CN110429182A - A kind of TiO2Combination electrode, the perovskite solar battery and preparation method thereof of AgNWs are embedded between bilayer film - Google Patents

Abstract

The invention provides a composite electrode with AgNWs embedded between _TiO2 double-layer films, a perovskite solar cell and a preparation method thereof. The preparation process of the composite electrode includes the preparation of a dense electron transport layer on _TiO2 and the deposition of AgNWs on the upper surface of _TiO2 . The preparation of the preparation and the preparation of the composite electrode of AgNWs embedded between the _TiO2 double-layer film; the present invention also protects the perovskite solar cell comprising the above composite electrode and its preparation method; the present invention effectively inhibits the formation of the perovskite film and the _TiO2 Space confines the charge, improves the separation and transport of excitons; at the same time increases the transmission speed of photoelectrons in the perovskite film, improves the photoelectric conversion efficiency and fill factor, and suppresses hysteresis; and improves the quality of the perovskite film and optimizes the perovskite film The contact with the lower hole transport layer effectively improves the photoelectric conversion efficiency of the device, which has high practical significance.

Description

A composite electrode with AgNWs embedded between TiO2 bilayer films, perovskite solar cell Pond and its preparation method

technical field

The invention relates to the field of light-emitting display technology, in particular to a composite electrode with AgNWs embedded between _TiO2 double-layer films, a perovskite solar cell and a preparation method thereof.

Background technique

Energy is the basis for the survival and development of human society. With the development of society, people's demand for energy has also shown an explosive growth trend, and the resulting energy shortage and ecological environment pollution have become increasingly prominent. At present, human research and development of more extensive new energy mainly includes: solar energy, water energy, nuclear energy, wind energy, hydrogen energy, biomass energy and geothermal energy. Among them, the clean energy represented by solar energy has incomparable advantages over other forms of energy. There are abundant solar energy reserves, and there is no transportation problem. The energy received by the earth from the sun every year is 30,000 times that of the world's total consumption. Therefore, it can be stored and utilized on the spot. At the same time, no waste water, waste gas, and waste will be discharged during the use of solar energy Wait.

There are three main methods of solar energy conversion: photochemical, photothermal and photoelectric conversion. Solar cells are technologies that use the photovoltaic effect of semiconductor devices for photoelectric conversion, which means that they can directly convert absorbed light energy into solar energy by receiving incident sunlight. The electromotive optical device is essentially a large-area p-n junction, and its working principle is to use the photovoltaic effect of the semiconductor p-n junction. Solar cells can be divided into silicon-based solar cells, inorganic compound thin-film solar cells, organic polymer thin-film solar cells, dye minhua solar cells, and perovskite solar cells according to the type of material.

Perovskite solar cells are a new type of high-efficiency thin-film solar cells that have emerged in recent years. The typical perovskite solar cell structure from bottom to top is: transparent conductive glass (photoanode), n-type semiconductor material (electron transport layer ), perovskite material (light absorption layer), p-type semiconductor material (hole transport layer), counter electrode (photocathode), which is mainly organic-inorganic hybrid lead halide perovskite CH ₃ NH ₃ The photoelectric performance of solar cell devices prepared with PbX ₃ as the light absorbing layer has been improved rapidly; in early 2015, Korea Research Institute of Chemical Technology (KRICT) passed NREL certification of perovskite solar cells with a photoelectric conversion efficiency of 22.1%, showing Very broad application prospects.

However, it is difficult to effectively adjust the balance of electron and hole transport per unit area and unit time of perovskite solar cells with traditional structures, which often leads to a decrease in the photoelectric conversion efficiency of perovskite cells.

AgNWs thin film has good optical transmittance and high electrical conductivity, therefore, it can be used as a transparent electrode for the fabrication of flat panel displays and solar cells. The tuning performed on AgNWs can enable a more balanced transfer of holes and electrons. Currently, perovskite solar cells containing TiO ₂ and AgNWs include only TiO ₂ without AgNWs cells and AgNWs on TiO ₂ layer cells; only TiO ₂ without AgNWs cells with the structure of ITO/TiO ₂ /MAPbIxCl ₃ -x/Spiro-OMeTAD/Ag has more surface charges, and the photoelectric conversion efficiency needs to be improved; the battery with AgNWs on the TiO ₂ layer, the structure: ITO/TiO ₂ -AgNWs (on the surface of TiO ₂ )/MAPbIxCl ₃ -x/Spiro-OMeTAD/Ag, the AgNWs in this structure is easy to form Ag-AgI with MAPbIxCl ₃ -x to form a recombination center, which reduces the photoelectric conversion efficiency of the battery.

Contents of the invention

The purpose of the present invention is to solve the deficiencies of the above-mentioned technologies, and to provide a preparation method of AgNWs composite electrode embedded between _TiO2 double-layer films, a perovskite solar cell and a preparation method, and AgNWs embedded between _TiO2 double-layer films can inhibit perovskite The formation of space-limited charges between the ore film and TiO ₂ improves the separation and transport of excitons; at the same time, it increases the transmission speed of photoelectrons in the perovskite film, improves the photoelectric conversion efficiency and fill factor, and suppresses hysteresis; it also makes the composite electrode and calcium The titanium layer is effectively separated to form a dense layer, which protects them from the iodine element of the perovskite to form a recombination center; and improves the quality of the perovskite film, optimizes the contact between the perovskite film and the underlying hole transport layer, and effectively The photoelectric conversion efficiency of the device is improved.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A preparation method of a composite electrode embedded with AgNWs between _TiO2 double-layer films, comprising the following steps:

S1. Preparation of TiO ₂ dense electron transport layer: Deposit the prepared TiO ₂ sol-gel on the substrate, dry and deposit again to make the surface smooth, and anneal in air atmosphere at 350-400°C for 30-40min to obtain TiO ₂ Dense electron transport layer;

S2. Preparation of electrodes with AgNWs deposited on the surface of _TiO2 : disperse AgNWs in ethylene glycol to obtain AgNWs dispersion with a mass concentration of 5 mg/mL, and then deposit the AgNWs dispersion on the _TiO2 dense electron transport layer obtained in S1 , and annealed at 180-200°C for 20-30min in an air atmosphere to obtain an electrode with AgNWs deposited on the upper surface of TiO ₂ ;

S3. Preparation of a composite electrode with AgNWs embedded between TiO ₂ double-layer films: the prepared TiO ₂ nanocrystals were deposited on the TiO 2 electrode deposited with AgNWs on the upper surface of TiO ₂ obtained in S2, and annealed at 100-300°C in air atmosphere for 10 ~120min, a composite electrode with AgNWs embedded between TiO ₂ bilayer films was obtained.

Preferably, the concentration of TiO2 sol-gel substance in S1 is 0.2mol/L;

The specific preparation process of the TiO2 sol-gel is as follows: tetrabutyl titanate, acetylacetone and ethanol are uniformly mixed according to the volume ratio of 2.39:1.06:17 to obtain solution A, and hydrochloric acid, deionized water and ethanol are mixed according to the volume ratio of 0.08:0.85 : 17 volume ratio mixed evenly to obtain solution B, solution B was added to solution A, stirred for 30-40min, placed for 24h for aging, to obtain TiO2 sol-gel.

Preferably, the drying temperature in S1 is 100° C., and the drying time is 10-20 minutes.

Preferably, the mass concentration of _TiO2 nanocrystals in the S3 is 150g/L;

The preparation process of the _TiO2 nanocrystals is as follows: tetrabutyl titanate and isopropanol are uniformly mixed according to the volume ratio of 3.7:1, stirred in an ice bath for 30-35 minutes, and then added with a volume fraction of 20-25% The glacial acetic acid aqueous solution was mixed evenly, and the mixed solution was hydrothermally reacted at 220° C. for 12 hours. After the reaction was completed, polyethylene glycol was added and concentrated by ultrasonic cleaning to obtain TiO ₂ nanocrystals with a mass concentration of 150 g/L.

The present invention also protects the composite electrode with AgNWs embedded between the TiO ₂ double-layer films prepared by the above preparation method.

The present invention also protects a method for preparing a perovskite solar cell comprising a composite electrode of AgNWs embedded between the above-mentioned _TiO2 double-layer films, comprising the following steps:

(1) Preparation of AgNWs composite electrodes embedded between TiO ₂ bilayer films;

(2) Under the protection of an inert gas, CH ₃ NH ₃ I and PbCl ₂ were uniformly mixed with DMF at a molar ratio of 3:1, and stirred at 60°C to obtain a perovskite precursor solution with a mass fraction of 30%;

(3) Deposit the perovskite precursor solution obtained in step (2) on the TiO ₂ bilayer film obtained in step (1) to intercalate the composite electrode of AgNWs, and perform staged annealing in the air atmosphere to obtain MAPbI _x Cl _3-x light absorbing layer;

(4) Spiro-OMeTAD solution is deposited on the MAPbI _x Cl _3-x light absorption layer that step (3) obtains and obtains the hole transport layer;

(5) Depositing an Ag electrode on the hole transport layer in step (4) to obtain a perovskite solar cell.

Preferably, the preparation process of Spiro-OMeTAD solution in step (4) is: mix Spiro-OMeTAD powder and chlorobenzene according to the solid-liquid ratio of 72.3mg: 1mL, then add the acetonitrile solution of lithium salt and tributylphosphoric acid in sequence ester and mixed and stirred for 1-1.5h to obtain a solution of Spiro-OMeTAD;

The concentration of the acetonitrile solution of the lithium salt is 520 mg/mL, and the volume ratio of the acetonitrile solution of the lithium salt, tributyl phosphate and chlorobenzene is 10.9:8.8:500.

Preferably, the staged annealing process in step (3) is: first annealing at 80° C. for 30 minutes, and then annealing at 100° C. for 60 minutes.

Preferably, in step (1), the substrate in the composite electrode embedded in AgNWs between _TiO2 double-layer thin films is an ITO glass substrate, and the pretreatment process of the substrate is: use boiling water, deionized water and dehydrated alcohol to clean respectively, step ( 2) The stirring time in 10～12h.

The present invention also protects the perovskite solar cell prepared by the above preparation method, which includes a composite electrode layer with AgNWs embedded between _TiO2 double-layer films, a MAPbI _x Cl _3-x light absorption layer, Spiro-OMeTAD hole transport layer and Ag electrode layer, the thickness of the composite electrode layer embedded with AgNWs between the TiO ₂ double-layer films is 50-200nm, and the thickness of the MAPbI _x Cl _3-x light absorption layer is 200-400nm , the thickness of the Spiro-OMeTAD hole transport layer is 10-150 nm, and the thickness of the Ag electrode layer is 100 nm.

Compared with the prior art, the beneficial effects of the present invention are as follows:

1. The present invention effectively inhibits the formation of space-limited charges between the perovskite film and TiO2 by embedding AgNWs composite electrodes between the _TiO2 double-layer films, and improves the separation and transport of excitons;

2. The invention improves the transmission speed of photoelectrons in the perovskite thin film, improves the photoelectric conversion efficiency and filling factor, and suppresses hysteresis.

3. The invention improves the roughness and the interface between TiO2 and perovskite by embedding AgNWs composite electrodes between _TiO2 double-layer films, and reduces the series resistance of perovskite solar cells.

4. The present invention embeds AgNWs into TiO2, and they are effectively separated from the perovskite layer to form a dense layer that protects them from the iodine element of the perovskite to form a recombination center.

5. The present invention improves the quality of the perovskite film and optimizes the contact between the perovskite film and the lower hole transport layer.

Description of drawings

Fig. 1 is the scanning figure of the compound electrode in embodiment 1 and comparative example 1 and the scanning figure of the MAPbI _x Cl _3-x light-absorbing layer thin film deposited on the compound electrode; Among Fig. 1: (a) is TiO ₂ -AgNWs ( The front view of the embedded) electrode; (b) the front view of the TiO ₂ -AgNWs (upper surface) electrode; (c) the MAPbI _x Cl _3-x light-absorbing layer film deposited on the TiO ₂ -AgNWs (embedded) electrode Scanning image; (d) is the scanning image of the MAPbI _x Cl _3-x light-absorbing layer film deposited on the TiO ₂ -AgNWs (upper surface) electrode;

Fig. 2 is the electrochemical impedance spectrum of the different perovskite solar cells prepared by embodiment 1, comparative example 1 and comparative example 2; Among Fig. 2: (a) is the electrochemical impedance spectrum tested under the open circuit voltage, (b) is the leakage current relationship curve of the solar cell in the dark state;

Fig. 3 is the XRD pattern of the MAPbI _x Cl _3-x light absorbing layer thin film deposited on the TiO ₂ -AgNWs (embedded) composite electrode of embodiment 1;

Fig. 4 is the J-V curve of the different perovskite solar cells prepared by embodiment 1, comparative example 1 and comparative example 2;

5 is a PCE histogram of 30 devices on the electron transport layer (ETL) in the perovskite solar cell of Example 1. FIG.

Detailed ways

The present invention will be described in detail below through specific implementation examples. The scope of the invention is not limited to this particular embodiment.

The preparation of AgNWs in the present invention refers to the following documents: 1. Yang Z, Wang M, Song X, et al.Engineering the plasmonic optical properties of cubic silvernanostructures based on Fano resonance[J].JOURNAL OF CHEMICAL PHYSICS,2013,139(16) :3669.2、Yang Z,Wang M,Song X,et al.High-performance ZnO/Ag Nanowire/ZnO composite film UV photodetectors with large area and low operatingvoltage[J].Journal of Materials Chemistry C,2014,2(21) :4312-4319.3, Yang Z, Wang M, Yan G, et al.An Improved Method to Synthesize Silver Nanorods and Study on Their Optical Properties e[J].Chemistry Letters,2013,42(9):1016-1017.

Example 1

This embodiment provides a method for preparing a perovskite solar cell comprising a composite electrode of AgNWs embedded between _TiO2 double-layer films, comprising the following steps:

(1) Preparation of a composite electrode with AgNWs embedded between TiO ₂ bilayer films;

S1. Preparation of TiO ₂ dense electron transport layer: Dissolve the mixed solution of 2.3856mL tetrabutyl titanate and 1.057mL acetylacetone in 17mL absolute ethanol, mix well to obtain A solution; mix 0.08125mL hydrochloric acid and 0.85mL Mix deionized water and 17mL of absolute ethanol evenly to obtain solution B; slowly add solution B to solution A and stir for 30min, then place it for 24h for aging to obtain _TiO sol-gel; spin the prepared _TiO sol-gel Coated on the ITO glass substrate which was cleaned and dried by boiling water, deionized water and absolute ethanol in sequence. Anneal at 100°C for 10 minutes, spin-coat again after drying to make the surface flat, that is, fill possible holes, and finally anneal in a muffle furnace at 400°C for 30 minutes in an air atmosphere to ensure the integrity of the TiO ₂ electron transport layer and obtain a dense TiO ₂ Electron transport layer;

S2. Preparation of electrodes with AgNWs deposited on the surface of TiO ₂ : disperse AgNWs in ethylene glycol to obtain an AgNWs dispersion with a mass concentration of 5 mg/mL, and then spin-coat the AgNWs dispersion on the TiO ₂ dense electron transport layer obtained in S1 Above, the rotation speed of the spin-coating process is 1000rpm, the spin-coating time is 20s, and annealed at 200°C for 20min in the air atmosphere to obtain an electrode with AgNWs deposited on the upper surface of TiO ₂ ;

S3. Preparation of a composite electrode with AgNWs embedded between _TiO2 double-layer films: Mix 37mL tetrabutyl titanate and 10mL isopropanol evenly, and stir in an ice bath for 30min, mix 80mL glacial acetic acid with 250mL deionized water to obtain Glacial acetic acid solution, mix the mixed solution of tetrabutyl titanate and isopropanol with the aqueous solution of glacial acetic acid evenly, react the mixed solution in a hydrothermal kettle at 220°C for 12 hours, add 4g of polyethylene glycol after the reaction is completed And ultrasonically cleaned and concentrated to obtain _TiO2 nanocrystals with a mass concentration of 150g/L; the prepared _TiO2 nanocrystals were spin-coated on the _TiO2 obtained by S2 on the electrode on which AgNWs were deposited on the upper surface, and in the muffle furnace in the air Annealing at 300°C for 30 minutes in the atmosphere can not only evaporate the residual solvent in the film, but also enhance the crystallinity of TiO ₂ nanocrystals, and obtain a composite electrode with a thickness of 50 TiO ₂ embedded in AgNWs between double-layer films;

(2) Transfer the composite electrode with AgNWs embedded between the TiO ₂ bilayer films into a nitrogen-filled glove box, mix CH ₃ NH ₃ I and PbCl ₂ with DMF at a molar ratio of 3:1, and stir at 60 °C 10h to obtain a mass fraction of 30% perovskite precursor solution;

(3) Spin-coat the perovskite precursor solution obtained in step (2) on the composite electrode embedded with AgNWs between the _TiO2 double-layer films obtained in step (1), the rotating speed of the spin-coating process is 4000rpm, and the spin-coating time is 40s, and perform staged annealing treatment in an air atmosphere in a muffle furnace, that is, annealing at 80°C for 30min, and then annealing at 100°C for 60min, to obtain a MAPbI _x Cl _3-x light-absorbing layer with a thickness of 200nm;

(4) Mix 72.3mg of Spiro-OMeTAD powder with 1mL of chlorobenzene evenly, then add 21.8μL of acetonitrile solution of lithium salt with a concentration of 520mg/mL and 17.6μL of tributyl phosphate and mix and stir for 1h to obtain Spiro-OMeTAD The dispersion liquid of Spiro-OMeTAD solution is deposited on the MAPbI _x Cl _3-x light absorbing layer that step (3) obtains, and the rotating speed of spin-coating process is 2000rpm, and spin-coating time is 30s, obtains the Spiro-OMeTAD that thickness is 150nm hole transport layer;

(5) Depositing an Ag electrode with a thickness of 100 nm on the Spiro-OMeTAD hole transport layer in step (4) to obtain a perovskite solar cell.

Example 2

The same structure as in Example 1, except that the thickness of the MAPbI _x Cl _3-x light absorbing layer is 400 nm.

Example 3

The structure is the same as in Example 1, except that the thickness of the AgNWs composite electrode layer is 200nm.

Example 4

The structure is the same as in Example 1, except that the thickness of the Spiro-OMeTAD hole transport layer is 10 nm.

Comparative example 1

The same process as in Example 1, except that the electrode in step (1) is the electrode on which AgNWs is deposited on the upper surface of TiO ₂ , that is, the structure of the perovskite cell is: ITO/TiO ₂ -AgNws (upper surface of TiO ₂ ) /MAPbIxCl3 _{-x /} Spiro-OMeTAD/Ag.

Comparative example 2

The process is the same as in Example 1, except that TiO ₂ is directly deposited on the substrate in step (1), that is, the structure of the perovskite cell is: ITO/TiO ₂ /MAPbI _x Cl _3-x /Spiro-OMeTAD/Ag .

We performed performance tests and morphology characterizations of the composite electrodes in the perovskite solar cells of Example 1, Comparative Example 1 and Comparative Example 2 and the corresponding batteries; we named the composite electrodes of Example 1 as TiO ₂ -AgNWs (embedded) electrode, the electrode in Comparative Example 1 is named TiO ₂ -AgNws (upper surface) electrode.

Fig. 1 is the scanning picture of the composite electrode in embodiment 1 and comparative example 1 and the scanning picture of the MAPbI _x Cl _3-x light absorbing layer thin film deposited on the composite electrode; Wherein (a) is TiO ₂ -AgNWs (embedded) The front view of the electrode; (b) the front view of the TiO ₂ -AgNWs (upper surface) electrode; (c) the scan of the MAPbI _x Cl _3-x light-absorbing layer film deposited on the TiO ₂ -AgNWs (embedded) electrode Figure; (d) is the scanning image of the MAPbI _x Cl _3-x light-absorbing layer film deposited on the electrode of TiO ₂ -AgNWs (upper surface); from Figure 1(c), it can be seen that TiO ₂ -AgNWs (embedded) The MAPbI _3-x Cl _x film deposited on the electrode shows a relatively smooth and uniform surface, which also shows that the TiO ₂ nanocrystals spin-coated on the Ag nanowire can improve the film-forming properties of the next layer of film, which is a planar The film formation of several functional layers below the MAPbI _3-x Cl _x perovskite solar cell lays a solid foundation, because the film formation of the film has a great relationship with the substrate, and a flat substrate is beneficial to the formation of the film; in Figure 1(d ), it can be seen that the surface of the MAPbI _x Cl _{3-x light -} absorbing layer film deposited on the TiO ₂ -AgNWs (upper surface) electrode has many wrinkles. On the grid-like AgNWs, the unevenness of the substrate is caused. On the other hand, it may be due to the reaction of the halogen ions in the MAPbI _3-x Cl _x film with the AgNWs, which has a certain destructive effect on the formation of the film.

Table 1 is a table of performance parameters of different perovskite solar cells prepared in Example 1, Comparative Example 1 and Comparative Example 2. It can be seen from Table 1 that TiO ₂ -AgNWs (embedded) electrodes can improve the transport and Separation to improve the photoelectric conversion efficiency of solar cells.

Table 1 Performance parameters of different perovskite solar cells

Fig. 2 is the electrochemical impedance spectrum of the different perovskite solar cells prepared in embodiment 1, comparative example 1 and comparative example 2, wherein (a) is the electrochemical impedance spectrum tested under the open circuit voltage, (b) is the dark state The leakage current relationship curve of the solar cell under the condition; from Figure 2 (a) and (b), it can be seen that the series resistance of the TiO ₂ -AgNWs (embedded) solar cell is significantly lower than that of the TiO ₂ dense layer, However, the series resistance of TiO ₂ -AgNWs (upper surface) solar cells is slightly reduced relative to that of TiO ₂ -AgNWs (embedded) solar cells, indicating that there is a gap between TiO ₂ and MAPbI _x Cl _3-x perovskite materials. The AgNWs did not play a role in reducing the resistance, the possible reason is because of the formation of silver halide, silver halide is a material with extremely poor conductivity; that is to say, in TiO ₂ and MAPbI _x Cl _3-x perovskite The main reason for the degradation of cell performance caused by AgNWs between materials may be due to the reduction of photoelectron flux caused by the recombination center or the damage between MAPbI _x Cl _3-x perovskite materials.

Fig. 3 is the XRD pattern of the MAPbI _x Cl _3-x light absorbing layer thin film deposited on the TiO ₂ -AgNWs (embedded) composite electrode of embodiment 1, as can be seen from Fig. 3, on the TiO ₂ -AgNWs (embedded) composite electrode No peak of AgI appears on the deposited MAPbI _x Cl _3-x light-absorbing layer film, indicating that the embedded AgNWs are effectively separated from the MAPbI _x Cl _3-x light-absorbing layer film.

Fig. 4 is the JV curve of the different perovskite solar cells prepared by embodiment 1, comparative example 1 and comparative example 2, and Fig. 5 is 30 electron transport layers (ETL) in the perovskite solar cell of embodiment 1 The PCE histogram of the device; as can be seen from Figure 4, there is a higher carrier density in the electrode embedded with AgNWs in Example 1 and in the device with only _TiO2 in Comparative Example 2, which is due to the reduction of the embedded AgNWs work function and raise the Fermi level of _TiO2 , thereby enhancing the built-in potential of the device; the regulation of the local charge density is critical for the balance of electron and hole fluxes. It can be seen from Figure 5 that embedding AgNWs in the _TiO2 dense layer in Example 1 can solve the problem of AgNWs forming Ag-AgI on top of the _TiO2 dense layer, and can improve the stability of the device; therefore, the device with embedded electrodes shows good repeatability.

Table 2 shows the photovoltaic parameters of the perovskite solar cell in Example 1 scanned from different directions. It can be seen from Table 2 that the solar cell device based on the embedded AgNWs composite electrode in Example 1 can reduce the J-V hysteresis in different scanning directions. And improve the average PCE.

Table 2 Scanning the photovoltaic parameters of the perovskite solar cell of Example 1 from different directions

Through the above performance tests, it can be seen that the hole transport ability is more matched to the AgNWs embedded in the _TiO2 film in Example 1, and the composite electrode simultaneously eliminates the space-confined charges and increases the surface potential of the _TiO2 compact layer. These results lead to an improvement in V _oc . According to the presented data, the performance of the perovskite solar cell of Example 1 is better than that of the perovskite solar cells of Comparative Example 1 and Comparative Example 2, and the perovskite solar cell fabricated with AgNWs embedded is better than only _TiO2 Performance of solar cells without AgNWs and _TiO2 -AgNWs (upper surface).

The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be It is regarded as the protection scope of the present invention.

Claims (10)

1. a kind of TiO₂The preparation method of the combination electrode of AgNWs is embedded between bilayer film, which comprises the following steps:

S1、TiO₂The preparation of fine and close electron transfer layer: the TiO that will be prepared₂In sol-gel deposition to substrate, after drying again Secondary deposition makes surfacing, and obtains TiO in 350~400 DEG C of 30~40min of annealing in air atmosphere₂Fine and close electron-transport Layer；

S2、TiO₂The preparation of the electrode of upper surface deposition AgNWs: it is 5mg/ that AgNWs, which is dispersed in ethylene glycol, and obtains mass concentration The AgNWs dispersion liquid of mL, is then deposited on the TiO that S1 is obtained for AgNWs dispersion liquid₂On fine and close electron transfer layer, and in air In 180~200 DEG C of 20~30min of annealing in atmosphere, TiO is obtained₂The electrode of upper surface deposition AgNWs；

S3、TiO₂The preparation of the combination electrode of AgNWs: the TiO that will be prepared is embedded between bilayer film₂It is nanocrystalline to deposit to S2 Obtained TiO₂Upper surface deposits on the electrode of AgNWs, and obtains in air atmosphere in 100~300 DEG C of 10~120min of annealing To TiO₂The combination electrode of AgNWs is embedded between bilayer film.

2. a kind of TiO according to claim 1₂The preparation method of the combination electrode of AgNWs is embedded between bilayer film, it is special Sign is, TiO in the S1₂The substance withdrawl syndrome of collosol and gel is 0.2mol/L；

The TiO₂The specific preparation process of collosol and gel are as follows: by butyl titanate, acetylacetone,2,4-pentanedione and ethyl alcohol according to 2.39:1.06: 17 volume ratio is uniformly mixed and obtains solution A, and hydrochloric acid, deionized water and ethyl alcohol are mixed according to the volume ratio of 0.08:0.85:17 Solution B uniformly is obtained, solution B is added in solution A, stirs 30~40min, placement is aged for 24 hours, obtains TiO₂Colloidal sol Gel.

3. a kind of TiO according to claim 1₂The preparation method of the combination electrode of AgNWs is embedded between bilayer film, it is special Sign is that drying temperature is 100 DEG C in the S1, and drying time is 10~20min.

4. a kind of TiO according to claim 1₂The preparation method of the combination electrode of AgNWs is embedded between bilayer film, it is special Sign is, TiO in the S3₂Nanocrystalline mass concentration is 150g/L；

The TiO₂Nanocrystalline preparation process are as follows: butyl titanate and isopropanol are uniformly mixed according to the volume ratio of 3.7:1, And 30~35min is stirred in ice bath, it adds the glacial acetic acid aqueous solution that volume fraction is 20~25% and is uniformly mixed, will mix Polyethylene glycol is added after the reaction was completed and is cleaned by ultrasonic concentration, obtaining mass concentration is 150g/ in 220 DEG C of hydro-thermal reaction 12h for liquid The TiO of L₂It is nanocrystalline.

5. the TiO that preparation method according to any one of claims 1 to 4 is prepared₂It is embedded in AgNWs's between bilayer film Combination electrode.

6. a kind of preparation method of perovskite solar battery, which is characterized in that include TiO in the perovskite solar battery₂ The combination electrode of AgNWs is embedded between bilayer film, comprising the following steps:

(1) TiO is prepared₂The combination electrode of AgNWs is embedded between bilayer film；

(2) under inert gas shielding, by CH₃NH₃I and PbCl₂It is uniformly mixed according to the molar ratio of 3:1 with DMF, and in 60 DEG C Stir to get the perovskite precursor solution that mass fraction is 30%；

(3) the perovskite precursor solution that step (2) obtains is deposited on the TiO that step (1) obtains₂It is embedded between bilayer film On the combination electrode of AgNWs, and stage annealing is carried out under air atmosphere, obtain MAPbI_xCl_3-xLight absorbing layer；

(4) MAPbI for obtaining Spiro-OMeTAD liquid deposition to step (3)_xCl_3-xHole transport is obtained on light absorbing layer Layer；

(5) Ag electrode is deposited on the hole transmission layer of step (4), obtains perovskite solar battery.

7. a kind of preparation method of perovskite solar battery according to claim 6, which is characterized in that in step (4) The process for preparation of Spiro-OMeTAD solution are as follows: mix Spiro-OMeTAD powder according to the solid-liquid ratio of 72.3mg:1mL with chlorobenzene Uniformly, sequentially add lithium salts acetonitrile solution and Tributyl phosphate ester and be mixed 1~1.5h obtain Spiro-OMeTAD Solution；

Wherein the acetonitrile solution concentration of lithium salts is 520mg/mL, the volume of the acetonitrile solution of lithium salts, Tributyl phosphate ester and chlorobenzene Than for 10.9:8.8:500.

8. a kind of preparation method of perovskite solar battery according to claim 6, which is characterized in that in step (3) The process of stage annealing are as follows: anneal 30min at prior to 80 DEG C, then in 100 DEG C of annealing 60min.

9. a kind of preparation method of perovskite solar battery according to claim 6, which is characterized in that in step (1) TiO₂The substrate being embedded in the combination electrode of AgNWs between bilayer film is ito glass substrate, the preprocessing process of substrate are as follows: point It is not cleaned successively using boiling water, deionized water and dehydrated alcohol, the mixing time in step (2) is 10~12h.

10. the perovskite solar battery obtained according to any preparation method of claim 6~9, which is characterized in that packet Include the TiO set gradually from bottom to top₂Composite electrode layers, the MAPbI of AgNWs are embedded between bilayer film_xCl_3-xLight absorbing layer, Spiro-OMeTAD hole transmission layer and Ag electrode layer, the TiO₂The thickness of the composite electrode layers of AgNWs is embedded between bilayer film Degree is 50~200nm, the MAPbI_xCl_3-xLight absorbing layer with a thickness of 200~400nm, the hole Spiro-OMeTAD passes Defeated layer with a thickness of 10~150nm, the Ag electrode layer with a thickness of 100nm.