CN113097388B - Perovskite battery based on composite electron transport layer and preparation method thereof - Google Patents
Perovskite battery based on composite electron transport layer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 17
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 52
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- 230000031700 light absorption Effects 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000005525 hole transport Effects 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 105
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 43
- 238000004528 spin coating Methods 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
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- 239000002245 particle Substances 0.000 claims description 22
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- 239000007864 aqueous solution Substances 0.000 claims description 19
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 2
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 claims description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
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- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
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- 230000000694 effects Effects 0.000 description 6
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- 238000009825 accumulation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
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- 239000001301 oxygen Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- IKUCKMMEQAYNPI-UHFFFAOYSA-N [Pb].CN.[I] Chemical compound [Pb].CN.[I] IKUCKMMEQAYNPI-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a perovskite battery based on a composite electron transport layer, which comprises a substrate material, a transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a counter electrode which are sequentially arranged from bottom to top; the electron transport layer is a composite electron transport layer and has a planar structure, the composite electron transport layer is composed of at least two metal oxides, and metal elements of the two metal oxides respectively have different electronegativity. According to the invention, the morphology structure and the electronic structure of the original tin oxide metal oxide transmission layer film are improved by compounding the metal tungsten oxide compound in the electron transmission layer, so that the energy level distribution and the carrier mobility change of the electron transmission layer are caused, the energy level arrangement which is more matched with the perovskite light absorption layer is obtained, the open circuit voltage and the carrier separation and collection efficiency are improved, the non-radiative recombination of an interface is reduced, the resistance loss is reduced, and the filling factor is improved, thereby improving the photovoltaic performance of the perovskite battery.
Description
Technical Field
The invention relates to the field of perovskite solar cells, in particular to a perovskite cell based on a composite electron transport layer and a preparation method thereof.
Background
Due to the rapid development of economy and the rapid population growth, the industrialization process is continuously advanced, and the energy shortage and the environmental pollution become two major difficulties facing the human beings at present. The rapid development of clean energy and renewable energy is the main solution at present. The solar cell converts light energy into electric energy, has the characteristics of cleanness and no pollution, and has very wide application prospect. Perovskite solar cells are a type of solar cells which are rapidly developed at present, and have the characteristics of high photoelectric conversion efficiency, low cost, simple preparation and the like. Over ten years of development, the rate of improvement has been rapidly increased from 3.8% to 25.5% in 2009.
The perovskite solar cell is divided into a planar structure and a mesoporous structure according to the structure, and mainly comprises a transparent electrode, an electron transmission layer, a perovskite light absorption layer material, a hole transmission material, a counter electrode and the like. The perovskite material absorbs light to generate photo-generated electrons and holes, and the photo-generated electrons and holes are respectively transmitted to the electron transmission layer and the hole transmission layer and are connected with an external circuit to form a loop to output electric energy. The main electron transport layer material at present is mainly metal oxide semiconductor with high chemical stability, wherein a film prepared from tin oxide solution is widely used with high light transmittance, high carrier mobility, strong ultraviolet stability and proper energy level matching degree, and the authentication efficiency of the tin dioxide perovskite battery at present reaches 23.3 percent. However, due to the fact that particle agglomeration exists in the commercial tin dioxide solution, dispersion stability of the colloidal solution is affected, compactness and coverage rate of the prepared film are poor, pinholes exist, tight contact between an electron transport layer and a perovskite light absorption layer is seriously affected, resistance loss (series resistance and parallel resistance) is increased, and improvement of device filling factors is inhibited (DOI: 10.1126/science. Ab8687; 10.1002/adma.202003990;10.1016/j. Chempr. 2020.04.013); in addition, the electron mobility of tin dioxide is still low compared to the usual hole materials (Spiro-ome tad) (DOI: 10.1038/s 41467-018-05760-x), resulting in interfacial charge accumulation and non-radiative recombination, which can result in hysteresis effects of current-voltage and open circuit voltage loss at bias voltages in different directions and loss of fill factor at low carrier extraction and collection capacities.
Therefore, it is very important to improve the dispersion stability of the tin dioxide colloidal solution and the electron mobility of the film, reduce the resistance loss, improve the filling factor, reduce the interface defect recombination caused by the accumulation of interface charges, optimize the energy level matching of the electron transport layer and the perovskite active layer, and reduce the open circuit voltage loss.
Disclosure of Invention
The following presents a simplified summary of embodiments of the invention in order to provide a basic understanding of some aspects of the invention. It should be understood that the following summary is not an exhaustive overview of the invention. It is not intended to identify key or critical elements of the invention or to delineate the scope of the invention. Its purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is discussed later.
Aiming at the problems of non-radiative recombination caused by interfacial charge accumulation when the photo-generated electrons of the perovskite solar cell are transferred to an electron transport layer by a perovskite absorption layer, resistance loss caused by non-tight interfacial contact between a perovskite film and the electron transport layer film, energy level mismatch between an active layer and the electron transport layer and the like caused by poor dispersion stability of a tin dioxide solution. The fill factor achieved by the present invention is the highest fill factor of a tin oxide perovskite cell.
According to one aspect of the present application, there is provided a perovskite battery based on a composite electron transport layer, comprising a substrate material, a transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a counter electrode, which are sequentially arranged from bottom to top; the electron transport layer is a composite electron transport layer and has a planar structure, the composite electron transport layer is composed of at least two metal oxides, and metal elements of the two metal oxides respectively have different electronegativity.
Furthermore, in the prior art, only one oxide is generally adopted as an electron transport layer, the particle size is generally 10-200nm, and in order to realize compact and uniform coverage of a hole-free electron transport layer without obviously increasing resistance, the invention discovers that two metal oxides are adopted for compounding, the particle size can be controlled at 5-50nm and 100-200nm respectively, and the thickness of a composite film is controlled at 20-80nm. After the two particles with different particle sizes are mutually doped, holes generated during spin coating can be filled, so that a more compact and uniformly covered electronic layer film is prepared, and the performance of the photovoltaic device is enhanced.
Further, the composite electron transport layer is composed of tin oxide and tungsten oxide aqueous solution, the volume ratio of the tin oxide solution to the tungsten oxide solution is 1:1-15:1 (the preferable ratio is 10:1), and the novel composite electron transport layer is of a planar structure. Among them, the tungsten oxide material itself has the advantages of high electron mobility, proper band gap width, high film light transmittance, strong oxygen vacancy tolerance, low material cost, etc., and is suitable for being used as the electron transport layer material of perovskite batteries, but the photoelectric conversion efficiency of the perovskite batteries using tungsten oxide as a single electron transport layer reported at present is still below 20% (DOI: 10.1016/j. Nanoen.2020.105564), so that the tungsten oxide is combined with other oxide materials to form a possible break. The highest conversion efficiency of perovskite cells prepared using tungsten oxide as an interface modification layer of titanium oxide or tin oxide has been reported to be 20.5% (DOI: 10.1016/j. Nanoen. 2019.06.021). Films prepared using commercial tin oxide colloidal solutions have been widely used as electron transport layers for perovskite batteries due to their low temperature solution preparation process and advantages of high stability, high electron mobility, etc., and the reported conversion efficiencies have exceeded 23% (DOI: 10.1038/nenergy.2016.177). However, there are also some common problems, one of which is that the current commercial tin dioxide colloid is easy to agglomerate into large particle particles due to the attractive effect of the van der Waals force among the particles, so that the solution dispersion stability is poor, holes are easy to appear when an electronic layer film is deposited by spin coating, the quality is affected, and the interface contact between the perovskite layer and the perovskite layer is affected, so that the photoelectric performance of the perovskite battery device is deteriorated. At present, no report of directly mixing a tungsten oxide aqueous solution and a tin oxide colloid solution to prepare a composite electron transport layer for a perovskite battery is explored, so the solution of the applicant is as follows: the mixed solution of tin oxide and tungsten oxide comprises a tin oxide colloid solution and a tungsten oxide water solution: the tin oxide colloid solution consists of colloid particles with the particle size of 5-50nm and alkaline solution (KOH) (ph is approximately equal to 12); the tungsten oxide aqueous solution consists of particles with the particle size of 100-200nm (namely, the particle size of tungsten oxide in the tungsten oxide aqueous solution is 100-200 nm). The tin oxide colloid solution may be generally a commercially available basic commercial tin oxide colloid solution. The tungsten oxide can react with alkaline solution to promote the coagulation-hydrolysis equilibrium state of colloid solution, and can fully regulate the dispersion stability of colloid, thereby improving the film quality of the electron transport layer and the interface contact between the transport layer and perovskite. And secondly, the situation that energy level mismatch exists between a film obtained by direct spin-coating deposition of a commercial tin oxide solution and a perovskite absorption layer causes serious voltage loss, and the undesirable device performance is obtained. After a certain amount of tungsten oxide water solution is added into the tin oxide solution, the electronic structure state of the tin oxide surface can be adjusted, so that the energy band structure of the tin oxide semiconductor can be adjusted, and the position which is more matched with the perovskite absorption layer can be reached. And thirdly, compared with a currently commonly used hole transport layer, the electron mobility of the tin oxide film deposited without modification is lower, so that the current-voltage hysteresis effect under bias scanning in different directions caused by unbalance of electron and hole extraction and transport is caused, after tungsten oxide is added, proper oxygen vacancies are introduced, the pH value is regulated, the electron mobility and the conductivity of the composite film are enhanced, and the hysteresis effect caused by unbalance of charge extraction and transport is reduced.
In the composite electron transport layer, tungsten oxide can react with alkaline tin oxide solution, so as to regulate the balance of hydrolysis-condensation reaction in the solution and promote the regrowth crystallization of tin oxide nanocrystalline; in addition to WO generated by the reaction 4 2- Can be adsorbed on the surface of tin oxide nano particles, reduce the degree of forming large agglomerates by commercialized tin oxide nano crystals and improve the tin dioxideDispersion stability of the solution. Therefore, the prepared composite electron transport film is more compact and uniform, can effectively enhance the interface contact with the perovskite absorption layer, is more reasonable in energy level matching with the perovskite absorption layer, improves the extraction and collection efficiency of photogenerated electrons in the perovskite layer, reduces non-radiative recombination and reduces resistance loss. The preparation process is simple and effective, the effect is obvious, the open-circuit voltage of the prepared perovskite battery is increased from 1.1V to 1.15V, the filling factor is increased from 83% to 85.8%, the highest filling factor of the tin dioxide-based perovskite battery reported so far is the highest filling factor, and the efficiency is finally increased from 21.7% to 23.6%, so that the perovskite battery has a wide application prospect.
Wherein the substrate material is hard transparent glass or flexible organic plastic.
The transparent electrode has the capability of collecting and transmitting electrons, is any one of indium tin oxide, fluorine tin oxide or aluminum zinc oxide, and has light transmittance of more than 70 percent and area resistance of less than 15 omega.
The perovskite light absorption layer material is ABX 3 Type A is Rb, cs, CH 3 NH 3 、HC(NH 2 ) 2 B is Pb, sn, cu, X is Cl, br, I, SCN, etc.; the perovskite light absorption layer and the plane electron transport layer can form a plane heterojunction; the thickness of the perovskite film is 100-1000nm.
The hole transport layer is Spiro-OMeTAD, P3HT, PTAA, cuI, cuSCN, cu 2 O、NiO x And MoO x One or more of the following.
The counter electrode is an opaque or semitransparent gold electrode, a silver electrode or a conductive carbon material electrode.
According to another aspect of the present application, there is provided a method for preparing a perovskite battery based on a composite electron transport layer, comprising the steps of:
step 1: configuration of (FAPbI) dissolved in polar solvent 3 ) x (MAPbBr 3 ) 1-x Perovskite precursor solution (perovskite precursor solution for short); preparing tin oxide colloid solution with dilution ratio as compact tin dioxide precursor solutionA liquid;
step 2: preparation of tungsten oxide solution: preparing self-made tungsten oxide aqueous solution into one part of aqueous dispersion with different concentrations of 0.2-5mg/ml, wherein the volume of each part is 1ml;
step 3: preparing a tin oxide-tungsten oxide composite electron transport layer precursor solution: taking 100ul (microliter) of solution from each tungsten oxide aqueous dispersion with different concentrations, respectively adding the solution into 1ml of compact tin dioxide precursor solution, and placing the solution into an ultrasonic device for ultrasonic dispersion for three times at room temperature, wherein the time length of each ultrasonic treatment is controlled to be 20min, so that the water in the ultrasonic device is prevented from boiling;
step 4: deposition of a tin oxide-tungsten oxide composite electron transport layer: before spin coating the tin oxide-tungsten oxide composite electron transport layer precursor solution of the step 3 on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15min; taking out the transparent electrode after plasma treatment, taking 100ul (microliter) of tin oxide-tungsten oxide composite electron transport layer precursor solution by using a pipetting gun, spin-coating, keeping the spin-coating rotation speed at 3000rpm for 30s, keeping the acceleration at 2000rpm/s, and annealing at 150 ℃ for 30min;
step 5: solution method preparation of perovskite light absorption layer: dropwise adding a perovskite precursor solution on the surface of the composite electron transport layer, dropwise adding a nonpolar solvent in the spin coating process to extract a polar solvent, and then annealing at 60-150 ℃ for 5-60min for crystallization; the thickness of the perovskite light absorbing layer is controlled to be 100-1000nm by adjusting the concentration of the perovskite precursor solution and the spin-coating rotating speed;
step 6: hole transport layer deposition: spin-coating a hole transport layer solution on the surface of the perovskite light absorption layer, and controlling the thickness to be 100-400nm by controlling the concentration and the rotating speed of the solution; the hole transport layer solution is a solution of the prior art, and will not be described in detail here;
step 7: and (3) depositing a counter electrode: and depositing a gold or silver electrode by adopting a thermal evaporation method, wherein the thickness is controlled to be 50-150nm.
Further, the solvent of the solution method in the step 5 comprises a polar solvent and a nonpolar solvent, wherein the polar solvent dissolves the perovskite material and comprises one or more of dimethylformamide, dimethyl sulfoxide and gamma-butyrolactone; the nonpolar solvent and perovskite material are mutually insoluble, and comprise one or more of benzene, toluene, 1, 2-xylene, 1, 3-xylene, 1, 4-xylene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, ethanol and isopropanol.
The invention is characterized in that the composite electron transport layer consists of tin oxide and tungsten oxide, wherein the tungsten oxide can react with alkaline tin oxide solution, the balance of hydrolysis-condensation reaction is controlled by adjusting the pH value in the solution, and the regrowth crystallization of tin oxide nanocrystalline is promoted; in addition to WO generated by the reaction 4 2- Can be adsorbed on the surface of tin oxide nano particles, reduces the degree of forming large agglomerates by commercialized tin oxide nano crystals, and improves the dispersion stability of tin dioxide solution. Therefore, the prepared composite electron transport film is more compact and uniform, and can effectively enhance the interface contact with the perovskite absorption layer; in addition, the tungsten oxide can introduce a proper amount of oxygen vacancies into the composite film, so that the electron mobility and the conductivity of the film are improved; meanwhile, the energy level matching between the composite electron transport layer film and the perovskite absorption layer is more reasonable, the extraction and collection efficiency of photo-generated electrons in the perovskite layer is improved, the non-radiative recombination is reduced, and the resistance loss is reduced. The preparation method is simple and effective in preparation process, obvious in effect, and capable of remarkably improving the open-circuit voltage and the filling factor of the prepared perovskite battery, wherein the open-circuit voltage is improved to 1.15V from 1.1V, the filling factor is improved to 85.8% from 83%, and the method is the highest filling factor of the tin dioxide-based perovskite battery, so that the efficiency is finally improved to 23.6% from 21.7%, and the method has a wide application prospect.
Drawings
The invention may be better understood by referring to the following description in conjunction with the accompanying drawings in which like or similar reference numerals are used to indicate like or similar elements throughout the several views. The accompanying drawings, which are included to provide a further illustration of the preferred embodiments of the invention and together with a further understanding of the principles and advantages of the invention, are incorporated in and constitute a part of this specification. Attached at
In the figure:
FIG. 1 is a comparative schematic diagram of the solution stability test of example 1 and comparative example 1;
FIG. 2 is a comparative schematic diagram of the test of the photoelectric properties of example 1 and comparative example 1;
FIG. 3 is a schematic diagram showing the conductivity test of the electron transport layers of example 1 and comparative example 1;
FIG. 4 is a schematic representation of XPS photoelectron spectroscopy test of example 1 and comparative example 1;
FIG. 5 is a schematic illustration of photoluminescence spectrum tests of example 1 and comparative example 1;
fig. 6 is a comparison schematic of electrochemical impedance spectroscopy test of example 1 and comparative example 1.
Detailed Description
Embodiments of the present invention will be described below with reference to the accompanying drawings. Elements and features described in one drawing or embodiment of the invention may be combined with elements and features shown in one or more other drawings or embodiments. It should be noted that the illustration and description of components and processes known to those skilled in the art, which are not relevant to the present invention, have been omitted in the drawings and description for the sake of clarity.
Example 1
The embodiment provides a construction method of a perovskite solar cell of a tin oxide-tungsten oxide metal oxide electron transport layer, which comprises the following steps:
step (1): configuration (FAPbI) 3 ) 0.92 (MAPbBr 3 ) 0.08 Precursor: pbI 2 Concentration 1.53M, FAI concentration 1.4M, MAPbBr concentration 0.11M, MACl concentration 0.5M, solvent Dimethylformamide (DMF) and (DMSO), wherein the solvent volume ratio is 8:1; preparing diluted commercial tin dioxide precursor (15 wt%) for dilution according to a mass ratio of 1:3 (tin oxide: deionized water);
step (2): preparing tungsten oxide aqueous dispersion liquid: the concentration is configured to be 0.2-5mg/ml;
step (3): configuration of tungsten oxide-tin oxide mixed precursor solution: adding tungsten oxide aqueous dispersion with different concentrations into a tin oxide aqueous solution with the same volume (100 ul) of 1ml, and performing ultrasonic dispersion for 1h;
step (4): adopting FTO conductive glass as a substrate and a transparent electrode, wherein the light transmittance is 80% and the area resistance is 15 omega;
step (5): deposition of a tin oxide-tungsten oxide composite electron transport layer: before spin coating the tungsten oxide-tin oxide mixed precursor solution in the step (3) on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15min; taking out the plasma treated transparent electrode, taking 100 (microliter) ul of tin oxide-tungsten oxide composite electron transport layer precursor solution by using a pipetting gun, spin-coating, keeping the rotating speed at 3000rpm for 30s, keeping the acceleration at 2000rpm/s, and annealing at 150 ℃ for 30min;
step (6): solution method preparation of perovskite light absorption layer: dropwise adding a perovskite precursor solution on the surface of the electron transport layer, dropwise adding a nonpolar solvent to extract a polar solvent in the spin coating process, and then annealing at 60-150 ℃ for 5-60min for crystallization; controlling the thickness of the perovskite light absorption layer to be 600nm by adjusting the concentration of the precursor solution and the spin-coating rotating speed;
step (7): hole transport layer deposition: spin-coating a hole transport layer solution on the surface of the perovskite light absorption layer, and controlling the thickness to be 200nm by controlling the concentration and the rotating speed of the solution;
step (8): and (3) depositing a counter electrode: depositing a silver electrode by adopting a thermal evaporation method, and controlling the thickness to be 120nm;
comparative example 1
The preparation method of the perovskite solar cell with the single tin oxide electron transport layer comprises the following steps:
(1) Configuration (FAPbI) 3 ) 0.92 (MAPbBr 3 ) 0.08 Precursor: pbI 2 Concentration 1.53M, FAI concentration 1.4M, MAPbBr concentration 0.11M, MACl concentration 0.5M, solvent Dimethylformamide (DMF) and (DMSO), wherein the solvent volume ratio is 8:1; preparing diluted commercial tin dioxide precursor (15 wt%) for dilution according to a mass ratio of 1:3 (tin oxide: deionized water);
(2) Adopting FTO conductive glass as a substrate and a transparent electrode, wherein the light transmittance is 80% and the area resistance is 15 omega;
(3) Deposition of a single tin oxide electron transport layer: before spin coating the dense tin dioxide precursor solution configured in the step 1) on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15min; taking out the transparent electrode subjected to plasma treatment, taking 100ul of solution by using a liquid-transfering gun, spin-coating, keeping the rotating speed at 3000rpm for 30s, and annealing at 150 ℃ for 30min at the acceleration of 2000 rpm/s;
(4) Solution method preparation of perovskite light absorption layer: dropwise adding a perovskite precursor solution on the surface of the electron transport layer, dropwise adding a nonpolar solvent to extract a polar solvent in the spin coating process, and then annealing at 60-150 ℃ for 5-60min for crystallization; controlling the thickness of the perovskite light absorption layer to be 600nm by adjusting the concentration of the precursor solution and the spin-coating rotating speed;
(5) Hole transport layer deposition: spin-coating a hole transport layer solution on the surface of the perovskite light absorption layer, and controlling the thickness to be 200nm by controlling the concentration and the rotating speed of the solution;
(6) And (3) depositing a counter electrode: depositing a silver electrode by adopting a thermal evaporation method, and controlling the thickness to be 120nm;
the materials and device performance tests for each example and the corresponding comparative example were as follows:
as shown in fig. 1, the initial tin oxide solution and the tin oxide solution after adding the tungsten oxide were compared, and as a result, it was found that the color of the tin oxide solution after adding the tungsten oxide was gradually clarified in the form of an original milky white flocculent, and the solution was stable for a long period of time to maintain a clarified state, which means that the tungsten oxide was able to adjust the hydrolysis-coagulation reaction equilibrium state of the commercial tin oxide nanocrystalline colloid, so that the dispersion of the colloid solution was more stable.
The solar cells of example 1 and comparative example 1 were placed under standard light intensity (Newport, AM 1.5g,100mw cm -2 ) The test is performed below. The measurement results are shown in fig. 1, the perovskite cell efficiency is improved to 23.6% by using tin oxide-tungsten oxide composite as an electron transport layer, and specific cell parameters are shown in the table.
Table 1 performance parameters of perovskite batteries
| Sample of | V OC (V) | J SC (mA cm -2 ) | FF(％) | PCE(％) |
| Single electron transport layer | 1.1 | 23.85 | 82.11 | 21.7 |
| Composite electron transport layer | 1.15 | 24 | 85.8 | 23.6 |
Fig. 3 shows a conductivity test of the electron transport layer, and a comparison shows that the conductivity of the composite electron transport layer is significantly higher than that of a single tin oxide electron transport layer, indicating that the composite electron transport layer is capable of rapidly conducting electrons.
FIG. 4 shows XPS photoelectron spectra of an electron transport layer, compared to find W 6+ W4f of (2) 5/2 And W4f 7/2 Appear at the 37.8 and 35.6eV locations indicating that tungsten oxide in the metal oxide composite electron transport layer was successfully deposited to tin oxide.
The photoluminescence spectra presented in fig. 5 show that the luminescence intensity on the metal oxide composite electron transport layer is weaker and the quenching is faster, indicating that the metal oxide composite electron transport layer has stronger electron extraction and collection capabilities, reducing non-radiative recombination due to interfacial charge accumulation; the electrochemical impedance spectra of fig. 6 are tested, and it is found through fitting that after adding tungsten oxide, the resistance loss is reduced (the series resistance is reduced, the composite resistance is increased, the transmission resistance is reduced), the charge collecting capacity is improved, the resistance loss is reduced, the increase of the filling factor is greatly promoted, and finally the photoelectric performance of the device is improved.
Example 2
The embodiment discloses a construction method of a ternary cationic perovskite battery of a tin oxide-oxide composite electron transport layer, which comprises the following steps:
(1) Configuration Cs 0.05 (MA 0.15 FA 0.85 ) 0.95 Pb(I 0.85 Br 0.15 ) 3 Precursor: csI concentration of 0.5M, pbI 2 1.2M, 1.1M FAI, 0.2M PbBr, 0.2M MABr, and Dimethylformamide (DMF) and (DMSO) as solvents, wherein the volume ratio of the solvents is 4:1; preparing diluted commercial tin dioxide precursor (15 wt%) for dilution according to a mass ratio of 1:3 (tin oxide: deionized water);
(2) Preparing tungsten oxide aqueous dispersion liquid: the concentration is configured to be 0.2-5mg/ml;
(3) Configuration of tungsten oxide-tin oxide mixed precursor solution: adding tungsten oxide aqueous dispersion with different concentrations into a tin oxide aqueous solution with the same volume (100 ul) of 1ml, and performing ultrasonic dispersion for 1h;
(4) Adopting FTO conductive glass as a substrate and a transparent electrode, wherein the light transmittance is 80% and the area resistance is 15 omega;
(5) Deposition of a tin oxide-tungsten oxide composite electron transport layer: before spin-coating the tungsten oxide-tin oxide mixed precursor solution configured in the step (3) on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15min; taking out the transparent electrode treated by plasma, taking 100 (microliter) ul of solution by using a pipetting gun, spin-coating, keeping the rotation speed at 3000rpm for 30s, and annealing at 150 ℃ for 30min at the acceleration of 2000 rpm/s;
(6) Solution method preparation of perovskite light absorption layer: dropwise adding a perovskite precursor solution on the surface of the electron transport layer, dropwise adding a nonpolar solvent to extract a polar solvent in the spin coating process, and then annealing at 100 ℃ for 60min for crystallization; controlling the thickness of the perovskite light absorption layer to be 400nm by adjusting the concentration of the precursor solution and the spin-coating rotating speed;
(7) Hole transport layer deposition: spin-coating a hole transport layer solution on the surface of the perovskite light absorption layer, and controlling the thickness to be 100nm by controlling the concentration and the rotating speed of the solution;
(8) And (3) depositing a counter electrode: depositing a gold electrode by adopting a thermal evaporation method, wherein the thickness is controlled to be 80nm;
example 3
The embodiment discloses a construction method of a methylamine lead-iodine perovskite battery of a tin oxide-tungsten oxide composite electron transport layer, which comprises the following steps:
(1) Configuring MAPbI 3 Precursor: pbI 2 Concentration 1.14M, MAI concentration 1.43M, solvent Dimethylformamide (DMF) and (DMSO), wherein the solvent volume ratio is 9:1; preparing diluted commercial tin dioxide precursor (15 wt%) for dilution according to a mass ratio of 1:3 (tin oxide: deionized water);
(2) Preparing tungsten oxide aqueous dispersion liquid: the concentration is configured to be 0.2-5mg/ml;
(3) Configuration of tungsten oxide-tin oxide mixed precursor solution: adding tungsten oxide aqueous dispersion with different concentrations into a tin oxide aqueous solution with the same volume (100 ul) of 1ml, and performing ultrasonic dispersion for 1h;
(4) Adopting FTO conductive glass as a substrate and a transparent electrode, wherein the light transmittance is 80% and the area resistance is 15 omega;
(5) Deposition of a tin oxide-tungsten oxide composite electron transport layer: before spin-coating the tungsten oxide-tin oxide mixed precursor solution configured in the step (3) on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15min; taking out the transparent electrode subjected to plasma treatment, taking 100ul of solution by using a liquid-transfering gun, spin-coating, keeping the rotating speed at 3000rpm for 30s, and annealing at 150 ℃ for 30min at the acceleration of 2000 rpm/s;
(6) Solution method preparation of perovskite light absorption layer: dropwise adding a perovskite precursor solution on the surface of the electron transport layer, dropwise adding a nonpolar solvent in the spin coating process to extract a polar solvent, and then annealing at 100 ℃ for 30min for crystallization; controlling the thickness of the perovskite light absorption layer to 300nm by adjusting the concentration of the precursor solution and the spin-coating rotating speed;
(7) Hole transport layer deposition: spin-coating a hole transport layer solution on the surface of the perovskite light absorption layer, and controlling the thickness to be 100nm by controlling the concentration and the rotating speed of the solution;
(8) And (3) depositing a counter electrode: depositing a silver electrode by adopting a thermal evaporation method, and controlling the thickness to be 120nm;
the above examples detail a perovskite battery based on a novel electron transport layer and a method of making the same. The energy level matching between the active layer and the transmission layer is improved through the composite electron transmission layer, the extracting and collecting capacity of carriers is improved, the recombination of electrons and holes at the interface is reduced, the resistance loss is reduced, the filling factor and the open-circuit voltage are effectively increased, and the photoelectric conversion efficiency of the perovskite battery is finally improved.
In the foregoing description of specific embodiments of the invention, features that are described and/or illustrated with respect to one embodiment may be used in the same or a similar way in one or more other embodiments in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein is taken to specify the presence of stated features, elements, steps or components, but does not preclude the presence or addition of one or more other features, elements, steps or components.
Furthermore, the methods of the present invention are not limited to being performed in the time sequence described in the specification, but may be performed in other time sequences, in parallel or independently. Therefore, the order of execution of the methods described in the present specification does not limit the technical scope of the present invention.
While the invention has been disclosed in the context of specific embodiments, it should be understood that all embodiments and examples described above are illustrative rather than limiting. Various modifications, improvements, or equivalents of the invention may occur to persons skilled in the art and are within the spirit and scope of the following claims. Such modifications, improvements, or equivalents are intended to be included within the scope of this invention.
Claims (7)
1. A perovskite battery based on a composite electron transport layer, characterized in that: comprises a substrate material, a transparent electrode, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a counter electrode which are sequentially arranged from bottom to top; the electron transport layer is a composite electron transport layer and has a planar structure, the composite electron transport layer is composed of at least two metal oxides, and metal elements of the two metal oxides respectively have different electronegativity; the particle sizes of the two metal oxides are respectively controlled to be 5-50nm and 100-200nm, and the thickness of the composite film after the two metal oxides are compounded is controlled to be 20-80nm;
the composite electron transport layer is formed by mixing tin oxide and tungsten oxide aqueous solution, wherein the mixed solution of the tin oxide and the tungsten oxide aqueous solution specifically comprises tin oxide colloid solution and tungsten oxide aqueous solution, and the volume ratio of the tin oxide colloid solution to the tungsten oxide aqueous solution is 1:1-15:1;
the tin oxide colloid solution consists of colloid particles with the particle size of 5-50nm and alkaline solution; the tungsten oxide aqueous solution consists of particles with the particle size of 100-200nm and the aqueous solution.
2. The composite electron transport layer-based perovskite battery of claim 1, wherein: the substrate material is hard transparent glass or flexible organic plastic.
3. The composite electron transport layer-based perovskite battery of claim 1, wherein: the transparent electrode is any one of indium tin oxide, fluorine tin oxide or aluminum zinc oxide, the transmittance of the transparent electrode is more than 70%, and the surface resistance is less than 15Ω.
4. The composite electron transport layer-based perovskite battery of claim 1, wherein: the perovskite light absorptionThe layer material is ABX 3 Type A is Rb, cs, CH 3 NH 3 、HC(NH 2 ) 2 B is one of Pb, sn and Cu, and X is one of Cl, br, I and SCN; the perovskite light absorption layer and the plane electron transport layer can form a plane heterojunction; the thickness of the perovskite film is 100-1000nm.
5. The composite electron transport layer-based perovskite battery of claim 1, wherein: the hole transport layer is Spiro-OMeTAD, P3HT, PTAA, cuI, cuSCN, cu 2 O, nickel oxide, and molybdenum oxide.
6. The method for manufacturing a perovskite battery based on a composite electron transport layer according to any one of claims 1 to 5, comprising the steps of:
step 1: configuration of (FAPbI) dissolved in polar solvent 3 ) 0.92 (MAPbBr 3 ) 0.08 A perovskite precursor solution; preparing a tin oxide colloid solution with a dilution ratio as a dense tin dioxide precursor solution;
step 2: preparation of tungsten oxide aqueous solution: preparing tungsten oxide aqueous dispersion liquid with different concentrations of 0.2-5mg/ml; the tin oxide colloid solution and the tungsten oxide aqueous solution form a composite electron transport layer; the volume ratio of the tin oxide colloid solution to the tungsten oxide aqueous solution is 1:1-15:1; the tin oxide colloid solution consists of colloid particles with the particle size of 5-50nm and alkaline solution; the tungsten oxide aqueous solution consists of particles with the particle size of 100-200nm and an aqueous solution;
step 3: preparing a tin oxide-tungsten oxide composite electron transport layer precursor solution: adding tungsten oxide aqueous dispersion liquid with different concentrations into a compact tin dioxide precursor solution according to the same volume, and placing the compact tin dioxide precursor solution into an ultrasonic device for ultrasonic dispersion to obtain a tin oxide-tungsten oxide composite electron transport layer precursor solution;
step 4: deposition of a tin oxide-tungsten oxide composite electron transport layer: before spin coating the tin oxide-tungsten oxide composite electron transport layer precursor solution of the step 3 on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15min; taking out the transparent electrode after plasma treatment, taking 100ul of tin oxide-tungsten oxide composite electron transport layer precursor solution by using a liquid-transferring gun, spin-coating, keeping the spin-coating rotation speed at 3000rpm for 30s, keeping the acceleration at 2000rpm/s, and annealing at 150 ℃ for 30min;
step 5: solution method preparation of perovskite light absorption layer: dropwise adding a perovskite precursor solution on the surface of the composite electron transport layer, dropwise adding a nonpolar solvent in the spin coating process to extract a polar solvent, and then annealing at 60-150 ℃ for 5-60min for crystallization; the thickness of the perovskite light absorption layer is controlled to be 100-1000nm by adjusting the concentration of the precursor solution of the front perovskite and the spin-coating rotating speed;
step 6: hole transport layer deposition: spin-coating a hole transport layer solution on the surface of the perovskite light absorption layer, and controlling the thickness to be 100-400nm by controlling the concentration and the rotating speed of the solution;
step 7: and (3) depositing a counter electrode: and depositing a gold or silver electrode by adopting a thermal evaporation method, wherein the thickness is controlled to be 50-150nm.
7. The method of manufacturing according to claim 6, wherein: the solvent of the solution method in the step 5 comprises a polar solvent and a nonpolar solvent, wherein the polar solvent dissolves perovskite materials and comprises one or more of dimethylformamide, dimethyl sulfoxide and gamma-butyrolactone; the nonpolar solvent and perovskite material are mutually insoluble, and comprise one or more of benzene, toluene, 1, 2-xylene, 1, 3-xylene, 1, 4-xylene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, ethanol and isopropanol.
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