CN112186107B - Tin-based perovskite solar cell with hole transport layer and preparation method thereof - Google Patents

Tin-based perovskite solar cell with hole transport layer and preparation method thereof Download PDF

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CN112186107B
CN112186107B CN202011033201.3A CN202011033201A CN112186107B CN 112186107 B CN112186107 B CN 112186107B CN 202011033201 A CN202011033201 A CN 202011033201A CN 112186107 B CN112186107 B CN 112186107B
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nickel oxide
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台启东
崔霞霞
王珍
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Wuhan University WHU
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Abstract

The invention belongs to the technical field of perovskite batteries, and discloses a tin-based perovskite solar cell with a hole transport layer and a preparation method thereof, wherein the tin-based perovskite solar cell sequentially comprises transparent conductive glass, the hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode from bottom to top; the hole transport layer is nickel oxide nano particles with the diameter of 5-10 nm. The preparation method comprises the following steps: cleaning and drying ITO glass to obtain an ITO glass substrate; preparing a nickel oxide nanoparticle hole transport layer; preparing a tin-based perovskite film; preparing an electron transport layer on the perovskite layer; a metal electrode is prepared on the electron transport layer to obtain a solar cell. The photoelectric conversion efficiency of the tin-based perovskite battery prepared by the invention is 7.42%. In addition, the battery maintains a stable output with an efficiency of about 7.4% in a maximum power point tracking range of 600s, which indicates that the battery has better stability.

Description

Tin-based perovskite solar cell with hole transport layer and preparation method thereof
Technical Field
The invention belongs to the technical field of perovskite batteries, and particularly relates to a tin-based perovskite solar cell with a hole transport layer and a preparation method thereof.
Background
Currently, organic-inorganic lead halides (APbX) 3 ，A＝Cs + Methyl Ammonium (MA) + ) Or methyl ether amine (FA) + )；X＝I - Or Br (Br) - ) Perovskite Solar Cells (PSCs) are receiving great attention due to their high efficiency, low cost and simple manufacturing process. However, the toxic Pb content of these perovskites has hindered the practical application of devices, resulting in the initiation of the use of lead-free or lead-free perovskites (ASnX 3, ASn x Pb 1-x X 3 ) Is a study of (a). Tin-based perovskite has many advantages, such as a suitable band gap (1.2-1.4 eV), low exciton binding energy, and high charge carrier mobility, and is a promising candidate for the preparation of efficient lead-free perovskite solar cells. But sex of Sn-based PSCsCan be inferior to lead-based due to the oxidative instability of tin-based perovskite.
For a trans-tin-based perovskite solar cell, PEDOT: PSS is one of the most popular hole transport materials because it has suitable mechanical properties, transparency and work function, however its disadvantages are not negligible, and its hydrophilic and acidic nature of the sulfonic acid groups can impair perovskite lifetime and stability, with instability to uv light. In addition, its high production cost limits its commercialization. It is therefore important to find inorganic materials that replace the organic hole layer.
The inorganic hole transport material has higher hole mobility and good stability, and becomes a good hole transport material. The valence band of nickel oxide matches that of many perovskite because of its wide forbidden band, good electron blocking and optical transparency. Is a promising hole transport material. However, preparing a hole transport layer of nickel oxide nanoparticles with high dispersibility and adjustable pH range from a low-temperature solution process remains a great challenge, and conventional methods for synthesizing nickel oxide nanoparticles by adjusting pH with sodium hydroxide require fixing pH to 10 to synthesize relatively ideal nickel oxide nanoparticles, which are difficult to control and difficult to disperse.
Through the above analysis, the problems and defects existing in the prior art are as follows:
(1) Perovskite Solar Cells (PSCs) of organic-inorganic lead halides are receiving widespread attention due to their high efficiency, low cost and simple manufacturing process. However, these perovskite materials contain a large amount of toxic metallic lead (Pb), which seriously hampers the practical application of the device.
(2) The common hole transport material PEDOT: PSS of the trans-perovskite battery has serious stability defects, which is unfavorable for the long-term reliability of the device.
(3) Nickel oxide is a stable hole transport material, in the prior art, the pH value of the nickel oxide nano particles is fixed to be 10 to synthesize the ideal nickel oxide nano particles by adjusting the pH value by using sodium hydroxide, the synthesis process is difficult to control, and the large-scale and low-cost commercial preparation is not facilitated.
The difficulty of solving the problems and the defects is as follows:
tin-based perovskite has excellent photoelectric properties, and is the most promising candidate material for preparing high-efficiency lead-free perovskite solar cells. The intrinsic stability of tin-based perovskite materials is poor, tin-based perovskite batteries are usually prepared in a trans-form, and the device performance and stability are severely dependent on the choice of hole transport material substrate. Therefore, searching for a novel hole material with excellent charge transmission performance and stable physicochemical properties and a simple and reliable preparation process thereof is one of key elements for preparing an efficient and stable tin-based lead-free perovskite solar cell.
The meaning of solving the problems and the defects is as follows:
the invention improves the performance and stability of the tin-based perovskite solar cell, optimizes the cell performance by improving the hole extraction efficiency, provides a new thought for developing the perovskite solar cell with a low-cost high-dispersion nickel oxide nanoparticle hole transport layer, synthesizes nickel oxide nanoparticles with good dispersibility in a wider pH range, and is suitable for large-scale application.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a tin-based perovskite solar cell of a hole transport layer and a preparation method thereof. In particular to a tin-based perovskite solar cell based on a nickel oxide nanoparticle hole transport layer with high dispersibility and wider synthetic pH range and a preparation method thereof. In particular to a trans-tin-based perovskite solar cell based on a nickel oxide hole transport layer which has high dispersibility and can be stably synthesized in a wider pH range and a preparation method thereof.
The invention discloses a tin-based perovskite solar cell with high dispersibility and wide synthetic PH range of nickel oxide nano particle hole transport layer, which is characterized by being prepared by the following preparation method: (1) Cleaning and drying ITO glass to obtain an ITO glass substrate; (2) preparing a nickel oxide nanoparticle hole transport layer; (3) preparing a tin-based perovskite thin film; (4) preparing an electron transport layer on the perovskite layer; (5) Preparing a metal electrode on the electron transport layer to obtain a solar cell;
preferably, the hole transport layer of the nickel oxide nanoparticle is prepared by adjusting the pH value by ammonia water.
Preferably, the preparation method of the tin-based perovskite solar cell of the nickel oxide nanoparticle hole transport layer comprises the following steps:
step 1, preparing nickel oxide nanoparticle dispersion liquid;
dissolving a certain amount of nickel nitrate hexahydrate in deionized water to prepare a black green precursor solution; then ammonia water is used for adjusting the PH value of the precursor solution, and the molar ratio of the ammonia water to the nickel nitrate is 1-5. The obtained precursor solution is aged, centrifuged, washed, dried and sintered to obtain deep black powder, and the obtained nickel oxide nano particles are dispersed into a mixed solution of deionized water and isopropanol to prepare nickel oxide nano particle dispersion liquid;
step 2, cleaning and drying the ITO base glass to obtain an ITO glass substrate;
step 3, coating the nickel oxide nanoparticle dispersion liquid prepared in the step one on an ITO glass substrate to prepare a hole transport layer;
step 4, preparing a tin-based perovskite absorption layer on the hole transport layer;
step 5, preparing an electron transport layer on the tin-based perovskite absorption layer;
step 6, evaporating the electrode on the electron transport layer
Preferably, in the step 1, 40-50 mmol of nickel nitrate hexahydrate is dissolved in 100mL of deionized water; then regulating the pH value of the precursor solution by using 30% ammonia water, aging the obtained precursor solution for one night, centrifuging, washing twice by using deionized water, vacuum drying and sintering the obtained product, and dispersing nickel oxide nano particles obtained after sintering into the volume ratio of deionized water to isopropanol (3-4) at the concentration of 5-10 mg/mL: and (3) preparing nickel oxide nanoparticle dispersion liquid in the mixed liquid of 1 minute.
Preferably, the centrifugal speed of the precursor solution is 5000-7000 rmp/s, and the centrifugal time is 5-10 min; the vacuum drying temperature is 80-100 ℃ and the drying time is 10-24 h; the dried product is sintered for 30 to 120 minutes at the temperature of 200 to 400 ℃.
Preferably, in the step 3, the nickel oxide nanoparticle dispersion liquid is coated on the ITO substrate by a spin coating method, and annealed for 10-30 min at the temperature of 100-200 ℃ on a heating plate; wherein the spin coating rotating speed is 2000-4000 rmp/s, and the spin coating time is 30-60 s.
Preferably, in step 4, the perovskite absorption layer material is ASnX 3 Or ASn x Pb 1-x X 3 Perovskite crystal, wherein a=cs + Methyl Ammonium (MA) + ) Or methyl ether amine (FA) + )；X＝I - Or Br (Br) - 。
Preferably, in step 5, PCBM is dissolved in chlorobenzene solution to prepare PCBM chlorobenzene solution with concentration of 20mg/mL, and the PCBM chlorobenzene solution is spin-coated on the perovskite absorption layer by a spin-coating method to prepare the electron transport layer, wherein the spin-coating speed is 1500-3000 rmp/s, and the spin-coating time is 40-60 s.
Preferably, in the step 6, the electrode is made of Ag or Al material, and the thickness of the electrode is 100-200 nm.
The invention further aims to provide a tin-based perovskite solar cell with high dispersibility and a hole transport layer of nickel oxide nano particles with a wider synthetic pH range, wherein the perovskite solar cell sequentially comprises transparent conductive glass (1), a hole transport layer (2), a perovskite absorption layer (3), an electron transport layer (4) and an electrode (5) from bottom to top; wherein the hole transport layer is nickel oxide nano particles with the diameter of 5-10 nm.
The nickel oxide nano particles are prepared by adjusting the pH value by ammonia water.
Another object of the present invention is to provide a solar device mounting the tin-based perovskite solar cell.
By combining all the technical schemes, the invention has the advantages and positive effects that:
the trans-tin-based perovskite solar cell provided by the invention comprises a transparent conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer and a metal electrode. Compared with the traditional method for synthesizing nickel oxide nano particles by adjusting the fixed pH value (PH=10) by sodium hydroxide, the method has the advantages that the hole transport layer of the nickel oxide nano particles is synthesized by ammonia water, can be synthesized stably in a soft and wider pH range, has better dispersibility, and is suitable for large-scale application. The nickel oxide nano particles with high dispersibility can be used as a hole transport layer to avoid contact between the perovskite light absorption layer and the transparent electrode, and prevent interface carriers from being compounded. The prepared trans-tin-based perovskite solar cell has excellent photovoltaic performance and better stability.
Advantages of the present invention compared to the prior art further include:
the invention discloses a tin-based perovskite solar cell with high dispersibility and a wide synthetic pH range of nickel oxide nanoparticle hole transport layer, wherein the hole transport layer of the cell is nickel oxide nanoparticle, the diameter size of the nanoparticle is 5-10nm, the method can obtain the nickel oxide nanoparticle hole transport layer with low cost and high dispersibility, in addition, the method can synthesize nickel oxide nanoparticle with high dispersibility in a wide pH range, and the nickel oxide nanoparticle with high dispersibility can be obtained in a certain pH range, so that the method is suitable for large-scale application. The method has the advantages of simple operation, low cost, good dispersibility, and the nickel oxide nano particles with high dispersibility can be used for preparing the hole transport layer with good flatness, uniform surface and excellent performance. The method improves the performance and stability of the tin-based perovskite solar cell, and improves the hole extraction efficiency by improving the dispersibility to obtain a compact film so as to optimize the cell performance. The photoelectric conversion efficiency of the battery prepared by the method is 7.42. In addition, a stable PCE of 7.42% for tin-based perovskite solar cells within a maximum power point tracking range of 600s indicates a better stability of the cells.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following description will briefly explain the drawings needed in the embodiments of the present application, and it is obvious that the drawings described below are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a perovskite solar cell prepared according to an embodiment of the present invention.
In fig. 1: 1. conductive glass; 2. a hole transport layer; 3. a perovskite absorber layer; 4. an electron transport layer; 5. an electrode.
Fig. 2 is an XRD pattern of the calcined nickel oxide nanoparticles provided by the examples of the present invention.
Fig. 3 is an SEM image of a nickel oxide nanoparticle thin film provided in an embodiment of the present invention.
Fig. 4 is a TEM image of nickel oxide nanoparticles provided by an embodiment of the present invention.
Fig. 5 is a graph of the absorption of uv and visible light of a nickel oxide nanoparticle film according to an embodiment of the present invention.
Fig. 6 is a J-V plot of a preferred battery of example 3 provided by an embodiment of the present invention.
Fig. 7 is a graph of the stability power in air of a preferred battery of example 3 provided by an embodiment of the present invention.
Fig. 8 is a J-V plot of the batteries of examples 1-5 provided by an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In view of the problems existing in the prior art, the present invention provides a tin-based perovskite solar cell with a hole transport layer and a preparation method thereof, and the present invention is described in detail below with reference to the accompanying drawings.
The invention provides a tin-based perovskite solar cell with high dispersibility and a nickel oxide nanoparticle hole transport layer with wider synthetic pH range, wherein the structure of the cell is shown in figure 1, and the cell sequentially comprises transparent conductive glass 1 (the thickness of a conductive layer is about 100-200 nm), a hole transport layer 2 (the thickness is 5-20 nm), a perovskite absorption layer 3 (the thickness is 100-500 nm), an electron transport layer (the thickness is 5-20 nm) 4 and an electrode 5 (the thickness is 50-200 nm) from bottom to top; wherein the hole transport layer is nickel oxide nano particles with the diameter of 5-10 nm.
The invention also provides a preparation method of the tin-based perovskite solar cell of the nickel oxide nanoparticle hole transport layer, which comprises the following steps:
step 1, preparing nickel oxide nanoparticle dispersion liquid;
(1) Dissolving 40-50 mmol of nickel nitrate hexahydrate in 100mL of deionized water; then regulating the pH value of the precursor solution by using 30% ammonia water, and uniformly stirring to obtain the precursor solution;
(2) Aging the precursor solution for one night, centrifuging the obtained precipitate at a centrifugation rate of 5000-7000 rmp/s for 5-10 min; washing twice with deionized water, and drying the obtained product in a vacuum drying oven at the vacuum drying temperature of 80-100 ℃ for 10-24 hours; grinding the dried product, and sintering the ground dried product in a muffle furnace at 200-400 ℃ for 30-120 min. The calcined product is nickel oxide nano particles.
The obtained nickel oxide nano particles are dispersed into deionized water or the volume ratio of the deionized water to isopropanol (3-4) at the concentration of 5-10 mg/mL: and (3) preparing nickel oxide nanoparticle dispersion liquid in the mixed liquid of 1 minute.
And 2, preparing the ITO glass substrate.
The ITO glass was cut to a size of 1.5X1.3 cm. Ultrasonic cleaning is carried out in deionized water, acetone and ethanol for 20-30 min respectively, and drying is carried out, thus being used as an ITO glass substrate for standby.
And 3, preparing a hole transport layer of the nickel oxide nano particles.
The nickel oxide nanoparticle dispersion liquid prepared in the step one was filtered with a 0.45 μm nylon filter by a solution spin coating method and spin-coated on an ITO glass substrate. Then annealing for 20-40 min on a hot plate at 100-200 ℃; preparing a nickel oxide nanoparticle hole transport layer; wherein the spin coating speed is 3000-5000 rpm, and the spin coating time is 30-60 s.
And 4, preparing the perovskite absorption layer.
(1) Preparing a perovskite absorption layer precursor liquid:
mixing 1M FAI, csI, methyl Ammonium (MAI) or methyl ether amine (FAI) with 1M DMSO, 0.1M Sncl 2 Or PbI is added into a certain amount of DMF, the volume ratio of DMF to DMSO is 9:1, and the perovskite precursor solution with the concentration of 1mol/L is prepared.
(2) Preparation of perovskite absorber layer
The perovskite precursor solution with the concentration of 1mol/L is spin-coated on the hole transmission layer through a spin-coating method, the spin-coating rotating speed is 4000-5000 rmp/s, the spin-coating time is 30-50 s, and Chlorobenzene (CB) is quickly dripped on the substrate at 11-15 s in the process. And then annealing at 70-100 ℃ for 5-15 min.
Step 5, preparing an electron transport layer
PCBM is dissolved in chlorobenzene solution to prepare PCBM chlorobenzene solution with concentration of 20mg/mL, and the PCBM chlorobenzene solution is spin-coated on the perovskite absorption layer by a spin coating method to prepare the electron transport layer, wherein the spin coating speed is 1500-3000 rmp/s, and the spin coating time is 40-60 s. All the procedures are full of N 2 Is carried out in a glove box.
Step 6, evaporating the electrode
Evaporating Ag or Al electrode on the electron transport layer by vapor deposition at a rate of
Figure BDA0002704417300000071
The thickness of the electrode is 50-200 nm.
In the present invention, referring to fig. 1, a schematic structural diagram of a perovskite solar cell prepared according to the present invention is shown.
Fig. 2 is an XRD pattern of the nickel oxide nanoparticles obtained after sintering in step 1 of example 1, and the average particle diameter size of the nickel oxide nanoparticles calculated by XRD is 8 to 10nm.
Fig. 3 is an SEM image of a nickel oxide nanoparticle film, from which it can be seen that the nickel oxide film has good flatness, uniform and dense surface, which also illustrates the high dispersibility of nickel oxide.
Fig. 4 is a TEM image of nickel oxide nanoparticles, and it can be seen from fig. 4 that the average particle size of the nickel oxide nanoparticles prepared by this method is 5 to 10nm, which is also consistent with the particle size calculated by XRD.
Fig. 5 is an ultraviolet-visible light absorption curve of a nickel oxide nanoparticle film, which illustrates that the nickel oxide nanoparticle film has high optical transmittance, which can reduce light absorption loss.
Fig. 6 is a J-V plot of the preferred device of example 3, and table 3 shows that the preferred cell has excellent photovoltaic performance, and device efficiency can reach 7.42%.
Fig. 7 is a graph showing the stable output of the preferred cell of example 3 in air, and it can be seen that the preferred cell has better stability.
Fig. 8 is a J-V plot of examples 1-5, table 1 shows that the photovoltaic performance of examples 1-5 is not substantially changed, the efficiency fluctuates between 5.84 and 6.6%, and in combination with table 3, examples 1-5 can be seen to be more stable in the PH range of 5-9, indicating that nickel oxide nanoparticles with better dispersibility can be synthesized in a wider PH range of 5-9, thereby obtaining a tin-based perovskite solar cell with more stable photovoltaic performance and excellent performance in a wider PH range.
The invention is further described below in connection with specific embodiments.
Example 1
Step 1, preparing nickel oxide nanoparticle dispersion liquid;
(1) 50mmol of nickel nitrate hexahydrate was dissolved in 100mL of deionized water; then, as shown in Table 3, the pH value of the precursor solution was adjusted to 5-6 with 30% ammonia (2.8 mL) in an amount of 1 time the amount of the nickel nitrate substance, and the precursor solution was obtained by stirring uniformly;
(2) Aging the precursor solution overnight, centrifuging the obtained precipitate at a centrifugation rate of 5000rmp/s for 5min; washing twice with deionized water, and drying the obtained product in a vacuum drying oven at a vacuum drying temperature of 100 ℃ for 12 hours; and grinding the dried product, and sintering the ground dried product in a muffle furnace at 270 ℃ for 120min. The calcined product is nickel oxide nano particles.
The nickel oxide nanoparticles were dispersed at a concentration of 8mg/mL into deionized water to isopropyl alcohol volume ratio 3: and (3) preparing nickel oxide nanoparticle dispersion liquid in the mixed liquid of 1 minute.
And 2, preparing the ITO glass substrate.
The ITO glass was cut to a size of 1.5X1.3 cm. Ultrasonic cleaning in deionized water, acetone and ethanol for 20min respectively, and blow-drying to obtain ITO glass substrate.
And 3, preparing a hole transport layer of the nickel oxide nano particles.
The nickel oxide nanoparticle dispersion liquid prepared in the step one was filtered with a 0.45 μm nylon filter by a solution spin coating method and spin-coated on an ITO glass substrate. Then annealing for 30min on a hot plate at 150 ℃; preparing a nickel oxide nanoparticle hole transport layer; wherein the spin-coating speed was 4000rpm and the spin-coating time was 40s.
And 4, preparing the perovskite absorption layer.
(1) Preparing a perovskite absorption layer precursor liquid:
1M FAI, 1M DMSO, 0.1M Sncl 2 Adding the perovskite precursor solution into a certain amount of DMF, wherein the volume ratio of DMF to DMSO is 9:1, and preparing the perovskite precursor solution with the concentration of 1 mol/L.
(2) Preparation of perovskite absorber layer
The perovskite precursor solution with the concentration of 1mol/L is spin-coated on the hole transmission layer through a spin coating method, the spin coating rotating speed is 5000rmp/s, the spin coating time is 30-50 s, in the process, chlorobenzene (CB) is rapidly dripped on the substrate at 13s, and then annealing is carried out for 5min at 70.
Step 5, preparing an electron transport layer
PCBM is dissolved in chlorobenzene solution to prepare PCBM chlorobenzene solution with concentration of 20mg/mL, and the PCBM chlorobenzene solution is spin-coated on the perovskite absorption layer by a spin coating method to prepare the electron transport layer, wherein the spin coating speed is 3000rmp/s, and the spin coating time is 40s. All the procedures are full of N 2 Is carried out in a glove box.
Step 6, evaporating the electrode
Vapor plating Ag electrode on electron transport layer by vapor plating at a rate of
Figure BDA0002704417300000091
The electrode thickness was 200nm.
Example 2
Step 1, preparing nickel oxide nanoparticle dispersion liquid;
(1) 50mmol of nickel nitrate hexahydrate was dissolved in 100mL of deionized water; then, as shown in Table 3, the pH value of the precursor solution was adjusted to 6-7 with 30% aqueous ammonia (5.6 mL) in an amount of 2 times the amount of the nickel nitrate substance, and the precursor solution was obtained by stirring uniformly;
other steps are as above
Example 3
Step 1, preparing nickel oxide nanoparticle dispersion liquid;
(1) 50mmol of nickel nitrate hexahydrate was dissolved in 100mL of deionized water; then, as shown in Table 3, the pH value of the precursor solution was adjusted to 7-8 with 30% aqueous ammonia (8.4 mL) in an amount of 3 times the amount of the nickel nitrate, and the precursor solution was obtained by stirring uniformly;
other steps are as above
Example 4
Step 1, preparing nickel oxide nanoparticle dispersion liquid;
(1) 50mmol of nickel nitrate hexahydrate was dissolved in 100mL of deionized water; then, as shown in Table 3, the pH of the precursor solution was adjusted to 8 with 30% aqueous ammonia (11.2 mL) in an amount of 4 times the amount of nickel nitrate, and the precursor solution was obtained by stirring uniformly;
other steps are as above
Example 5
Step 1, preparing nickel oxide nanoparticle dispersion liquid;
(1) 50mmol of nickel nitrate hexahydrate was dissolved in 100mL of deionized water; then, as shown in Table 3, the pH of the precursor solution was adjusted to 8-9 with 30% aqueous ammonia (14 mL) in an amount of 5 times the amount of nickel nitrate, and the precursor solution was obtained by stirring uniformly;
other steps are the same as above;
the amount of ammonia water of 6 times the amount of the nickel nitrate material shown in Table 3 was added dropwise to prepare a battery having no photovoltaic property, so that the J-V curve of FIG. 8 was free of 6 times the amount of the nickel nitrate material.
TABLE 1 photovoltaic performance parameters of tin-based perovskite solar cells with different aqueous ammonia addition levels (corresponding to examples 1-5)
Figure BDA0002704417300000111
Table 2 example 3 photovoltaic performance parameters of preferred cells
Figure BDA0002704417300000112
TABLE 3 pH and yield of precursor solutions with different aqueous ammonia dropwise addition amounts
Ammonia addition multiple PH value
1 5-6
2 6-7
3 7-8
4 8
5 8-9
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the terms "upper," "lower," "left," "right," "inner," "outer," "front," "rear," "head," "tail," and the like are used as an orientation or positional relationship based on that shown in the drawings, merely to facilitate description of the invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (9)

1. The tin-based perovskite solar cell based on the nickel oxide nano-particle hole transport layer with high dispersibility and wide synthetic pH range is characterized in that the tin-based perovskite solar cell based on the nickel oxide nano-particle hole transport layer with high dispersibility and wide synthetic pH range sequentially comprises transparent conductive glass, a hole transport layer, a perovskite absorption layer, an electron transport layer and an electrode from bottom to top;
the hole transport layer is nickel oxide nano particles with the diameter of 8-10 nm;
the preparation method of the nickel oxide nano-particles comprises the following steps: dissolving a certain amount of nickel nitrate hexahydrate into deionized water to prepare dark green precursor solution; then ammonia water is used for adjusting the pH value of the precursor solution to be 5-9, and the molar ratio of the ammonia water to the nickel nitrate is 1-5; the obtained precursor solution is aged, centrifuged, washed, dried and sintered to obtain the nickel oxide nano particles which are deep black powder.
2. A method for preparing a tin-based perovskite solar cell based on a nickel oxide nanoparticle hole transport layer with high dispersibility and a wide synthetic pH range, the method comprising:
cleaning and drying ITO glass to obtain an ITO glass substrate;
preparing a nickel oxide nanoparticle hole transport layer;
preparing a tin-based perovskite film;
preparing an electron transport layer on the perovskite layer;
preparing a metal electrode on the electron transport layer to obtain a solar cell;
the preparation method of the nickel oxide nano-particles comprises the following steps: dissolving a certain amount of nickel nitrate hexahydrate into deionized water to prepare dark green precursor solution; then ammonia water is used for adjusting the pH value of the precursor solution to be 5-9, and the molar ratio of the ammonia water to the nickel nitrate is 1-5; the obtained precursor solution is aged, centrifuged, washed, dried and sintered to obtain the nickel oxide nano particles which are deep black powder.
3. The method of claim 2, wherein the hole transport layer of nickel oxide nanoparticles is prepared with ammonia to adjust pH.
4. The preparation method according to claim 2, characterized in that it comprises in particular:
step 1, preparing nickel oxide nanoparticle dispersion liquid: dissolving a certain amount of nickel nitrate hexahydrate into deionized water to prepare dark green precursor solution; then ammonia water is used for adjusting the pH value of the precursor solution, and the molar ratio of the ammonia water to the nickel nitrate is 1-5; the obtained precursor solution is aged, centrifuged, washed, dried and sintered to obtain deep black powder, and the obtained nickel oxide nano particles are dispersed into a mixed solution of deionized water and isopropanol to prepare nickel oxide nano particle dispersion liquid;
step 2, cleaning and drying the ITO base glass to obtain an ITO glass substrate;
step 3, coating the nickel oxide nanoparticle dispersion liquid prepared in the step 1 on an ITO glass substrate to prepare a hole transport layer;
step 4, preparing a tin-based perovskite absorption layer on the hole transport layer;
step 5, preparing an electron transport layer on the tin-based perovskite absorption layer;
and 6, evaporating an electrode on the electron transport layer.
5. The method according to claim 4, wherein in step 1, 40-50 mmol of nickel nitrate hexahydrate is dissolved in 100mL of deionized water; then regulating the pH value of the precursor solution by using 30% ammonia water, aging the obtained precursor solution for one night, centrifuging, washing twice by using deionized water, vacuum drying and sintering the obtained product, and dispersing the nickel oxide nano particles obtained after sintering into the volume ratio of deionized water to isopropanol (3-4) at the concentration of 5-10 mg/mL: 1, preparing nickel oxide nanoparticle dispersion liquid in the mixed liquid;
the precursor solution has a centrifugal speed of 5000-7000 rpm and a centrifugal time of 5-10 min, and is dried at a vacuum temperature of 80-100 ℃ for 10-24 h; and sintering the dried product at 200-400 ℃ for 30-120 min.
6. The preparation method of claim 4, wherein in the step 3, the dispersion of nickel oxide nanoparticles is coated on the ITO substrate by spin coating, and annealed at 100-200 ℃ on a heating plate for 10-30 min; the spin coating rotating speed is 2000-4000 rpm, and the spin coating time is 30-60 s;
in the step 4, the perovskite absorption layer material is ASnX 3 Or ASn x Pb 1-x X 3 Perovskite crystals, a=cs, methyl Ammonium (MA) or methyl ether amine (FA); x=i or Br.
7. The method according to claim 4, wherein in step 5, PCBM is dissolved in a chlorobenzene solution to prepare a PCBM chlorobenzene solution with a concentration of 20mg/mL, and the PCBM chlorobenzene solution is spin-coated on the perovskite absorption layer by spin-coating to prepare the electron transport layer, the spin-coating speed is 1500-3000 rpm, and the spin-coating time is 40-60 s.
8. The method according to claim 4, wherein in the step 6, the electrode is made of Ag or Al, and the thickness of the electrode is 100-200 nm.
9. A solar device carrying the tin-based perovskite solar cell according to claim 1.
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