CN110224069B - Perovskite solar cell with waterproof function and preparation method thereof - Google Patents
Perovskite solar cell with waterproof function and preparation method thereof Download PDFInfo
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- CN110224069B CN110224069B CN201910509950.XA CN201910509950A CN110224069B CN 110224069 B CN110224069 B CN 110224069B CN 201910509950 A CN201910509950 A CN 201910509950A CN 110224069 B CN110224069 B CN 110224069B
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- H10K71/10—Deposition of organic active material
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Abstract
The invention discloses a perovskite solar cell with a waterproof function and a preparation method thereof, wherein the method comprises the following steps: sequentially preparing each functional layer on a substrate; preparing an ionic liquid layer on the outermost functional layer, wherein the ionic liquid layer is made of a functional group with a hydrophobic characteristic as a cation, a C = C double bond is contained at the tail end of a branched chain, and a halogen element ion I is used as an anion of the ionic liquid ‑ 、Br ‑ 、Cl ‑ And F ‑ An ionic liquid of one of (1); and preparing a metal electrode on the ionic liquid layer to obtain the perovskite solar cell. According to the invention, by utilizing the property that the ionic liquid with C = C double bonds is heated in the air to polymerize, a layer of reticular ionic liquid can be formed on the surface of the perovskite solar cell, and the hydrophobic characteristic of the ionic liquid is added, so that the surface waterproof effect can be achieved, and the moisture resistance of the perovskite solar cell is obviously improved. When the ionic liquid is deposited on the surface, the transmission of charges can not be blocked, and therefore the reduction of the conversion efficiency of the perovskite solar cell can not be caused.
Description
Technical Field
The invention belongs to the technical field of photovoltaics, and particularly relates to a perovskite solar cell with a waterproof function and a preparation method thereof.
Background
The perovskite solar cell is a latest generation thin film solar cell developed based on a dye-sensitized solar cell, and is widely concerned all over the world by virtue of the advantages of high efficiency and low cost. At present, the highest efficiency of perovskite solar cell authentication is broken through by 23%, and the perovskite solar cell authentication can be comparable with the traditional silicon solar cell and has considerable industrialization prospect. However, the instability problem of perovskite materials is the biggest obstacle on the way to their commercial application. Among various factors which can cause the decomposition of perovskite materials, water is strictly avoided, and a waterproof layer is deposited on the surface of the perovskite solar cell, so that the improvement of the humidity stability of the cell is particularly important.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a perovskite solar cell with a waterproof function, and the humidity stability of the cell is improved.
The technical scheme of the invention is as follows: a preparation method of a perovskite solar cell with a waterproof function comprises the following steps:
(1) Sequentially preparing each functional layer on a substrate;
(2) Preparing an ionic liquid layer on the outermost functional layer, wherein the ionic liquid layer is made of a functional group with a hydrophobic characteristic as a cation, a C = C double bond is contained at the tail end of a branched chain, and a halogen element ion I is used as an anion of the ionic liquid - 、Br - 、Cl - And F - An ionic liquid of one of (1);
(3) And preparing a metal electrode on the ionic liquid layer to obtain the perovskite solar cell.
The ionic liquid is a green salt substance with a plurality of special properties, has the advantages of various types, high thermal stability and chemical stability, wide operable temperature range, strong conductivity and the like, and has a plurality of special physical and chemical properties by designing the ionic liquids with different structures. The ionic liquid consists of organic positive ions and negative ions, and C = C double bonds exist in organic positive ion structures of some hydrophobic ionic liquids.
Preferably, the substrate is an FTO glass substrate, in the step (1), a part of the substrate is etched first, the substrate is divided into an etched region and an unetched region, and then an electron transport layer, a perovskite absorption layer, and a hole transport layer are sequentially prepared on the etched region and the unetched region.
Preferably, in the step (2), the ionic liquid is dispersed in an isopropanol solution, and the ionic liquid layer is prepared by a spin coating method.
Preferably, the concentration of the isopropanol solution is 1-5mg/mL, when the ionic liquid layer is prepared by a spin coating method, 30-100 microliters of ionic liquid is dripped, the spin coating speed is 3000-4000 rpm, and after the spin coating is finished, a sample is heated in the air at the temperature of 40-50 ℃.
Preferably, the material of the electron transport layer is TiO 2 ZnO and SnO 2 The electron transport layer is prepared by a sol-gel method, a spray pyrolysis method or a magnetron sputtering method.
Preferably, the perovskite absorption layer is made of a material with a chemical formula of ABX 3 A compound of the form (I) wherein A is Cs, rb, CH 3 NH 3 And CH 2 (NH 2 ) 2 B is Pb, and X is one or two of I or Br; the perovskite absorption layer is prepared by a spin coating method, a thermal evaporation method or a blade coating method.
Preferably, the material of the hole transport layer is bis (trifluoromethanesulfonyl) imide Lithium (LITFSI) doped Spiro-OMeTAD, and the hole transport layer is prepared by spin coating.
Preferably, the metal electrode is a gold electrode, and the metal electrode is prepared by a thermal evaporation method.
Preferably, the FTO glass substrate comprises an FTO transparent conductive layer, and the edge of the ionic liquid layer extends downwards to cover the functional layer and extends to the FTO transparent conductive layer.
The invention also provides the perovskite solar cell with the waterproof function prepared by the preparation method of the perovskite solar cell with the waterproof function.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention utilizes the property that the ionic liquid with C = C double bonds is heated in the air to generate polymerization, can form a layer of reticular ionic liquid on the surface of the perovskite solar cell, and can play a role of surface water resistance by adding the hydrophobic characteristic of the ionic liquid, thereby obviously improving the moisture resistance of the perovskite solar cell.
(2) The ionic liquid has good conductivity, so that when the ionic liquid is deposited on the surface, the transmission of charges can not be blocked, and the attenuation of the conversion efficiency of the perovskite solar cell can not be caused.
(3) The ionic liquid has various types and strong designability, and the ionic liquid with similar structure can be further subjected to structure optimization on the basis of the method, so that the possibility of improving other performances of the device is obtained.
(4) The invention has simple process and low cost, and is suitable for future commercial application.
Drawings
Fig. 1 is a schematic structural view of a perovskite solar cell having a waterproof function according to the present invention.
Fig. 2 is a schematic structural diagram of an ionic liquid.
FIG. 3 is a graph comparing J-V curves of batteries.
Fig. 4 is a graph of the results of stability tests in air for cells with and without an ionic liquid layer.
Fig. 5 is a graph comparing hydrophobic performance of batteries with and without an ionic liquid layer.
Detailed Description
Example 1
A method for preparing a perovskite solar cell, comprising the following steps, as shown in fig. 1:
(1) The FTO conductive glass is used as a substrate 1, the FTO conductive glass is provided with an FTO transparent conductive layer 2, firstly, zinc powder and dilute hydrochloric acid are used for reaction, part of FTO is etched, then, deionized water, ethanol, acetone and isopropanol are respectively used for ultrasonic cleaning, and after being dried by nitrogen, the FTO transparent conductive layer is placed in an ozone cleaning machine for processing for 15 minutes.
(2) Subsequently, the electron transport layer 3 is prepared by first preparing a dense layer of TiO by spray pyrolysis 2 Preparing a required solution, dissolving 200 mu L of diisopropyl di (acetylacetonate) titanate in 6mL of isopropanol, putting the solution into a spray nozzle, placing a substrate on a flat furnace at 450 ℃, driving the spray to spray by using oxygen, adjusting the gas flow and the spraying height of gas, uniformly spraying the solution on the substrate, and continuing to heat at 450 ℃ for 30 minutes after the spraying is finished. Cooling to normal temperature, taking out, and performing TiO by using spin coating method 2 Preparation of the skeleton layer, 1g of TiO are initially introduced 2 The slurry was dissolved in 9mL of ethanol and stirred for 12 hours. 50 mu L of the solution is added dropwise to the prepared TiO 2 Spin-coating the substrate of the dense layer at 2000rpm for 20 seconds, placing the substrate on a flat plate furnace for heat treatment, wherein the heat treatment comprises the steps of heating to 125 ℃ at normal temperature for 5 minutes, keeping the temperature for 10 minutes, heating to 250 ℃ for 5 minutes, keeping the temperature for 10 minutes, heating to 350 ℃ for 5 minutes, keeping the temperature for 10 minutes, heating to 450 ℃ for 5 minutes, keeping the temperature for 10 minutes, heating to 500 ℃ for 5 minutes, finishing the heat treatment after keeping the temperature for 20 minutes, cooling to normal temperature, taking out the substrate, and placing the substrate in a glove box for later use.
(3) The perovskite layer 4 is prepared by a one-step method, firstly perovskite precursor solution is prepared, and 1.5mmol of lead iodide and 1.5mmol of CH 3 NH 3 I is added into dimethyl sulfoxide, stirred for 5 hours at 60 ℃ for standby, 60 mu L of perovskite precursor solution is dripped and completely covered on TiO 2 After 12 seconds of spin coating at 2000rpm (acceleration: 200 rpm), 30 seconds of high-speed spin coating at 4000rpm (acceleration: 3000 rpm) was performed, 110. Mu.L of chlorobenzene was dropped at 20 seconds at high speed, and after completion of the spin coating, the substrate was placed on a heating stage and heated at 100 ℃ for 1 hour.
(4) Preparation of the hole transport layer 5 was then carried out by spin coating by dissolving 56.78mg of Spiro-OMeTAD in 0.8mL of chlorobenzene, followed by addition of 14. Mu.L of a LiTFSI solution (520 mg/mL of acetonitrile), 23.2. Mu.L of a Co (III) TFSI solution (300 mg/mL of acetonitrile), and 23.0. Mu.L of tetra-tert-butylpyridine as dopants. And the spin coating of the hole transport layer is to take 30 mu L of solution to be dripped on the perovskite layer, spin coating is carried out at 4000rpm for 30 seconds, and the preparation of the hole transport layer is finished.
(5) The ionic liquid layer 6 was prepared by spin coating by dissolving the ionic liquid 1,3-bis (4-vinylbenzyl) imidazolium chloride (structure shown in fig. 2) in isopropanol at a concentration of 2mg/mL, dropping 30 μ L of the solution onto the hole transport layer, spin coating at 4000rpm for 30 seconds, taking out the glove box after preparation, and heating at 50 ℃ for 10 minutes in air.
(6) Then, redundant parts are respectively wiped off by DMSO and acetonitrile, and the gold electrode is sent into a thermal evaporator to be prepared by thermal evaporation, and the thickness of the gold electrode is about 70 nm.
The J-V curve of the prepared battery is shown in FIG. 3, when the ionic liquid layer is not prepared, the photoelectric efficiency of the battery is 18.15 percent, and the short-circuit current (J) sc ) Open circuit voltage (V) oc ) The Filling Factors (FF) are 22.18mA/cm respectively 2 1.064v,76.9%; after preparation of the upper ionic liquid layer, the cell efficiency was 17.91%, J sc 、V oc FF of 22.09mA/cm respectively 2 1.057v,76.7%, there was no significant reduction, which means that the ionic liquid layer did not affect the charge transport properties of the cell.
When the perovskite solar cell is placed in air, decomposition of the perovskite is caused due to penetration of moisture in the air into the perovskite material. The cell with and without the ionic liquid layer was left in air with a humidity of 40% to 50% as shown in fig. 4 for stability test results in air without any encapsulation of the cell device. A group of J-V curves are tested at intervals to obtain the change of each parameter of the device along with the time, and it can be seen that after 1 month, the energy conversion efficiency of the perovskite solar cell with the ionic liquid layer still keeps 90% of the initial value, while the cell without the ionic liquid layer only keeps 23% of the initial efficiency, which shows that the stability of the device in the air is obviously improved after the ionic liquid is added.
According to the invention, the perovskite solar cell covered by the ionic liquid layer or not is subjected to a water contact angle test, so that the hydrophobic performance of the surface of the device is compared, as shown in fig. 5, the surface contact angle formed by the device covered by the water layer and the ionic liquid layer or not is 64.2 degrees, and the contact angle is raised to 96.3 degrees after the ionic liquid layer is added, which indicates that after the ionic liquid layer is deposited, the formed hydrophobic net structure can protect the perovskite solar cell and prevent water from entering the device, namely the polymerized ionic liquid plays a role of a waterproof layer.
It is to be understood that the described embodiments are merely some embodiments of the invention and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a perovskite solar cell with a waterproof function is characterized by comprising the following steps:
(1) Sequentially preparing each functional layer on a substrate;
(2) Preparing an ionic liquid layer on the outermost functional layer, wherein the ionic liquid layer is made of a functional group with a hydrophobic characteristic as a cation, a C = C double bond is contained at the tail end of a branched chain, and a halogen element ion I is used as an anion of the ionic liquid - 、Br - 、Cl - And F - An ionic liquid of one of (a);
(3) Preparing a metal electrode on the ionic liquid layer to obtain the perovskite solar cell;
the substrate is an FTO glass substrate, in the step (1), part of the substrate is etched firstly, the substrate is divided into an etched area and an unetched area, and then an electron transmission layer, a perovskite absorption layer and a hole transmission layer are sequentially prepared on the etched area and the unetched area;
the FTO glass substrate comprises an FTO transparent conductive layer, and the edge of the ionic liquid layer extends downwards to cover the functional layer and extends to the FTO transparent conductive layer.
2. The method for producing a perovskite solar cell having a waterproof function as claimed in claim 1, wherein in the step (2), the ionic liquid is dispersed in an isopropyl alcohol solution and is produced by a spin coating method to obtain an ionic liquid layer.
3. The method for preparing the perovskite solar cell with the waterproof function as claimed in claim 2, wherein the concentration of the isopropanol solution is 1-5mg/mL, 30-100 microliters of the ionic liquid is dripped when the ionic liquid layer is prepared by the spin coating method, the spin coating speed is 3000-4000 rpm, and the sample is heated in the air at the temperature of 40-50 ℃ after the spin coating is completed.
4. The method for producing the perovskite solar cell having the water-repellent function as claimed in claim 1 or 3, wherein the material of the electron transport layer is TiO 2 ZnO and SnO 2 The electron transport layer is prepared by a sol-gel method, a spray pyrolysis method or a magnetron sputtering method.
5. The method for producing the perovskite solar cell having the water-repellent function as claimed in claim 1 or 3, wherein the material of the perovskite absorption layer is represented by the chemical formula ABX 3 A compound of the form (I) wherein A is Cs, rb, CH 3 NH 3 And CH 2 (NH 2 ) 2 B is Pb, and X is one or two of I or Br; the perovskite absorption layer is prepared by a spin coating method, a thermal evaporation method or a blade coating method.
6. The method for preparing a perovskite solar cell with a waterproof function as claimed in claim 1 or 3, wherein the material of the hole transport layer is a lithium bis (trifluoromethanesulfonyl) imide doped Spiro-OMeTAD, and the hole transport layer is prepared by a spin coating method.
7. The method for producing the perovskite solar cell having the waterproof function as claimed in claim 1 or 3, wherein the metal electrode is a gold electrode, and the metal electrode is produced by a thermal evaporation method.
8. The perovskite solar cell with the waterproof function prepared by the preparation method of the perovskite solar cell with the waterproof function as claimed in any one of claims 1 to 7.
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