CN115472746B - Photovoltaic cell for underwater environment and manufacturing process thereof - Google Patents
Photovoltaic cell for underwater environment and manufacturing process thereof Download PDFInfo
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Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a photovoltaic cell for underwater environment and a manufacturing process thereof, wherein a light absorbing material is a lead-based perovskite semiconductor; the photovoltaic cell with the wide band gap can be used for underwater photovoltaic power generation, and the problem that the prior art is difficult to supply power for underwater electric equipment for a long time is solved. The main structure of the battery comprises a bendable metal substrate, a hole transmission material, a hole modification layer, a perovskite light absorption material, a passivation layer, an electron transmission layer, a transparent electrode and the like. The band gap of the perovskite light absorption layer in the underwater photovoltaic cell is wider (about 1.9-2.5 eV), so that lead-bromine-formamidine tri-FAPbBr 3 Perovskite materials are used as the basis, and perovskite light absorption materials with different band gaps are selected according to different water depths.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a photovoltaic cell for an underwater environment and a manufacturing process thereof.
Background
The perovskite solar cell is a novel photovoltaic cell technology, has a large adjustable light absorption range, and has the characteristics of easy processing, low cost and the like. In recent years, the photoelectric conversion efficiency of perovskite solar cells has been rapidly improved to a level of 25.7%, but the development of practical applications is limited.
Along with the continuous development progress and age transition of society, the application of the flexible photovoltaic cell devices is increasingly important, and the flexible photovoltaic cell devices have the characteristics of light weight, flexibility, bending and the like, have higher use flexibility and have wide use fields. At present, a flexible photovoltaic device mainly uses a plastic transparent substrate such as polyethylene terephthalate (PET), polyethylene 2, 6-naphthylacetate (PEN) and the like, and has excellent bending performance, but the substrate strength is very low, so that the transparent conductive layer and the light absorption layer are easily damaged in the use process, and the performance of the battery is quickly attenuated and the practicability is poor. The invention aims at the problems, adopts bendable metal as a substrate, has strength and flexibility, and has more application value.
The perovskite material has good weak light response, can adjust the band gap, and can be perfectly matched with applications with different water depths. From 2-100m water depth, corresponding to band gaps of 1.9 eV-2.5 eV, photovoltaic cells for underwater scenes are still blank at present, and under the prospect of prosperous development of industries such as detectors, underwater robots, aquaculture and the like, the realization of an underwater autonomous power supply system is urgent.
Disclosure of Invention
In order to solve or partially solve the problems existing in the related art, the present application provides a photovoltaic cell for an underwater environment and a manufacturing process thereof. According to the invention, the metal with rigidity and flexibility is taken as the substrate skeleton of the underwater photovoltaic device, the characteristics that the perovskite can realize the flexible device and the weak light response performance is excellent are fully exerted, and the trans-perovskite solar cell which can be widely applied in both underwater and natural environments is developed. Perovskite batteries with different band gaps correspond to underwater power generation performances with different depths, and can achieve maximization of photoelectric conversion efficiency.
The first aspect of the application provides a photovoltaic cell for underwater environment, wherein the photovoltaic cell is of a p-i-n structure, and the bottom layer and the top layer are respectively a bendable metal substrate, a hole transport layer, a hole modification layer, a perovskite light absorption layer, an interface passivation layer, an electron transport layer and a transparent conductive layer.
Further, the bendable metal substrate comprises an alloy of iron, copper and nickel, wherein the thickness of the alloy is 30-200 mu m.
Further, the hole transport layer is made of nickel oxide NiO x Or nickel oxide NiO x Mesoporous inorganic hole conductor composite structure, or nickel oxide NiO x Organic functional molecule modified layer structure.
Further, the hole modification layer comprises carbazole molecules containing fluorine F, chlorine Cl, bromine Br and iodine I functional groups.
Further, the light absorbing layer is a three-dimensional perovskite or a two-dimensional/three-dimensional composite perovskite material treated by a two-dimensional interface, the thickness of the three-dimensional perovskite material is 300-1000nm, the three-dimensional perovskite material is based on lead bromide tri-FAPbBr 3 formamidine, the band gap is 2.26eV, and monovalent cations or halogen are simultaneously adoptedDoping of ions of formula FA x MA y Cs 1-x-y PbCl a Br 3-a-b I b Cl or I is less than or equal to 30 percent, and the monovalent cations comprise, but are not limited to methylamine MA, formamidine FA and cesium Cs; the doped halide ions are chlorine Cl, bromine Br and iodine I.
Further, the interface passivation layer comprises a surface interface modification layer and an interface defect passivation layer, wherein the surface interface modification layer comprises organic functional molecules, a two-dimensional perovskite material, an inorganic two-dimensional perovskite material or zinc sulfide ZnS, lead sulfide PbS and carbon 60C60.
Further, the interface modification material used for the interface passivation layer comprises:
1) Bulky functional amine organic compounds of different chain lengths; 2) An organic molecular interface passivating agent; 3) Self-assembled molecules or polymers with specific functions; 4) An inorganic compound.
Further, the electron transport layer adopts titanium oxide TiO 2 Tin oxide SnO 2 Zinc oxide ZnO and niobium oxide Nb 2 O 5 One or more of zinc sulfide ZnS forms a film with the thickness of 30-300 nm.
Further, the transparent conductive layer comprises a transparent conductive electrode of indium doped zinc oxide IZO, aluminum doped zinc oxide AZO, indium doped tin oxide ITO and indium doped tungsten oxide IWO.
The second aspect of the present application provides a process for manufacturing a photovoltaic cell for an underwater environment, comprising the steps of:
s1, cleaning the bendable metal substrate with purified water or isopropyl alcohol IPA, and drying with a hot air blower for later use.
S2, preparing a layer of uniform and compact nickel oxide NiO on the bendable metal substrate by an electron beam evaporation mode x Thin film with thickness of 10-20nm.
S3, preparing carbazole solutions (the concentration is 0.05-1mmol L) containing fluorine, chlorine, bromine and iodine with different concentrations -1 ) Deposited to NiO by knife coating x Annealing the substrate at 80-100 ℃ for 1-8 minutes to obtain a uniform and compact carbazole modified film;
s4, preparing perovskite precursor liquid, treating the substrate obtained in the step S3 by using an oxygen plasma machine for 20 minutes, then dripping the perovskite precursor liquid on the edge of the substrate, scraping the substrate at a speed of 1-3mm/S by using a scraper, blowing nitrogen for about 30 seconds under the pressure of 0.1-2MPa, then annealing at 60 ℃ for 5 minutes, annealing at 140 ℃ for 20 minutes, and cooling to room temperature;
s5, preparing an interface passivation layer on the surface of the perovskite film by a thermal evaporation method on the surface of the perovskite, wherein the interface passivation layer is magnesium fluoride MgF x The thickness is 5-50nm.
S6, depositing an electron transport layer on the surface of the passivation layer by an electron beam evaporation technology, wherein the electron transport layer is niobium oxide Nb 2 O 5 Tin oxide SnO 2 A composite electron transport layer with a thickness of 10-50nm;
s7, preparing a transparent conducting layer on the surface of the electron transport layer by means of magnetron sputtering and the like: indium doped zinc oxide IZO.
Alternatively, S3 may also be: nickel oxide NiO x The film is completely immersed in carbazole solution (concentration of 0.05-1mmol L) containing fluorine F, chlorine Cl, bromine Br, iodine I -1 ) Heating at 20-50 deg.c for 0.5-10 min, washing with isopropyl alcohol IPA for 2-3 times, and annealing at 80-100 deg.c for 2-8 min to obtain homogeneous and compact carbazole modified film.
Further, the perovskite precursor liquid in S4 comprises lead bromide tri-FAPbBr 3 precursor liquid and FAPbBr 2.7 I 0.3 Precursor liquid, FAPbBr 2.4 I 0.6 Precursor liquid, FAPbBr 2.1 I 0.9 Precursor liquid, FAPbBr 2.7 Cl 0.3 Precursor liquid, FAPbBr 2.4 Cl 0.6 Precursor liquid, FAPbBr 2.1 Cl 0.9 Precursor liquid.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed.
The beneficial technical effects of the invention are as follows:
the photovoltaic cell for the underwater environment, which is designed by the invention, can be applied to environments with different water depths by adjusting different band gaps of perovskite, the prepared wide band gap photovoltaic cell can realize underwater photovoltaic power generation, the long-term power requirement of an underwater appliance can be met, the high-efficiency and long-term power supply of external equipment can be realized, and the problem that the long-term power supply of underwater electric equipment is difficult in the prior art is solved.
The invention selects stainless steel material as the substrate, the stainless steel has certain flexibility and rigidity, can be repeatedly bent, and even can be bent into a circle with the diameter of about 2 cm, and the photovoltaic cell prepared by the invention overcomes the defects of performance reduction and the like of the common flexible cell caused by a plurality of bending times.
Drawings
FIG. 1 is a schematic diagram of the device structure of a flexible perovskite solar cell with a bendable metal substrate according to the present invention;
FIG. 2 is a schematic illustration of bending of a bendable metal-substrate perovskite solar cell device of the invention;
FIG. 3 shows the molecular structural formula of carbazole derivatives containing fluorine F, chlorine Cl, bromine Br and iodine I in the invention;
FIG. 4 is a schematic diagram of a carbazole solution impregnation method in the present invention.
Detailed Description
Alternative embodiments of the present application will be described in more detail below with reference to the accompanying drawings. While the drawings illustrate alternative embodiments of the present application, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The terminology used in the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
The invention applies for a photovoltaic cell used in underwater environment and a manufacturing process thereof by combining the following drawings
The detailed description is as follows:
the application provides a photovoltaic cell for an underwater environment, which is of a p-i-n structure, wherein a bendable metal substrate, a hole transport layer, a hole modification layer, a perovskite light absorption layer, an interface passivation layer, an electron transport layer and a transparent conductive layer are arranged from bottom to top. The water has a strong absorption effect on sunlight, and the absorption capability of the water on solar spectrums of different wave bands is different, so that the penetration depths of the sunlight of different wave bands are different, the photoelectric efficiency of the high-efficiency photovoltaic cell on the ground can become very low, and the light absorption range of the perovskite material is required to be correspondingly adjusted to realize the excellent photoelectric conversion capability. According to theoretical simulation, according to the difference of the depth of water, the optimal band gap of perovskite is between 1.9 and 2.5eV, and the optimal band gap of photovoltaic cell suitable for ground is between 1.45 and 1.9 eV.
In one embodiment of the present application, the flexible metal substrate is made of a metal material with flexibility and rigidity, including but not limited to an alloy of iron, copper, nickel and the like, and is applied to an underwater environment, and the flexible metal substrate has corrosion resistance and other characteristics, and can resist weak corrosion media such as air, steam, water and the like and also resist corrosion of seawater. The method is divided into the following steps according to the tissue state: martensitic steels, ferritic steels, austenitic-ferritic (duplex) stainless steels, precipitation-hardenable stainless steels, and the like; in addition, the components can be divided into: chromium stainless steel, chromium nickel stainless steel, chromium manganese nitrogen stainless steel, and the like. Contains C, cr, ni, ti, mn, N, nb, mo, si, cu and other elements including 200, 300, 400, 500, 600, etc.
In one embodiment of the present application, the bendable metal substrate has a thickness of 30-200 μm.
In one embodiment of the present application, the hole transport layer is nickel oxide NiO x Or nickel oxide NiO x Mesoporous inorganic hole conductor composite structure, or nickel oxide NiO x Organic functional molecule modified layer structure
In one embodiment of the present application, the hole-modifying layer is, but not limited to, a carbazole-based molecule containing a functional group such as fluorine, chlorine, bromine, or iodine.
In one embodiment of the present application, the light-absorbing layer is a three-dimensional perovskite or a two-dimensional/three-dimensional composite perovskite material treated with a two-dimensional interface, and the thickness of the light-absorbing layer is 300-1000nm, and the light-absorbing layer is prepared by a doctor blade or coating method.
In one embodiment of the present application, the three-dimensional perovskite material, the underwater photovoltaic is based on lead bromide tri-FAPbBr 3 formamidine, has a bandgap of 2.26eV, and can be doped with monovalent cations or halide ions, and has a molecular formula of FA x MA y Cs 1-x-y PbCl a Br 3-a-b I b The proportion of chlorine Cl or iodine I is less than or equal to 30%, namely the material is bromine-rich perovskite.
In one embodiment of the present application, the doped monovalent cations include, but are not limited to, methylamine MA + Formamidine FA + Cesium Cs + The method comprises the steps of carrying out a first treatment on the surface of the The doped halide ion is chlorine Cl - Bromine Br - Iodine I - 。
In one embodiment of the application, the interface passivation layer comprises a surface interface modification layer and an interface defect passivation layer, wherein the surface interface modification layer comprises organic functional molecules, a two-dimensional perovskite material, an inorganic two-dimensional perovskite material or zinc sulfide ZnS, lead sulfide PbS and carbon 60C60, and plays a role in passivating the surface defects of the perovskite light absorbing material and improving interface contact between perovskite and the charge transmission layer.
In one embodiment of the present application, the interface defect passivation layer is formed from modified materials including, but not limited to, the following: 1) The amine organic compound with different chain lengths and large volume is selected from one or more of phenethylamine salt PEAX, guanidine salt GAX, dimethylamine salt DMAX, ethylamine salt EAX, butylamine salt BAX, methyl triethylamine salt MTEAX, etcWherein X can be one of chlorine Cl, bromine Br or iodine I; 2) Organic molecular interface passivating agents such as lewis acids, bases, amphoteric compounds, fullerene derivatives (PCBM, C60, etc.), mainly small organic molecules containing amino, sulfur S, fluorine F, chlorine Cl, bromine Br, iodine I elements; 3) Or self-assembled molecules, polymers, etc. with specific functions, such as fullerene derivatives and aromatic acids; 4) Inorganic compounds, e.g. sulfides, lithium fluoride LiF, magnesium fluoride (MgF 2 ,MgF x ) Carbon 60C60, inorganic two-dimensional perovskite material, hybrid two-dimensional perovskite material, and the like.
In one embodiment of the present application, the electron transport layer is made of titanium oxide TiO 2 Tin oxide SnO 2 Zinc oxide ZnO and niobium oxide Nb 2 O 5 Inorganic compound materials such as zinc sulfide ZnS and the like form films, or a composite structure of two or more of them. The thickness is 30-300 nm, and the microstructure is a compact film.
In one embodiment of the present application, the transparent conductive layer includes, but is not limited to, indium doped zinc oxide IZO, aluminum doped zinc oxide AZO, indium doped tin oxide ITO, indium doped tungsten oxide IWO, and other transparent conductive electrodes.
The invention also provides a manufacturing process of the photovoltaic cell for the underwater environment, which comprises the following steps of:
s1, cleaning the bendable metal substrate with purified water or isopropyl alcohol IPA, and drying with a hot air blower for later use.
S2, preparing a layer of uniform and compact nickel oxide NiO on the bendable metal substrate by an electron beam evaporation mode x Thin film with thickness of 10-20nm.
S3, preparing carbazole solutions (the concentration is 0.05-1mmol L) containing fluorine, chlorine, bromine and iodine with different concentrations -1 ) Deposited on nickel oxide NiO by knife coating x Annealing the substrate at 80-100 ℃ for 1-8 minutes to obtain a uniform and compact carbazole modified film;
s4, preparing perovskite precursor liquid, treating the substrate obtained in the step S3 by using an oxygen plasma machine for 20 minutes, then dripping the perovskite precursor liquid on the edge of the substrate, scraping the substrate at the speed of 1-3mm/S by using a scraper, blowing for about 30 seconds by using 0.1-2Mpa nitrogen, then annealing at 60 ℃ for 5 minutes, annealing at 140 ℃ for 20 minutes, and cooling to room temperature;
s5, preparing an interface passivation layer on the surface of the perovskite film by a thermal evaporation method on the surface of the perovskite, wherein the interface passivation layer is magnesium fluoride MgF x The thickness is 5-50nm.
S6, depositing an electron transport layer on the surface of the passivation layer by an electron beam evaporation technology, wherein the electron transport layer is niobium oxide Nb 2 O 5 Tin oxide SnO 2 A composite electron transport layer with a thickness of 10-50nm;
s7, preparing a transparent conducting layer on the surface of the electron transport layer by means of magnetron sputtering and the like: indium doped zinc oxide IZO.
In an alternative embodiment of the present application, S3 may be: nickel oxide NiO x The film is completely immersed in carbazole solution (concentration is 0.05-1mmol L) -1 ) Heating at 20-50 deg.c for 0.5-10 min, washing with isopropyl alcohol IPA for 2-3 times, and annealing at 80-100 deg.c for 2-8 min to obtain homogeneous and compact carbazole modified film.
In one embodiment of the present application, the perovskite precursor solution in S4 includes lead bromide tri-FAPbBr 3 precursor solution of formamidine, FAPbBr 2.7 I 0.3 Precursor liquid, FAPbBr 2.4 I 0.6 Precursor liquid, FAPbBr 2.1 I 0.9 Precursor liquid, FAPbBr 2.7 Cl 0.3 Precursor liquid, FAPbBr 2.4 Cl 0.6 Precursor liquid, FAPbBr 2.1 Cl 0.9 Precursor liquid.
For clarity, the following examples are provided in detail.
Example 1
This example provides a wide bandgap perovskite (lead-bromo-formamidine trippbbr) with a bandgap of 2.26eV 3 ) A method of manufacturing a solar cell, the method comprising:
1. the bendable metal substrate is cleaned by purified water and isopropyl alcohol IPA, and is dried by a hot air blower for standby.
2. Preparing a layer of uniform and compact nickel oxide NiO on a bendable metal substrate by an electron beam evaporation mode x Thin film with thickness of 10-20nm.
3. The prepared carbazole solutions containing fluorine or chlorine or bromine or iodine with different concentrations (concentration is 0.05-1mmol L -1 ) Deposited on nickel oxide NiO by knife coating x Annealing the substrate at 80-100 ℃ for 1-8 minutes to obtain a uniform and compact carbazole modified film; carbazole molecule modified nickel oxide NiO x Not only can reduce interface non-radiative recombination, but also can effectively promote hole transport and improve nickel oxide NiO x The energy band arrangement of the device and the filling factor FF of the device are improved, and the photoelectric performance of the device is further improved.
4. Perovskite precursor liquid: 1.2mmol of formamidine bromide FABr and 1.2mmol of lead bromide PbBr 2 The mixture is dissolved in 750uL of N, N-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO, stirred evenly by magnetic force, aged for 12 hours and filtered for standby.
And (3) treating the substrate obtained in the step (3) for 20 minutes by using an oxygen plasma machine, then dripping the perovskite precursor on the edge of the substrate, scraping the substrate with a scraper at a speed of 1-3mm/s, blowing nitrogen for about 30 seconds under the pressure of 0.1-2MPa, then annealing at 60 ℃ for 5 minutes, annealing at 140 ℃ for 20 minutes, and cooling to room temperature.
5. Preparing an interface passivation layer on the surface of the perovskite film by a thermal evaporation method on the surface of the perovskite film: mgF of magnesium fluoride x The thickness is 5-50nm.
6. Preparing an electron transport layer by depositing an electron beam evaporation technology on the surface of the passivation layer: niobium oxide Nb 2 O 5 Tin oxide SnO 2 And the thickness of the composite electron transport layer is 10-50nm.
7. Preparing a transparent conductive layer on the surface of the electron transport layer by means of magnetron sputtering and the like: indium doped zinc oxide IZO, thus obtaining a complete titanium ore solar cell device, and the statistics of the device performance parameters are shown in table 1.
The flexible perovskite solar cell with the bendable metal substrate has certain flexibility, certain rigidity and large bending degree, can be bent into a circle with the diameter of about 2 cm as shown in fig. 2, can be mounted on the surfaces of different substrates to supply power, and can be applied to different requirements.
Example 2
The embodiment provides a method for preparing a hole modified layer by solution method chemical adsorption, which comprises the following steps:
nickel oxide NiO x The film is completely immersed in carbazole solution (concentration of 0.05-1mmol L) containing fluorine or chlorine or bromine or iodine -1 ) Heating at 20-50 deg.c for 0.5-10 min, washing with isopropyl alcohol IPA for 2-3 times, and annealing at 80-100 deg.c for 2-8 min to obtain homogeneous and compact carbazole modified film. The coverage rate of the film obtained by the dipping method is higher and more uniform, and the substrate with a complex shape can be uniformly coated, so that the cost of required equipment is low, and the dipping method is very suitable for large-area production and preparation.
The remaining preparation steps were the same as in example 1.
Example 3
The embodiment provides a preparation method of a zinc sulfide ZnS interface modified lead-bromine-formamidine-three-FAPbBr 3 solar cell, which comprises the following steps:
depositing a zinc sulfide ZnS interface modification layer with the thickness of <5nm on the perovskite substrate by atomic layer deposition ALD or a sol method.
On the one hand, the zinc sulfide ZnS is an inorganic substance, so that the light transmittance is good and the stability is high; on the other hand, as the zinc sulfide ZnS has the characteristic of electron transmission, the interface modification can play a dual-function role, so that not only can the extraction and transmission of electrons be accelerated, but also the perovskite surface can be modified, the surface defect density is reduced, and the performance and stability of the device are improved.
The rest of the procedure is the same as in example 1. The device performance parameter statistics are shown in table 2.
Example 4
The embodiment provides a preparation method of a bendable perovskite solar cell with a bendable metal substrate, wherein the band gap of the bendable perovskite solar cell ranges from 1.90 eV to 2.26eV, and the preparation method comprises the following steps:
FAPbBr 2.7 I 0.3 precursor liquid: 104.97mg of formamidine hydrobromide FABr,62.17mg of formamidineHydroiodinated FAI and 440.41mg lead bromide PbBr 2 The mixture was stirred magnetically in 750uL of n, n-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO and aged for 12 hours and pre-filtered. The formula corresponds to the band gap of 2.10eV, and can realize high-efficiency stable operation in a water depth environment of 10-20 meters of pure water.
FAPbBr 2.4 I 0.6 Precursor liquid: 59.98mg of formamidine hydrobromide FABr,124.34mg of formamidine hydroiodide FAI and 440.41mg of lead bromide PbBr 2 The mixture was stirred magnetically in 750uL of n, n-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO and aged for 12 hours and pre-filtered. The formula corresponds to the band gap of 1.98eV, and can realize high-efficiency stable operation in a water depth environment of 5-10 meters of pure water.
FAPbBr 2.1 I 0.9 Precursor liquid: 14.99mg of formamidine hydrobromide FABr,186.52mg of formamidine hydroiodide FAI and 440.41mg of lead bromide PbBr 2 The mixture was stirred magnetically in 750uL of n, n-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO and aged for 12 hours and pre-filtered. The formula corresponds to the band gap of 1.83eV, and can realize high-efficiency stable operation in a water depth environment of 0-5 meters of pure water.
The remaining steps were the same as in example 1. The band gap, absorbance range and corresponding optimum water depths for the perovskite are shown in table 3 and the device performance parameter statistics are shown in table 4.
Example 5
The embodiment provides a preparation method of a bendable perovskite solar cell with a bendable metal substrate, wherein the band gap of the bendable perovskite solar cell ranges from 2.26eV to 2.50eV, and the preparation method comprises the following steps:
FAPbBr 2.7 Cl 0.3 precursor liquid: 104.97mg of formamidine hydrobromide FABr,28.99mg of formamidine hydrochloride FACl and 440.41mg of lead bromide PbBr 2 The mixture was stirred magnetically in 750uL of n, n-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO and aged for 12 hours and pre-filtered. The formula corresponds to the band gap of 2.34eV, and can realize high-efficiency stable operation in a water depth environment of 40-60 meters of pure water.
FAPbBr 2.4 Cl 0.6 Precursor liquid: 59.98mg of formamidine hydrobromide FABr,57.97mg of formamidine hydrochloride FACl and440.41mg of lead bromide PbBr 2 The mixture was stirred magnetically in 750uL of n, n-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO and aged for 12 hours and pre-filtered. The formula corresponds to the band gap of 2.41eV, and can realize high-efficiency stable operation in a water depth environment of 60-80 meters of pure water.
FAPbBr 2.1 Cl 0.9 Precursor liquid: 14.99mg of formamidine hydrobromide FABr,86.96mg of formamidine hydrochloride FACl and 440.41mg of lead bromide PbBr 2 The mixture was stirred magnetically in 750uL of n, n-dimethylformamide DMF and 250uL of dimethyl sulfoxide DMSO and aged for 12 hours and pre-filtered. The formula corresponds to the band gap of 2.48eV, and can realize high-efficiency stable operation in a water depth environment of 80-100 meters of pure water.
The remaining steps were the same as in example 1. The band gap, absorbance range and corresponding optimum water depths for the perovskite are shown in table 5 and the statistics of device performance parameters are shown in table 6.
TABLE 1 statistics of device Performance parameters obtained by different modification methods
Note that: j (J) SC : short circuit current density; v (V) OC : an open circuit voltage; FF: a fill factor; PCE: energy conversion efficiency
TABLE 2 statistics of device Performance parameters from different modification methods
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
Note that: * The corresponding optimal water depth is the depth of water in a pure water environment.
Tables 1 and 2 are statistics of device performance parameters obtained by different modification methods, respectively;
tables 3 and 5 are band gap, absorbance range and corresponding optimum pure water depths, respectively, for different types of perovskite;
tables 4 and 6 are device performance parameter statistics for different types of perovskite, respectively.
The foregoing description of the embodiments of the present application is illustrative, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the improvement of technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (7)
1. The preparation method of the photovoltaic cell for the underwater environment is characterized in that the cell has a p-i-n structure, and comprises a bendable metal substrate, a hole transport layer, a hole modification layer, a perovskite light absorption layer, an interface passivation layer, an electron transport layer and a transparent conductive layer from bottom to top; the light absorption layer is a three-dimensional perovskite or a two-dimensional/three-dimensional composite perovskite material treated by a two-dimensional interface, the thickness of the three-dimensional perovskite material is 300-1000nm, and the three-dimensional perovskite material is lead formamidine bromine trippbbr 3 Based on a band gap of 2.26eV, doped with monovalentCation or halogen ion with molecular formula of FA x MA y Cs 1-x-y PbCl a Br 3-a-b I b The proportion of chlorine Cl or iodine I is less than or equal to 30%, the monovalent cations comprise methylamine MA, formamidine FA and cesium Cs, and the doped halide ions are Cl chlorine, br bromine and I iodine; the hole transport layer is nickel oxide NiO x A film; the cavity modification layer is carbazole molecules containing fluorine, chlorine, bromine and iodine functional groups; the interface passivation layer is magnesium fluoride MgF X Or zinc sulfide ZnS;
the preparation of the photovoltaic cell comprises the following steps:
s1, cleaning a bendable metal substrate with purified water or isopropyl alcohol IPA, and drying the bendable metal substrate with a hot air blower for later use;
s2, preparing a layer of uniform and compact nickel oxide NiO on the bendable metal substrate by means of electron beam evaporation or magnetron sputtering x A film, a hole transport layer is obtained;
s3, preparing the mixture with the concentration of 0.05-1mmol L -1 Is deposited on nickel oxide NiO by a doctor blade method x Annealing the substrate at 80-100 ℃ for 1-8 minutes to obtain a uniform and compact hole modified layer;
s4, preparing perovskite precursor liquid, treating the substrate obtained in the step S3 by using an oxygen plasma machine for 20 minutes, then dripping the perovskite precursor liquid on the edge of the substrate, scraping the substrate at a speed of 1-3mm/S by using a scraper, blowing nitrogen for about 30 seconds under the pressure of 0.1-2MPa, then annealing at 60 ℃ for 5 minutes, annealing at 140 ℃ for 20 minutes, and cooling to room temperature to obtain a perovskite light absorption layer;
s5, preparing an interface passivation layer on the surface of the perovskite light absorption layer by a thermal evaporation method;
s6, depositing an electron transport layer on the surface of the interface passivation layer by an electron beam evaporation method;
s7, preparing a transparent conductive layer on the surface of the electron transport layer through magnetron sputtering.
2. The method of claim 1, wherein the bendable metal substrate comprises an alloy of iron, copper, nickel, the alloy having a thickness of 30-200 μm.
3. The method according to claim 1, wherein the electron transport layer is made of titanium oxide TiO 2 Tin oxide SnO 2 Zinc oxide ZnO and niobium oxide Nb 2 O 5 One or more of zinc sulfide ZnS forms a film with the thickness of 30-300 nm.
4. The method of claim 1, wherein the transparent conductive layer comprises a transparent conductive electrode of indium doped zinc oxide IZO, aluminum doped zinc oxide AZO, indium doped tin oxide ITO, indium doped tungsten oxide IWO.
5. The method of claim 1, wherein S3 is further selected from the group consisting of: nickel oxide NiO x The film is completely immersed into the solution containing fluorine, chlorine, bromine and iodine with the concentration of 0.05-1mmol L -1 Heating at 20-50 ℃ for 0.5-10 min, then cleaning with isopropyl alcohol IPA for 2-3 times, and annealing at 80-100 ℃ for 2-8 min on a heating table to obtain the uniform and compact carbazole modified film.
6. The method according to claim 1, wherein the perovskite precursor solution in S4 comprises lead bromide tri-FAPbBr 3 precursor solution of formamidine, FAPbBr 2.7 I 0.3 Precursor liquid, FAPbBr 2.4 I 0.6 Precursor liquid, FAPbBr 2.1 I 0.9 Precursor liquid, FAPbBr 2.7 Cl 0.3 Precursor liquid, FAPbBr 2.4 Cl 0.6 Precursor liquid, FAPbBr 2.1 Cl 0.9 Precursor liquid.
7. A photovoltaic cell for use in an underwater environment prepared by the method of any one of claims 1 to 6.
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