perovskite battery as claimed in claim 1, wherein the compact electron transport layer 3 is made of at least one of PCBM, TiO2, ZnO, SnO2, H-PDI and F-PDI.
6. The method for preparing the carbon electrode mesoscopic perovskite battery as claimed in claim 1, wherein the mesoporous electron transport layer 4 is made of at least one of PCBM, TiO2, ZnO, SnO2, H-PDI and F-PDI.
7. The method for preparing the carbon electrode mesoscopic perovskite battery as claimed in claim 1, wherein the perovskite light absorption layer 5 is made of an organic-inorganic hybrid perovskite with a general formula of ABX 3; wherein A is at least one of CH3NH3+ (MA +), CH (CH2)2+ (FA +), and Cs +, B is one of Pb2+, Sn2+, Ge2+, and X is at least one of Cl-, Br-, and I-.
8. A perovskite battery produced by the production method according to any one of claims 1 to 7.
9. A perovskite battery assembly characterized by being formed by electrically connecting a plurality of perovskite batteries prepared by the preparation method as claimed in claims 1 to 7.
10. A perovskite battery power generation system comprising a plurality of electrically connected perovskite battery components as defined in claim 9.
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| CN116322083A (en) * | 2023-05-16 | 2023-06-23 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and electric equipment |
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| CN116322083A (en) * | 2023-05-16 | 2023-06-23 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and electric equipment |
| CN116322083B (en) * | 2023-05-16 | 2023-11-24 | 宁德时代新能源科技股份有限公司 | Perovskite battery, photovoltaic module, photovoltaic power generation system and electric equipment |
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