CN115802775A - Perovskite solar cell, preparation method and shutter - Google Patents
Perovskite solar cell, preparation method and shutter Download PDFInfo
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- CN115802775A CN115802775A CN202310033692.9A CN202310033692A CN115802775A CN 115802775 A CN115802775 A CN 115802775A CN 202310033692 A CN202310033692 A CN 202310033692A CN 115802775 A CN115802775 A CN 115802775A
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- 239000000463 material Substances 0.000 claims abstract description 73
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- 230000005525 hole transport Effects 0.000 claims abstract description 24
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- 239000000243 solution Substances 0.000 claims description 68
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- NMVVJCLUYUWBSZ-UHFFFAOYSA-N aminomethylideneazanium;chloride Chemical compound Cl.NC=N NMVVJCLUYUWBSZ-UHFFFAOYSA-N 0.000 description 1
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a perovskite solar cell, a preparation method and a shutter, wherein the preparation method comprises the preparation of a perovskite film layer, and is characterized in that: the preparation method of the perovskite film layer comprises the following steps: the preparation method comprises the following steps of (1) spin-coating DL-2-amino-3-phosphonopropionic acid and perovskite film layer materials on a hole transport layer to form a film; the perovskite film layer material comprises PbX a And a first material, the first material being capable of reacting with the PbX a Coordinate to form ABX 3 The crystal form compound or the perovskite film layer material comprises a second material, and the second material is ABX 3 A crystal form compound, wherein A and B are positive ions, and B is Pb 2+ X is an anion, a =2. The preparation method effectively reduces the defect density of the perovskite battery and improves the stability and efficiency of the battery.
Description
Technical Field
The invention relates to a solar cell, in particular to a perovskite solar cell, a preparation method and a shutter formed by the perovskite solar cell.
Background
As a clean energy source, solar energy can meet the increasing global energy demand. Among the numerous optoelectronic devices, perovskite solar cells are of interest due to their higher power conversion efficiency and lower manufacturing costs. Compared with a crystalline silicon battery, the perovskite battery has the advantages of light weight, flexibility, high weak light response and translucency, and has wide application in the aspects of photovoltaic integrated buildings, intelligent windows, light photovoltaic roofs and the like.
The perovskite battery is mainly problematic in that the stability and efficiency of the battery are insufficient, and the requirement of long-term continuous operation cannot be met. The sources of instability and low efficiency are mainly defect states on the surface of the perovskite film layer. Defects of a perovskite film layer in the battery can capture photon-generated carriers, increase the recombination of the photon-generated carriers and reduce the utilization efficiency of the carriers. Moreover, the position of the defect is an energy active position, and the factors causing the perovskite decomposition such as moisture, light, heat and the like generally act from the defect, so that the defect becomes a decomposition site. Therefore, the defect density of the perovskite film layer is reduced, the utilization efficiency of photon-generated carriers can be effectively improved, and the stability and efficiency of the battery are improved.
Disclosure of Invention
It is an object of the present invention to improve the efficiency and thermal stability of perovskite solar cells.
Based on the purpose, the invention provides a preparation method of the perovskite solar cell, which overcomes the interface defect of the perovskite film layer by performing interface modification on the perovskite film layer, and further improves the thermal stability and efficiency of the perovskite solar cell.
On the other hand, the invention provides a perovskite solar cell, wherein the perovskite film layer of the perovskite solar cell is provided with an interface modification material, so that the interface defect of the perovskite film layer can be overcome, and the efficiency of the perovskite solar cell is improved by 8.4%.
On the other hand, the invention provides the shutter prepared by using the perovskite solar cell, and the shutter can convert solar energy into electric energy while realizing a ventilation window, so that the energy consumption is saved, and the shutter is green and environment-friendly.
The specific scheme adopted is as follows:
the preparation method of the perovskite solar cell comprises the steps of pretreatment of a substrate and hole transmissionThe preparation method of the perovskite film layer comprises the following steps of: the preparation method comprises the following steps of (1) spin-coating DL-2-amino-3-phosphonopropionic acid and perovskite film layer materials on a hole transport layer to form a film; the perovskite film layer material comprises PbX a And a first material, the first material and the PbX a Coordination enables the formation of ABX 3 The crystal form compound or the perovskite film layer material comprises a second material, and the second material is ABX 3 A crystalline compound, wherein A and B are different cations and B is Pb 2 + X is an anion, a =2.
Secondly, the perovskite solar cell comprises a perovskite film layer, wherein the perovskite film layer is made of DL-2-amino-3-phosphonopropionic acid and a perovskite film layer material; the perovskite film layer material comprises PbX a And a first material, the first material and the PbX a Coordination enables the formation of ABX 3 The crystal form compound or the perovskite film layer material comprises a second material, and the second material is ABX 3 A crystal compound, wherein A and B are different cations, and B is Pb 2+ And X is an anion.
In a preferable embodiment, a is one or a combination of several of methylamino, amidino, cesium, rubidium.
The first material is one or a combination of more of formamidine iodine (FAI), formamidine bromine (FABr), formamidine chloride (FACL), methylamine iodine (MAI), methylamine bromine (MABr), methylamine chloride (MACl), cesium iodide (CsI), rubidium iodide (RbI), cesium chloride (CsCl) and rubidium chloride (RbCl). The second material is formamidine lead iodide (FAPbI) 3 ）。
As a preferable scheme, the preparation method of the perovskite film layer comprises the following steps:
a preparing a precursor solution, the precursor solution comprising
Solution one: lead iodide (PbI) 2 ) And DL-2-amino-3-phosphonopropionic acid, as a preferable embodiment, the mass ratio of the lead iodide to the DL-2-amino-3-phosphonopropionic acid is 635；
Solution II: a mixed solution of formamidine iodine, methylamine bromide and methylamine chloride;
b spin-coating the solution on the hole transport layer, and drying to form PbI 2 A film layer;
c two-spin coating the solution on PbI 2 Forming a perovskite film layer on the film layer;
d, annealing and cooling.
As a preferable scheme, the preparation method of the perovskite film layer comprises the following steps:
a preparing precursor solution, wherein the precursor solution is FAPBI 3 MACl, DL-2-amino-3-phosphonopropionic acid in DMF/DMSO;
b, coating the precursor solution on the hole transport layer;
c, dripping chlorobenzene on the film layer;
d, annealing in the nitrogen atmosphere, and cooling to form the perovskite film layer.
The MACl is added into the perovskite film layer material, so that the size of crystal grains in the perovskite film layer can be effectively increased, the crystallization performance of perovskite crystals is improved, and the transmission efficiency of current carriers is further improved.
As a preferred embodiment, a =2,pbx a Is PbI 2 、PbBr 2 Or PbCl 2 Preferably PbI 2 The DL-2-amino-3-phosphonopropionic acid is reacted with PbI 2 The molar ratio of (2) to (0.001) is 0.001 to 0.1, if the molar ratio is lower than 0.001, effective passivation cannot be carried out, so that the defect density is still in a higher level, and if the molar ratio is higher than 0.1, part of DL-2-amino-3-phosphonopropionic acid is remained unnecessarily, so that the transmission of current carriers is influenced, and the film layer is negatively influenced.
As a preferable scheme, the mixing proportion of the formamidine iodine, the methylamine bromide and the methylamine chloride is (85 to 95): (8 to 10): (10 to 13). Still preferably, the mixing ratio of the formamidine iodine, the methylamine bromide and the methylamine chloride is 1100.
As a preferable scheme, the thickness of the perovskite film layer is 600-800nm, the perovskite film layer is a core film layer of the battery, and the addition of DL-2-amino-3-phosphonopropionic acid has certain influence on the light absorption and the carrier transmission efficiency of the perovskite film layer. When the thickness is less than 600nm, part of light rays cannot be fully absorbed, and when the thickness is more than 800nm, current carriers in the perovskite film layer cannot be effectively transmitted.
As a preferable scheme, the preparation method of the electron transport layer comprises the following steps:
a, evaporating a C60 material onto a perovskite film layer at the speed of 0.02nm/s by using a thermal evaporation mode to form a C60 film layer, wherein the thickness is 20nm;
and b, evaporating a BCP material onto the C60 film layer at the speed of 0.015nm/s in a thermal evaporation mode, wherein the thickness of the BCP material is 7nm, and thus obtaining the electron transport layer.
Thirdly, the louver comprises a plurality of louver blades, and the perovskite solar cell is arranged on the blades. The perovskite solar cell can be directly used as a shutter blade or loaded on the blade substrate.
Has the advantages that: a source of perovskite solar cell instability and inefficiency is the defect state in the perovskite film layer. According to the invention, the defect state is effectively passivated by introducing the efficient passivation group, so that the density of the defect state is reduced, the extraction and transmission capability of the charge is improved, and the stability and the conversion efficiency of the battery are improved.
The invention carries out passivation of a film layer and reduction of defect state density by adding fluorine DL-2-amino-3-phosphonopropionic acid. DL-2-amino-3-phosphonopropionic acid having NH 2 And S = O, C = O bond, NH 2 And surplus or deficient electron clouds in S = O, C = O bonds can form interactions with different defects, effectively passivate defects such as iodine vacancies, stabilize defects and reduce the density of defect states.
The invention can improve the film forming property of the perovskite thin film, improve the efficiency of the perovskite battery and the thermal stability of the perovskite battery, and the data shows that the battery efficiency of adding DL-2-amino-3-phosphonopropionic acid to modify the perovskite film is improved by 8.4 percent compared with the battery without adding DL-2-amino-3-phosphonopropionic acid.
Drawings
FIG. 1 is a block diagram of a perovskite solar cell;
FIG. 2 is a graph of voltage versus current density for example 1 and comparative example 1;
FIG. 3 normalized efficiency plots for example 2 and comparative example 2;
FIG. 4 is a schematic view of the structure of the blind;
FIG. 5 optoelectronic parameters of perovskite cells treated via DL-2-amino-3-phosphonopropionic acid in example 1 and untreated in comparative example 1.
Detailed Description
The present invention is described in further detail below in the form of specific embodiments, but it should be understood that the scope of the present invention is not limited by the specific embodiments.
Perovskite solar cell: a novel solar cell has the characteristics of green, light weight and high transparency, and can be in a p-i-n structure as shown in figure 1. The perovskite battery is composed of a substrate 1, a hole transport layer 2, a perovskite film layer 3, an electron transport layer 4 and an electrode layer 5. The perovskite layer is the core of the whole device and is responsible for absorbing light energy and generating electron-hole pairs, and the separation, collection and flow of the electron-hole pairs are the sources of electric energy generation. The specific principle is as follows: when sunlight is incident on the perovskite film layer 3, most of light energy is absorbed, and electrons absorb the energy of photons to generate energy band-to-band transition, so that electron hole pairs are formed. Due to the selective nature of the hole transport layer 2 and the electron transport layer 4, holes will migrate from the perovskite film layer 3 to the hole transport layer 2, while electrons will migrate in the direction of the electron transport layer 4. The holes and the electrons are respectively transmitted to the corresponding transmission layers and further collected by the corresponding electrodes.
A shutter: the shutter is the current household articles for use, is used for the French window usually, has decoration and practical function concurrently, and the structure includes a plurality of rotatable blades, can realize opening and shutting of shutter through rotatory blade.
The preparation method of the perovskite solar cell comprises the following steps: pretreating a substrate; preparing a hole transport layer; preparing a perovskite film layer containing a passivating agent; preparing an electron transport layer; preparing an electrode; and (5) packaging the battery.
The following steps are respectively introduced by concrete implementation steps:
pretreatment of the substrate: selecting a flexible substrate, preferably a full-spectrum transparent material or a spectrum transparent material required by perovskite, preferably a flexible PET/ITO substrate, wherein the transmissivity of the substrate in the solar energy action waveband of the perovskite is more than 80%, and the specific processing steps are as follows:
a, cleaning by using a cleaning agent to remove dust particles on the surface of a substrate;
b, cleaning with deionized water to remove a cleaning agent and water-soluble impurities;
c, cleaning the substrate surface by acetone to remove oily organic matters;
d, cleaning the isopropanol to remove oily organic matters and acetone;
e, drying by using a nitrogen gun after cleaning is finished, and treating in an ultraviolet ozone treater. Blow-dry through the nitrogen gun, can avoid the dust to remain, increase the cleanliness of basement, get rid of the remaining organic matter of leaving behind the washing through ultraviolet ozone treatment and remain, like acetone, isopropyl alcohol etc..
Preparation of hole transport layer: the hole transport layer material is formed on the substrate by spin coating, evaporation coating or dipping film forming, the hole transport layer material is preferably organic hole transport material, which can be poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), polymer of 3-hexylthiophene (P3 HT), 2PACz, meO-2PACz, me-4PACz, me-2PACz, etc., the following is specifically explained by taking the selected high molecular polymer poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) as an example:
a, dissolving a high molecular polymer poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] in an organic solvent chlorobenzene and filtering,
b spin coating the filtered solution on a PET/ITO substrate
c, annealing.
Preparing a perovskite film layer: after being mixed with DL-2-amino-3-phosphono propionic acid, the perovskite film material is coated on the hole transport layer by spin coating or dipping, and the perovskite film material comprises PbX a And material one, material one and PbX a Coordinate to form ABX 3 Crystal form compoundAs the perovskite film layer material, a =2, or the perovskite film layer material is ABX 3 A crystalline compound, wherein A, B are cations, X is an anion, ABX 3 The crystal structure is cubic crystal, A is arranged at the vertex of the angle of the cubic crystal, B is arranged at the center of the body of the cubic crystal, X is arranged at the center of the face of the cubic crystal, specifically, A is organic ion, B is Pb 2+ 。
First, the perovskite film layer material formed by coordination of formamidine iodine, methylamine bromide, methylamine chloride and lead iodide is taken as an example for explanation:
a preparing a precursor solution, the precursor solution comprising
Solution one: a mixed solution of lead iodide and DL-2-amino-3-phosphonopropionic acid;
solution II: a mixed solution of formamidine iodine, methylamine bromide and methylamine chloride;
b spin-coating the solution on the hole transport layer, and drying to form PbI 2 A film layer;
c two-spin coating the solution on PbI 2 Forming a perovskite film layer on the film layer;
d, annealing and cooling.
Secondly, the following description will be given by taking the example of the perovskite film material formed by coordination of formamidine iodine and lead iodide as follows:
a, preparing a precursor solution, wherein the precursor solution is PbI 2 A solution of formamidine iodide, DL-2-amino-3-phosphonopropionic acid in DMF/DMSO
b, coating the precursor solution on the hole transport layer;
c, dropwise adding chlorobenzene on the film layer;
d, annealing in a nitrogen atmosphere, and cooling to form the perovskite film layer.
DL-2-amino-3-phosphonopropionic acid having NH 2 And S = O, C = O bond, aiming at a perovskite crystal form formed by coordination of formamidine iodine, methylamine bromine, methylamine chlorine and lead iodide, wherein the defects of iodine vacancy and the like existing in the perovskite crystal form formed by coordination of formamidine iodine and lead iodide can overcome the defects through interaction of surplus or deficient electron cloud and the defects, and further the stability of the perovskite layer is improved.
Preparation of an electron transport layer: forming a film of an electron transport layer material on the perovskite film layer material by spin coating, evaporation or dipping to form the electron transport layer, wherein the electron transport layer material can be an inorganic electron transport material or an organic electron transport material, and is described as C60:
a, forming a C60 film layer on the perovskite film layer by using a vapor deposition film forming mode;
b, forming a film on the C60 film layer by using a BCP (benzocyclobutene) film forming mode;
and (5) preparing the electron transport layer.
BCP (2, 9-dimethyl-4, 7-diphenyl phenanthroline) is used as a hole blocking material and can block photo-generated holes in the perovskite from being transmitted to an electrode on one side for extracting electrons, C60 (fullerene material) is used as an electron transmission layer material and can extract photo-generated electrons generated in the perovskite, and the two materials are matched with each other to improve the hole transmission efficiency.
The electrode material is copper, and the battery packaging material is PET and packaging glue.
The invention passivates and modifies the film layer by introducing the additive and the like, and the functional group of the additive can be effectively paired with the defect state, thereby reducing the influence of the defect on the current carrier. The reduced defect state density can effectively inhibit the decomposition of perovskite and improve the efficiency and stability.
The perovskite solar cell manufactured by the method is integrated on the shutter, and the specific structure is as follows: the perovskite solar cell is used as the blade of the shutter, at least one perovskite solar cell is arranged on each blade, the perovskite solar cells on the same blade are connected in series, the perovskite solar cells on different blades are connected in parallel and then are connected with the energy storage device, and as the perovskite solar cell overcomes the defect of a perovskite film layer by introducing DL-2-amino-3-phosphonopropionic acid, the stability and the efficiency of the cell are improved, when the perovskite solar cell is applied to the shutter, the service life of the shutter can be prolonged, the practicability of the shutter is enhanced, and the possibility of popularizing the perovskite solar cell on household articles is increased.
The above-described scheme is described in detail below by way of specific examples.
Example 1
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a chlorobenzene solution of PTAA: 2mg of PTAA was dissolved in 1mL of chlorobenzene, stirred with shaking, and filtered using a 0.45 μm filter cartridge for standby, to filter out impurities in the solution and prevent formation of macroscopic pores.
b PbI 2 Mixed solution with DL-2-amino-3-phosphonopropionic acid: 635mg of PbI 2 And 1mg of DL-2-amino-3-phosphonopropionic acid were dissolved in 0.90mL of N-Dimethylformamide (DMF) and 0.1mL of dimethyl sulfoxide (DMSO), stirred at 100 ℃ for 30min until completely dissolved, and filtered using a 0.45 μm filter element for use.
c FAI/MABr/MACl solution: 1100mg of FAI, 112mg of MABr, and 130mg of MACl powder were dissolved in 15mL of isopropyl alcohol solution (IPA), sufficiently stirred until the solution was clear, and filtered using a 0.45 μm filter cartridge for use.
(2) Pretreatment of the substrate:
the PET/ITO flexible substrate was first ultrasonically cleaned in deionized water for 30 minutes, then ultrasonically cleaned in acetone for 30 minutes, and finally ultrasonically cleaned in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and placed in an ultraviolet ozone processor for 30 minutes for further use.
(3) Preparation of hole transport layer:
a solution of PTAA in chlorobenzene was spin-coated onto an ITO substrate at a spin-coating rate of 3000rpm for 30s, followed by annealing at 100 ℃ for 10min.
(4) Preparing a perovskite film layer:
a prepared PbI 2 The mixed solution with DL-2-amino-3-phosphonopropionic acid is spin-coated on the PTAA film layer at the speed of 1500rpm for 40s;
b subsequent natural drying for 3 minutes under nitrogen atmosphere to form PbI 2 A film layer;
c, spin coating the prepared FAI/MABr/MACl solution to PbI 2 On the film, the speed is 1800rpm, the time is 30s;
d subsequently annealing at 135 deg.C for 20min, and cooling to obtain perovskite film with thickness of about 630nm.
(5) Preparation of an electron transport layer:
c60 and BCP materials are respectively evaporated on the perovskite film layer in a thermal evaporation mode, the thickness is 20nm and 7nm respectively, and the speed is 0.02nm/s and 0.015nm/s respectively.
(6) Preparing an electrode:
a layer of 200nm copper (Cu) is evaporated on the surface of the BCP by a thermal evaporation mode to be used as an electrode.
(7) Battery packaging
And (3) taking a PET packaging layer to sandwich an active layer of the battery to form a sandwich structure, coating ultraviolet curing glue on a non-electrode position, irradiating for 5min under an ultraviolet lamp to form solid glue, and packaging the battery between two layers of PET substrates.
Example 2
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a chlorobenzene solution of PTAA: 2mg of PTAA was dissolved in 1mL of chlorobenzene, stirred with shaking, and filtered through a 0.45 μm filter element for use.
b amitraz lead iodide (FAPBI) 3 ) Mixed solution with DL-2-amino-3-phosphonopropionic acid: 1550mg FAPBI 3 The powder, 61mg MACl and 2mg DL-2-amino-3-phosphonopropionic acid were dissolved in 1mL DMF/DMSO solution at a volume ratio of DMF/DMSO of 4, heated at 100 ℃ and stirred for 30min to completely dissolve, and filtered using a 0.45 μm filter cartridge for use;
(2) Pretreatment of the substrate:
a, ultrasonically cleaning an ITO glass substrate in deionized water for 30 minutes;
b ultrasonic cleaning in acetone for 30 minutes;
c ultrasonic cleaning in isopropyl alcohol (IPA) for 30 minutes;
and d, drying by using a nitrogen gun, and treating in an ultraviolet ozone treater for 30 minutes for later use.
(3) Preparation of hole transport layer:
a solution of PTAA in chlorobenzene was spin-coated onto the ITO substrate at a spin-coating rate of 3000rpm for 30s, followed by annealing at 100 ℃ for 10min.
(4) Preparing a perovskite film layer:
a, spin-coating a prepared formamidine lead-iodine solution on a PTAA film layer at the speed of 5000rpm for 40s;
b, dripping 100 mu L of anti-solvent chlorobenzene at the 20 th s after the coating is started;
c, annealing at 135 ℃ for 20min, and cooling for later use, wherein the thickness of the prepared perovskite film layer is about 700 nm.
(5) Preparation of an electron transport layer:
and respectively evaporating C60 and BCP materials onto the modified perovskite film layer by using a thermal evaporation mode, wherein the thicknesses are respectively 20nm and 7nm, and the rates are respectively 0.02nm/s and 0.015nm/s.
(6) Preparing an electrode:
a layer of 150nm silver (Ag) is evaporated on the surface of the BCP by a thermal evaporation mode to be used as an electrode.
(7) Battery packaging
And (3) taking a PET packaging layer to sandwich an active layer of the battery to form a sandwich structure, coating ultraviolet curing glue on a non-electrode position, irradiating for 5min under an ultraviolet lamp to form solid glue, and packaging the battery between two layers of PET substrates.
Comparative example 1
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a chlorobenzene solution of PTAA: 2mg of PTAA was dissolved in 1mL of chlorobenzene, stirred with shaking, and filtered using a 0.45 μm filter cartridge for standby, to filter out impurities in the solution and prevent formation of macroscopic pores.
b PbI 2 Solution: 635mg of PbI 2 Dissolved in 0.90mL of N-N Dimethylformamide (DMF) and 0.1mL of dimethyl sulfoxide (DMSO), heated at 100 ℃ and stirred for 30min to completely dissolve, and filtered using a 0.45 μm filter element for use.
c FAI/MABr/MACl solution: 1100mg of FAI, 112mg of MABr, and 130mg of MACl powder were dissolved in 15mL of isopropyl alcohol solution (IPA), sufficiently stirred until the solution was clear, and filtered using a 0.45 μm filter cartridge for use.
(2) Pretreatment of the substrate:
the ITO glass substrate was first ultrasonically cleaned in deionized water for 30 minutes, then ultrasonically cleaned in acetone for 30 minutes, and finally ultrasonically cleaned in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and placed in an ultraviolet ozone processor for 30 minutes for standby.
(3) Preparation of hole transport layer:
a solution of PTAA in chlorobenzene was spin-coated onto the ITO substrate at a spin-coating rate of 3000rpm for 30s, followed by annealing at 100 ℃ for 10min.
(4) Preparing a perovskite film layer:
a prepared PbI 2 The solution is coated on the PTAA film layer in a spinning mode, the speed is 1500rpm, and the time is 40s;
b subsequent natural drying under nitrogen atmosphere for 3 minutes to form PbI 2 A film layer;
c, spin coating the prepared FAI/MABr/MACl solution to PbI 2 On the film, the speed is 1800rpm, the time is 30s;
d, annealing at 135 ℃ for 20min, and cooling for later use, wherein the thickness of the prepared perovskite film layer is about 630nm.
(5) Preparation of an electron transport layer:
c60 and BCP materials are respectively evaporated on the perovskite film layer in a thermal evaporation mode, the thickness of the perovskite film layer is 20nm and 7nm, and the speed is 0.02nm/s and 0.015nm/s respectively.
(6) Preparing an electrode:
a layer of 200nm copper (Cu) is evaporated on the surface of BCP by a thermal evaporation mode to be used as an electrode.
(7) Battery packaging
And (3) taking a PET packaging layer to sandwich an active layer of the battery to form a sandwich structure, coating ultraviolet curing glue on a non-electrode position, irradiating for 5min under an ultraviolet lamp to form solid glue, and packaging the battery between two layers of PET substrates.
Comparative example 2
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a chlorobenzene solution of PTAA: 2mg of PTAA was dissolved in 1mL of chlorobenzene, stirred with shaking, and filtered through a 0.45 μm filter element for use.
b formamidine lead iodine solution: 1550mg FAPbI 3 The powder and 61mg MACl were dissolved in 1mL of DMF/DMSO solution at a volume ratio of DMF/DMSO of 4, heated at 100 ℃ and stirred for 30min to dissolve completely, and filtered using a 0.45 μm filter cartridge before use.
(2) Pretreatment of the substrate:
a, ultrasonically cleaning an ITO glass substrate in deionized water for 30 minutes;
b ultrasonic cleaning in acetone for 30 minutes;
c ultrasonic cleaning in isopropyl alcohol (IPA) for 30 minutes;
and d, drying by using a nitrogen gun, and treating in an ultraviolet ozone treater for 30 minutes for later use.
(3) Preparation of hole transport layer:
a solution of PTAA in chlorobenzene was spin-coated onto the ITO substrate at a spin-coating rate of 3000rpm for 30s, followed by annealing at 100 ℃ for 10min.
(4) Preparing a perovskite film layer:
a, spin-coating a prepared formamidine lead-iodine solution on a PTAA film layer at the speed of 5000rpm for 40s;
b, dripping 100 mu L of anti-solvent chlorobenzene at the 20 th s;
c, annealing at 135 ℃ for 20min, and cooling for later use, wherein the thickness of the prepared perovskite film layer is about 700 nm.
(5) Preparation of an electron transport layer:
and respectively evaporating C60 and BCP materials onto the modified perovskite film layer by using a thermal evaporation mode, wherein the thicknesses are respectively 20nm and 7nm, and the rates are respectively 0.02nm/s and 0.015nm/s.
(6) Preparing an electrode:
a layer of 150nm silver (Ag) is evaporated on the surface of the BCP by a thermal evaporation mode to be used as an electrode.
(7) Battery packaging
And (3) taking a PET packaging layer to sandwich an active layer of the battery to form a sandwich structure, coating ultraviolet curing glue on a non-electrode position, irradiating for 5min under an ultraviolet lamp to form solid glue, and packaging the battery between two layers of PET substrates.
The perovskite solar cells obtained in example 1 and comparative example 1 were subjected to voltage-current density curve test in a nitrogen glove box with a test step size of 0.02V, and corresponding current density-voltage curves were obtained by measuring the corresponding current density value at each input voltage, as shown in fig. 2. The photoelectric parameter test is carried out on the compound, as shown in fig. 5, it can be known that after DL-2-amino-3-phosphonopropionic acid is added, the open-circuit voltage and the fill factor of the cell are both effectively improved, the improvement of the open-circuit voltage is derived from the improvement of quasi-fermi level splitting degree, and the improvement of splitting is derived from the reduction of the surface recombination of current carriers, which indicates that the defect is effectively passivated and the recombination center is reduced by the addition of the additive. The improvement of the filling factor comes from the optimization of a carrier transmission channel, and the main reason is the reduction of the defect state.
The perovskite solar cell devices obtained in example 2 and comparative example 2 were packaged, the devices were placed on a heating stage at 85 degrees celsius so that the devices operated at the maximum power point, and the output power thereof was measured to obtain the curve shown in fig. 3. The stability of the solar cell device added with DL-2-amino-3-phosphonopropionic acid perovskite obtained from FIG. 3 is significantly higher than that of the non-added cell device, and the main source is the decomposition of perovskite. The defect states in the perovskite solar cell are effectively eliminated by adding the additive, and the stability of the device is improved.
Example 3
Compared with the embodiment 1, the difference is that the perovskite film layer material is different, so that part of PbBr is adopted 2 Alternative PbI in example 1 2 In this example, pbBr 2 Molar weight and PbI 2 The molar ratio of the perovskite to the amino-3-phosphonopropionic acid is 1.
Example 4
The perovskite solar cell obtained in example 1 was integrated on a louver comprising several parallel arranged blades 6, the lightweight flexible perovskite solar cell being the blade 6 of the louver.
The line connection form of the perovskite solar cell is set as follows: the perovskite solar cells on the same blade 6 are connected in series and then are connected in parallel with the perovskite solar cells on different blades 6 and then are led to the energy storage device, and positive and negative electric wires of the cells are respectively led out from two ends of the blade 6.
The connection mode of a plurality of blades 6 on the shutter adopts the connection mode of the blades in the existing shutter, and the connection mode is as follows: punch at the both ends of blade 6 as connecting rope hole 8, connect rope 7 and wear to establish in connecting rope hole 8, a plurality of blades 6 set up on connecting rope 7 through connecting rope hole 8, still are provided with on every blade 6 and adjust rope 9, adjust the shutter angle that opens and shuts through the pull regulation rope 9, and the connected mode of adjusting rope 9 and blade 6 is prior art, no longer gives unnecessary details. The electric wires of the positive and negative poles of the battery can be arranged to be led out from the connecting rope hole 8 and connected to the energy storage device.
The foregoing shows and describes the general principles and broad features of the present invention and the advantages of the present patent. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are intended to be illustrative of one or more embodiments of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (12)
1. A preparation method of a perovskite solar cell comprises the preparation of a perovskite film layer, and is characterized in that: the preparation method of the perovskite film layer comprises the following steps: the preparation method comprises the following steps of (1) spin-coating DL-2-amino-3-phosphonopropionic acid and perovskite film layer materials on a hole transport layer to form a film; the perovskite film layer material comprises PbX a And a first material, the first material being capable of reacting with the PbX a Coordinate to form ABX 3 Crystalline compound, or perovskite film layer material bagComprises a second material, wherein the second material is ABX 3 A crystal form compound, wherein A and B are positive ions, and B is Pb 2+ X is an anion, a =2.
2. The method of manufacturing a perovskite solar cell as claimed in claim 1, characterized in that: the perovskite film layer material is PbI 2 、PbBr 2 A combination of at least two or more of FAI, MAI and MACl.
3. The method of manufacturing a perovskite solar cell as claimed in claim 1, characterized in that: the PbX is a Is PbI 2 The first material is FAI, MABr and MACl;
the preparation method of the perovskite film layer comprises the following steps:
a preparing a precursor solution, the precursor solution comprising
Solution one: pbI 2 And DL-2-amino-3-phosphonopropionic acid;
solution II: mixed solution of FAI, MABr and MACl;
b spin-coating the solution on the hole transport layer, and drying to form PbI 2 A film layer;
c double-spin coating the solution on PbI 2 Forming a perovskite film layer on the film layer;
d, annealing and cooling.
4. The method of manufacturing a perovskite solar cell as claimed in claim 1, characterized in that: the perovskite film layer material is FAPBI 3 And MACl;
the preparation method of the perovskite film layer comprises the following steps:
a, preparing a precursor solution, wherein the precursor solution is FAPbI 3 MACl, DL-2-amino-3-phosphonopropionic acid in DMF/DMSO;
b, coating the precursor solution on the hole transport layer;
c, dropwise adding chlorobenzene on the film layer;
d, annealing in a nitrogen atmosphere, and cooling to form the perovskite film layer.
5. The method of manufacturing a perovskite solar cell as claimed in claim 1, characterized in that: the DL-2-amino-3-phosphonopropionic acid is reacted with PbX a The molar ratio of (B) is 0.001 to 0.01.
6. The method of manufacturing a perovskite solar cell as claimed in claim 3, characterized in that: the mass mixing ratio of FAI, MABr and MACl is 90:9:12.
7. a perovskite solar cell comprising a perovskite film layer, characterized in that: the perovskite film layer comprises DL-2-amino-3-phosphonopropionic acid and perovskite film layer materials; the perovskite film layer material comprises PbX a And a first material, the first material and the PbX a Coordination enables the formation of ABX 3 The crystal form compound or the perovskite film layer material comprises a second material, and the second material is ABX 3 A crystal form compound, wherein A and B are positive ions, and B is Pb 2+ X is an anion, a =2.
8. The perovskite solar cell of claim 7, wherein: a is one of methylamino, amidino, cesium ion and rubidium ion, and X is I - 、Cl - 、 Br - One or a combination of several of them.
9. The perovskite solar cell of claim 7, wherein: the first material is organic salt, and the organic salt is one or a combination of several of FAI, FABr, FACL, MAI, MABr and MACl.
10. The perovskite solar cell of claim 7, wherein: the thickness of the perovskite film layer is 600-800nm.
11. The perovskite solar cell of claim 7, wherein: the perovskite film layer is obtained by the method I or the method II:
the method comprises the following steps: the perovskite film layer material comprises PbI 2 FAI, MABr and MACl;
the preparation method of the perovskite film layer comprises the following steps:
a preparing a precursor solution, the precursor solution comprising
Solution one: pbI 2 And DL-2-amino-3-phosphonopropionic acid;
solution II: mixed solution of FAI, MABr and MACl;
b spin-coating the solution on the hole transport layer, drying to form PbI 2 A film layer;
c double-spin coating the solution on PbI 2 Forming a perovskite film layer on the film layer;
d, annealing and cooling;
the second method comprises the following steps: the perovskite film layer material is PbI 2 FAI and MACl;
the preparation method of the perovskite film layer comprises the following steps:
a, preparing a precursor solution, wherein the precursor solution is PbI 2 A solution of FAI, MACl, DL-2-amino-3-phosphonopropionic acid dissolved in DMF/DMSO;
b, coating the precursor solution on a hole transport layer;
c, dropwise adding chlorobenzene on the film layer;
d, annealing in the nitrogen atmosphere, and cooling to form the perovskite film layer.
12. A blind, characterized in that: comprising a plurality of leaves having disposed thereon the perovskite solar cell of claim 7.
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