CN113097388A - 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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- 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
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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 transmission layer is a composite electron transmission layer and has a planar structure, the composite electron transmission layer is composed of at least two metal oxides, and metal elements of the two metal oxides have different electronegativities respectively. According to the invention, by compounding the metal tungsten oxide compound in the electron transmission layer, the morphological structure and the electronic structure of the original tin oxide metal oxide transmission layer film are improved, 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, the filling factor is improved, and the photovoltaic performance of the perovskite cell is improved.
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, the rapid increase of population and the continuous promotion of industrialization, the shortage of energy and environmental pollution become two major problems facing the present human beings. 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. The perovskite solar cell is a type of solar cell which is rapidly developed at present, and has the characteristics of high photoelectric conversion efficiency, low cost, simple preparation and the like. Over a decade of development, the 3.8% has increased rapidly from 2009 to 25.5%.
The perovskite solar cell can be divided into a planar structure and a mesoporous structure according to structural division, 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 generates light to generate electrons and holes after absorbing the light, the electrons and the 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, and the loop outputs electric energy. At present, the main electron transport layer material is mainly a metal oxide semiconductor with high chemical stability, wherein a thin film prepared by a 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 current tin dioxide perovskite battery reaches 23.3%. But because the commercial tin dioxide solution has particle agglomeration, the dispersion stability of the colloidal solution is influenced, the compactness and poor coverage of the prepared film are caused, pinholes exist, the close contact between the electron transport layer and the perovskite light absorption layer is seriously influenced, the resistance loss (series resistance and parallel resistance) is increased, and the improvement of the filling factor of a device is inhibited (DOI: 10.1126/science.abb8687; 10.1002/adma.202003990; 10.1016/j.chempr.2020.04.013); in addition, the electron mobility of tin dioxide is still low (DOI:10.1038/s41467-018-05760-x) compared to the commonly used hole material (Spiro-OMeTAD), resulting in interfacial charge accumulation and non-radiative recombination, which causes current-voltage hysteresis effects and loss of open circuit voltage at different directional biases and loss of fill factor at low carrier extraction and collection capability.
Therefore, the method has the advantages of improving the dispersion stability of the tin dioxide colloidal solution and the electron mobility of the film, reducing the resistance loss, improving the filling factor, reducing the interface defect recombination caused by the accumulation of interface charges, optimizing the energy level matching of the electron transmission layer and the perovskite active layer, and reducing the loss of open-circuit voltage, and is very important.
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 determine the key or critical elements of the present invention, nor is it intended to limit the scope of the present invention. Its sole 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 generated by interface charge accumulation when the photoproduction electrons of the perovskite solar cell are transferred to an electron transmission layer from a perovskite absorption layer and the problems of resistance loss caused by untight interface contact between a perovskite film and an electron transmission layer film due to poor dispersion stability of a tin dioxide solution, energy level mismatching between an active layer and the transmission layer and the like, the invention provides a method for improving the appearance structure and the electronic structure of the original tin oxide metal oxide transmission layer film by compounding a metal tungsten oxide compound in the electron transmission layer so as to cause energy level distribution and carrier mobility change of the electron transmission layer, obtain energy level arrangement which is more matched with a perovskite light absorption layer, improve open-circuit voltage and carrier separation and collection efficiency, reduce non-radiative recombination of an interface, reduce resistance loss and improve a filling factor, thereby improving the photovoltaic performance of the perovskite cell. The fill factor achieved by the present invention is the highest fill factor for tin oxide perovskite cells.
According to one aspect of the application, a perovskite battery based on a composite electron transport layer is provided, 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 arranged from bottom to top in sequence; the electron transmission layer is a composite electron transmission layer and has a planar structure, the composite electron transmission layer is composed of at least two metal oxides, and metal elements of the two metal oxides have different electronegativities respectively.
Furthermore, in the prior art, only one oxide is generally used as the electron transport layer, the particle size is generally 10-200nm, and in order to realize the compact and uniform coverage of the electron transport layer without holes and without significantly increasing the resistance, tests show that the invention adopts two metal oxides for compounding, the particle size can be controlled to be 5-50nm and 100-200nm respectively, and the thickness of the composite film is controlled to be 20-80 nm. After the two particles with different particle sizes are doped with each other, 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 a photovoltaic device is enhanced.
Furthermore, 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, tungsten oxide material itself has the advantages of high electron mobility, suitable band gap width, high thin film light transmittance, strong oxygen vacancy tolerance and low material cost, and is suitable for being used as an electron transport layer material of perovskite cells, but the photoelectric conversion efficiency of the perovskite cells using tungsten oxide as a single electron transport layer is still below 20% (DOI:10.1016/j. nanoen.2020.105564) reported at present, so that the tungsten oxide is combined with other oxide materials to be a possible breakthrough. It has been reported that the conversion efficiency of perovskite cells prepared using tungsten oxide as an interface modification layer for titanium oxide or tin oxide has reached up to 20.5% (DOI: 10.1016/j.nanoen.2019.06.021). Thin films prepared using commercial tin oxide colloidal solutions have been widely used as electron transport layers for perovskite cells due to their low temperature solution preparation process and advantages of high stability, high electron mobility, etc., and the reported conversion efficiency has exceeded 23% (DOI: 10.1038/nergy.2016.177). However, there are some common problems, one of which is that the commercial tin dioxide colloid is easy to agglomerate into large particles due to the attractive force of van der waals force between particles, resulting in poor dispersion stability of the solution, and voids are easy to occur when the electronic layer thin film is deposited by spin coating, which affects the quality and interface contact with the perovskite layer, and deteriorates the photoelectric properties of the perovskite cell device. At present, no report of preparing a composite electron transport layer for a perovskite battery by directly mixing a tungsten oxide aqueous solution and a tin oxide colloidal solution is explored, so that the solution of the applicant is as follows: the mixed solution of tin oxide and tungsten oxide comprises a tin oxide colloidal solution and a tungsten oxide aqueous solution: the tin oxide colloidal solution consists of colloidal particles with the particle size of 5-50nm and alkaline solution (KOH) (ph is approximately equal to 12); the tungsten oxide aqueous solution is composed of particles with the particle size of 100-200nm (namely the tungsten oxide particle size in the tungsten oxide aqueous solution is 100-200nm) and an aqueous solution. As the colloidal tin oxide solution, there can be generally used a commercially available alkaline commercial colloidal tin oxide solution. Tungsten oxide in the film can chemically react with alkaline solution to promote the condensation-hydrolysis equilibrium state of colloidal solution, and can fully adjust the dispersion stability of colloid, thereby improving the quality of the electron transport layer film and the interface contact between the transport layer and the perovskite. And secondly, the situation that the energy level mismatch exists between the film obtained by directly spin-coating and depositing the commercial tin oxide solution and the perovskite absorption layer causes serious voltage loss and obtains the undesirable device performance. After a certain amount of tungsten oxide aqueous 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 is adjusted, and the position which is more matched with the perovskite absorption layer is reached. And thirdly, the electron mobility of the tin oxide film obtained by deposition without modification is lower than that of a hole transport layer commonly used at present, so that a current-voltage hysteresis effect under bias scanning in different directions caused by unbalanced extraction and transmission of electrons and holes is caused, and after the tungsten oxide is added, proper oxygen vacancies are introduced, the pH value is adjusted, the electron mobility and the conductivity of the composite film are enhanced, so that the hysteresis effect caused by unbalanced extraction and transmission of charges is reduced.
In the composite electron transport layer, tungsten oxide can react with alkaline tin oxide solution, so that the hydrolysis-condensation reaction balance in the solution is adjusted, and the regrowth and crystallization of tin oxide nanocrystals are promoted; in addition reaction of WO4 2-Can be adsorbed on the surface of the tin oxide nano-particles, reduces the degree of forming large aggregates of commercial tin oxide nano-crystals, and improves the dispersion stability of the tin dioxide solution. Therefore, the prepared composite electron transmission 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 photo-generated 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 filling factor is the highest filling factor of the stannic oxide-based perovskite battery reported so far, the efficiency is finally increased from 21.7% to 23.6%, and the preparation method has wide application prospects.
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 the transmittance of more than 70 percent and the surface resistance of less than 15 omega.
The perovskite light absorption layer material is ABX3Type A is Rb, Cs and CH3NH3、HC(NH2)2B is Pb, Sn, Cu, X is Cl, Br, I, SCN, etc.; the perovskite light absorption layer and the plane electron transmission layer can form a plane heterojunction; the thickness of the perovskite thin film is 100-1000 nm.
The hole transport layer is made of Spiro-OMeTAD, P3HT, PTAA, CuI, CuSCN, Cu2O、NiOxAnd MoOxOne or more of。
The counter electrode is an opaque or semitransparent gold or 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: configured to be dissolved in polar solvents (FAPBI)3)x(MAPbBr3)1-xPerovskite precursor solution (perovskite precursor solution for short); preparing a tin oxide colloidal solution with a dilution ratio as a dense tin dioxide precursor solution;
step 2: preparation of tungsten oxide solution: preparing the self-made tungsten oxide aqueous solution into aqueous dispersions with different concentrations of 0.2-5mg/ml, wherein the volume of each aqueous dispersion is 1 ml;
and step 3: preparing a precursor solution of a tin oxide-tungsten oxide composite electron transport layer: taking 100ul (microliter) of solution from each part of tungsten oxide aqueous dispersion with different concentrations, respectively adding the solution into a compact tin dioxide precursor solution with the volume of 1ml, placing the solution in an ultrasonic device at room temperature for ultrasonic dispersion for three times, and controlling the ultrasonic time length for each time to be 20min so as to avoid boiling of water in the ultrasonic device;
and 4, step 4: deposition of tin oxide-tungsten oxide composite electron transport layer: before the tin oxide-tungsten oxide composite electron transport layer precursor solution in the step 3 is coated on the surface of the transparent electrode in a spin mode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15 min; 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 liquid-transferring gun, spin-coating at the rotating speed of 3000rpm for 30s and the acceleration of 2000rpm/s, and annealing at 150 ℃ for 30 min;
and 5: solution method preparation of perovskite light absorption layer: dripping perovskite precursor solution on the surface of the composite electron transport layer, dripping non-polar solvent to extract polar solvent in the spin coating process, 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 perovskite precursor solution and the spin coating rotating speed;
step 6: deposition of a hole transport layer: 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 adopts a solution in the prior art, and is not detailed here;
and 7: and (3) deposition of a counter electrode: depositing gold or silver electrode by thermal evaporation method, and controlling thickness to 50-150 nm.
Further, the solvent of the solution process in the step 5 comprises a polar solvent and a non-polar solvent, wherein the polar solvent dissolves the perovskite material, and comprises one or more of dimethylformamide, dimethyl sulfoxide and gamma-butyrolactone; the non-polar solvent is mutually insoluble with the perovskite material and comprises 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 is composed of tin oxide and tungsten oxide, wherein the tungsten oxide can react with alkaline tin oxide solution, and the pH value in the solution is adjusted to control the hydrolysis-condensation reaction balance and promote the regrowth crystallization of tin oxide nano-crystals; in addition reaction of WO4 2-Can be adsorbed on the surface of the tin oxide nano-particles, reduces the degree of forming large aggregates of commercial tin oxide nano-crystals, and improves the dispersion stability of the tin dioxide solution. Therefore, the prepared composite electron transmission 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 in 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 transmission 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 and obvious in effect, the open-circuit voltage and the filling factor of the prepared perovskite battery are remarkably improved, the open-circuit voltage is increased from 1.1V to 1.15V, the filling factor is increased from 83% to 85.8%, the filling factor is the highest filling factor of the tin dioxide-based perovskite battery, and finally the efficiency is increased from 21.7%The yield is increased to 23.6 percent, and the method has 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 reference numerals are used throughout the figures to indicate like or similar parts. The accompanying drawings, which are incorporated in and form a part of this specification, illustrate preferred embodiments of the present invention and, together with the detailed description, serve to further explain the principles and advantages of the invention. On the attachment
In the figure:
FIG. 1 is a schematic comparison of the solution stability tests of example 1 and comparative example 1;
FIG. 2 is a comparison of the photoelectric property tests of example 1 and comparative example 1;
FIG. 3 is a schematic diagram of conductivity tests of the electron transport layers of example 1 and comparative example 1;
FIG. 4 is a schematic diagram of XPS photoelectron spectroscopy tests of example 1 and comparative example 1;
FIG. 5 is a schematic diagram of photoluminescence spectrum testing of example 1 and comparative example 1;
FIG. 6 is a comparison of electrochemical impedance spectroscopy tests 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 depicted in one drawing or one 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 figures and description omit representation and description of components and processes that are not relevant to the present invention and that are known to those of ordinary skill in the art for the sake of clarity.
Example 1
The embodiment provides a method for constructing a perovskite solar cell of a tin oxide-tungsten oxide electron transport layer, which comprises the following steps:
step (1): configuration (FAPBI)3)0.92(MAPbBr3)0.08Precursor: PbI2Concentration of 1.53M, FAI concentration of 1.4M, MAPbBr concentration of 0.11M, MACl of 0.5M, solvent of Dimethylformamide (DMF) and (DMSO), wherein the volume ratio of the solvent is 8: 1; preparing a 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: the preparation concentration is 0.2-5 mg/ml;
and (3): preparing a tungsten oxide-tin oxide mixed precursor solution: adding tungsten oxide aqueous dispersions with different concentrations into 1ml of tin oxide aqueous solution with the same volume (100ul), and ultrasonically dispersing for 1 h;
and (4): FTO conductive glass is used as a substrate and a transparent electrode, the light transmittance is 80%, and the surface resistance is 15 omega;
and (5): deposition of tin oxide-tungsten oxide composite electron transport layer: before the tungsten oxide-tin oxide mixed precursor solution in the step (3) is spin-coated on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15 min; taking out the transparent electrode subjected to plasma treatment, spin-coating 100 (microliter) ul of tin oxide-tungsten oxide composite electron transport layer precursor solution by using a liquid-transferring gun, keeping the rotation speed at 3000rpm for 30s, accelerating the rotation speed at 2000rpm/s, and annealing at 150 ℃ for 30 min;
and (6): solution method preparation of perovskite light absorption layer: dripping perovskite precursor solution on the surface of the electron transport layer, dripping non-polar solvent to extract 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;
and (7): deposition of a hole transport layer: 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;
and (8): and (3) deposition of a counter electrode: depositing a silver electrode by adopting a thermal evaporation method, and controlling the thickness to be 120 nm;
comparative example 1
The comparative example is a preparation method of a perovskite solar cell with a single tin oxide electron transport layer, and comprises the following steps:
(1) configuration (FAPBI)3)0.92(MAPbBr3)0.08Precursor: PbI2Concentration of 1.53M, FAI concentration of 1.4M, MAPbBr concentration of 0.11M, MACl of 0.5M, solvent of Dimethylformamide (DMF) and (DMSO), wherein the volume ratio of the solvent is 8: 1; preparing a diluted commercial tin dioxide precursor (15 wt%) for dilution according to a mass ratio of 1:3 (tin oxide: deionized water);
(2) FTO conductive glass is used as a substrate and a transparent electrode, the light transmittance is 80%, and the surface resistance is 15 omega;
(3) deposition of a single tin oxide electron transport layer: before the dense tin dioxide precursor solution prepared in the step 1) is spin-coated on the surface of the transparent electrode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15 min; taking out the transparent electrode subjected to plasma treatment, taking 100ul of solution by using a liquid-transfering gun, spin-coating at the rotating speed of 3000rpm for 30s and the acceleration of 2000rpm/s, and annealing at 150 ℃ for 30 min;
(4) solution method preparation of perovskite light absorption layer: dripping perovskite precursor solution on the surface of the electron transport layer, dripping non-polar solvent to extract 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) deposition of a hole transport layer: 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) deposition of a counter electrode: depositing a silver electrode by adopting a thermal evaporation method, and controlling the thickness to be 120 nm;
the materials and device performance tests for each example and corresponding comparative example were as follows:
as shown in fig. 1, when comparing the initial tin oxide solution and the tin oxide solution after adding tungsten oxide, it was found that the tin oxide solution after adding tungsten oxide has the original milky flocculent color and gradually becomes clear, and can stably maintain the clear state for a long time, which indicates that tungsten oxide can adjust the reaction equilibrium state of hydrolysis-agglomeration of the commercial tin oxide nanocrystalline colloid, and make the colloidal solution disperse more stably.
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 was performed. The measurement result is shown in fig. 1, the perovskite cell efficiency is improved to 23.6% by adopting the tin oxide-tungsten oxide compound as the electron transport layer, and the specific cell parameters are shown in the table.
TABLE 1 Performance parameters of perovskite batteries
| Sample (I) | VOC(V) | JSC(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 conductivity tests of the electron transport layer, and 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 can rapidly conduct electrons.
FIG. 4 shows XPS photoelectron spectroscopy of an electron transport layer, comparing to find W6+W4f5/2And W4f7/2The appearance at 37.8 and 35.6eV indicates that tungsten oxide in the metal oxide composite electron transport layer was successfully deposited to tin oxide.
The photoluminescence spectrum shown in fig. 5 shows that the luminescence intensity on the metal oxide composite electron transport layer is weaker and the quenching is faster, which indicates that the metal oxide composite electron transport layer has stronger electron extraction and collection capability and reduces non-radiative recombination generated by interface charge accumulation; fig. 6 shows electrochemical impedance spectroscopy, and it is found by fitting that the addition of tungsten oxide reduces the resistance loss (the series resistance is reduced, the composite resistance is increased, and the transmission resistance is reduced), the charge collection capability is improved, and the resistance loss is reduced, thereby greatly promoting the increase of the fill factor and finally improving the photoelectric performance of the device.
Example 2
The embodiment discloses a construction method of a ternary cation perovskite battery of a tin oxide-oxide composite electron transport layer, which comprises the following steps:
(1) configuration of Cs0.05(MA0.15FA0.85)0.95Pb(I0.85Br0.15)3Precursor: CsI concentration of 0.5M, PbI2The concentration is 1.2M, the FAI concentration is 1.1M, the PbBr concentration is 0.2M, the MABr concentration is 0.2M, and the solvents are Dimethylformamide (DMF) and (DMSO), wherein the volume ratio of the solvents is 4: 1; preparing a 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: the preparation concentration is 0.2-5 mg/ml;
(3) preparing a tungsten oxide-tin oxide mixed precursor solution: adding tungsten oxide aqueous dispersions with different concentrations into 1ml of tin oxide aqueous solution with the same volume (100ul), and ultrasonically dispersing for 1 h;
(4) FTO conductive glass is used as a substrate and a transparent electrode, the light transmittance is 80%, and the surface resistance is 15 omega;
(5) deposition of tin oxide-tungsten oxide composite electron transport layer: placing the transparent electrode in ultraviolet-ozone plasma for treatment for 15min before spin-coating the tungsten oxide-tin oxide mixed precursor solution prepared in the step (3) on the surface of the transparent electrode; taking out the transparent electrode subjected to plasma treatment, taking 100 (microliter) ul of solution by using a liquid-transfering gun, spin-coating at the rotating speed of 3000rpm for 30s and the acceleration of 2000rpm/s, and annealing at 150 ℃ for 30 min;
(6) solution method preparation of perovskite light absorption layer: dripping perovskite precursor solution on the surface of the electron transport layer, dripping non-polar solvent to extract 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) deposition of a hole transport layer: 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) deposition of a counter electrode: depositing a gold electrode by a thermal evaporation method, and controlling the thickness to be 80 nm;
example 3
The embodiment discloses a construction method of a methylamine lead perovskite battery of a tin oxide-tungsten oxide composite electron transport layer, which comprises the following steps:
(1) configuring MAPbi3Precursor: PbI2Concentration 1.14M, MAI concentration 1.43M, solvent Dimethylformamide (DMF) and (DMSO), wherein the solvent volume ratio is 9: 1; preparing a 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: the preparation concentration is 0.2-5 mg/ml;
(3) preparing a tungsten oxide-tin oxide mixed precursor solution: adding tungsten oxide aqueous dispersions with different concentrations into 1ml of tin oxide aqueous solution with the same volume (100ul), and ultrasonically dispersing for 1 h;
(4) FTO conductive glass is used as a substrate and a transparent electrode, the light transmittance is 80%, and the surface resistance is 15 omega;
(5) deposition of tin oxide-tungsten oxide composite electron transport layer: placing the transparent electrode in ultraviolet-ozone plasma for treatment for 15min before spin-coating the tungsten oxide-tin oxide mixed precursor solution prepared in the step (3) on the surface of the transparent electrode; taking out the transparent electrode subjected to plasma treatment, taking 100ul of solution by using a liquid-transfering gun, spin-coating at the rotating speed of 3000rpm for 30s and the acceleration of 2000rpm/s, and annealing at 150 ℃ for 30 min;
(6) solution method preparation of perovskite light absorption layer: dripping perovskite precursor solution on the surface of the electron transport layer, dripping non-polar solvent to extract polar solvent in the spin coating process, and then annealing at 100 ℃ for 30min for crystallization; controlling the thickness of the perovskite light absorption layer to be 300nm by adjusting the concentration of the precursor solution and the spin-coating rotating speed;
(7) deposition of a hole transport layer: 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) deposition of a counter electrode: depositing a silver electrode by adopting a thermal evaporation method, and controlling the thickness to be 120 nm;
the above examples detail a perovskite battery based on a novel electron transport layer and a preparation method thereof provided by the invention. The energy level matching between the active layer and the transmission layer is improved through the composite electron transmission layer, the extraction and collection capacity of carriers is improved, the electron and hole recombination at an 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 described and/or illustrated with respect to one embodiment may be used in the same or 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.
In addition, the method of the present invention is not limited to be performed in the time sequence described in the specification, and may be performed in other time sequences, in parallel, or independently. Therefore, the order of execution of the methods described in this specification does not limit the technical scope of the present invention.
While the present invention has been disclosed above by the description of specific embodiments thereof, it should be understood that all of the embodiments and examples described above are illustrative and not restrictive. Various modifications, improvements and equivalents of the invention may be devised by those skilled in the art within the spirit and scope of the appended claims. Such modifications, improvements and equivalents are also intended to be included within the scope of the present invention.
Claims (10)
1. A perovskite battery based on compound electron transport layer which characterized in that: comprises a substrate material, a transparent electrode, an electron transmission layer, a perovskite light absorption layer, a hole transmission layer and a counter electrode which are arranged from bottom to top in sequence; the electron transmission layer is a composite electron transmission layer and has a planar structure, the composite electron transmission layer is composed of at least two metal oxides, and metal elements of the two metal oxides have different electronegativities respectively.
2. The composite electron transport layer based perovskite battery of claim 1, wherein: the particle diameters 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 20-80 nm.
3. The composite electron transport layer based perovskite battery as claimed in claim 1 or 2, wherein: the composite electron transport layer is formed by mixing tin oxide and tungsten oxide aqueous solution, and the volume ratio of the tin oxide solution to the tungsten oxide solution is 1:1-15: 1.
4. The composite electron transport layer based perovskite battery of claim 3, wherein: the mixed solution of the tin oxide and the tungsten oxide aqueous solution specifically comprises a tin oxide colloidal solution and a tungsten oxide aqueous solution, wherein the tin oxide colloidal solution consists of colloidal particles with the particle size of 5-50nm and an alkaline solution; the tungsten oxide aqueous solution is composed of particles with the particle size of 100-200nm and an aqueous solution.
5. The composite electron transport layer based perovskite battery of claim 1, wherein: the substrate material is hard transparent glass or flexible organic plastic.
6. 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 15 omega.
7. The composite electron transport layer based perovskite battery of claim 1, wherein: the perovskite light absorption layer material is ABX3Type A is Rb, Cs and CH3NH3、HC(NH2)2B is Pb, Sn, Cu, X is Cl, Br, I, SCN, etc.; the perovskite light absorption layer and the plane electron transmission layer can form a plane heterojunction; the thickness of the perovskite thin film is 100-1000 nm.
8. The composite electron transport layer based perovskite battery of claim 1, wherein: the hole transport layer is made of Spiro-OMeTAD, P3HT, PTAA, CuI, CuSCN, Cu2O、NiOxAnd MoOxOne or more of (a).
9. The method for preparing a perovskite battery based on a composite electron transport layer according to any one of claims 1 to 8, comprising the steps of:
step 1: configured to be dissolved in polar solvents (FAPBI)3)x(MAPbBr3)1-xA perovskite precursor solution; tin oxide adhesive with dilution ratioThe bulk solution is used as a dense tin dioxide precursor solution;
step 2: preparation of tungsten oxide solution: preparing tungsten oxide aqueous dispersion with different concentrations of 0.2-5 mg/ml;
and step 3: preparing a precursor solution of a tin oxide-tungsten oxide composite electron transport layer: adding tungsten oxide aqueous dispersions with different concentrations into the compact tin dioxide precursor solution according to the same volume, and placing the solution in an ultrasonic device for ultrasonic dispersion to obtain a tin oxide-tungsten oxide composite electron transport layer precursor solution;
and 4, step 4: deposition of tin oxide-tungsten oxide composite electron transport layer: before the tin oxide-tungsten oxide composite electron transport layer precursor solution in the step 3 is coated on the surface of the transparent electrode in a spin mode, placing the transparent electrode in ultraviolet-ozone for plasma treatment for 15 min; 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 to carry out spin coating, keeping the spin coating at the rotating speed of 3000rpm for 30s, accelerating at the rotating speed of 2000rpm/s, and annealing at 150 ℃ for 30 min;
and 5: solution method preparation of perovskite light absorption layer: dripping perovskite precursor solution on the surface of the composite electron transport layer, dripping non-polar solvent to extract polar solvent in the spin coating process, 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 perovskite precursor solution and the spin-coating rotating speed;
step 6: deposition of a hole transport layer: 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;
and 7: and (3) deposition of a counter electrode: depositing gold or silver electrode by thermal evaporation method, and controlling thickness to 50-150 nm.
10. The method of claim 9, wherein: the solvent of the solution method in the step 5 comprises a polar solvent and a non-polar solvent, wherein the polar solvent dissolves the perovskite material and comprises one or more of dimethylformamide, dimethyl sulfoxide and gamma-butyrolactone; the non-polar solvent is mutually insoluble with the perovskite material and comprises 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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