CN111106250A - Perovskite solar cell with nano titanium dioxide/polyurethane protective layer - Google Patents
Perovskite solar cell with nano titanium dioxide/polyurethane protective layer Download PDFInfo
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- CN111106250A CN111106250A CN201811271667.XA CN201811271667A CN111106250A CN 111106250 A CN111106250 A CN 111106250A CN 201811271667 A CN201811271667 A CN 201811271667A CN 111106250 A CN111106250 A CN 111106250A
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- Y02E10/00—Energy generation through renewable energy sources
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Abstract
The invention relates to a perovskite solar cell with a nano titanium dioxide/polyurethane protective layer, which comprises: a conductive glass; a hole transport layer on the conductive glass; a perovskite light absorption layer located on the hole transport layer; a nano titanium dioxide/polyurethane layer located on the perovskite light absorption layer; the electron transmission layer is positioned on the nano titanium dioxide/polyurethane layer; a hole blocking layer on the electron transport layer; and the counter electrode is positioned on the hole blocking layer. According to the embodiment of the invention, the nano titanium dioxide/polyurethane layer is prepared on the perovskite light absorption layer to serve as the hydrophobic coating, and the nano titanium dioxide/polyurethane layer has good hydrophobicity and can prevent the perovskite film from contacting with oxygen and water vapor when covering the perovskite light absorption layer, so that the decomposition of the perovskite material is slowed down, the service life of the perovskite solar cell is prolonged, and a foundation is laid for the industrialization of the perovskite solar cell.
Description
Technical Field
The invention belongs to the technical field of photoelectricity, and particularly relates to a perovskite solar cell with a nano titanium dioxide/polyurethane protective layer.
Background
In recent years, the solar cell technology is rapidly developed, and perovskite cells become a type of cells which are in the spotlight, and the device efficiency is rapidly improved from 3.8% in 2009 to 22.7%. The perovskite battery has the advantages of high conversion efficiency, simple preparation, wide material, low cost and the like, and has very wide application prospect.
A solar cell is a device that converts light energy into electric energy using a photovoltaic effect. As a light absorption material of a solar cell, a perovskite material plays a role in absorbing incident light in a device, has a strong absorption band in a visible light region and a near infrared region, and is a necessary condition for realizing high efficiency of the perovskite solar cell. In the perovskite material, the band gap can be regulated and controlled through the components of the constituent elements, so that a more appropriate absorption band gap is obtained. The perovskite battery has low preparation cost and can be prepared by a simple solution method, and is an energy material with great potential and capable of large-scale commercial production.
However, although perovskite materials are easy to synthesize and relatively cheap, perovskite materials are very sensitive to oxygen and humidity, and the crystal structure of the perovskite materials is damaged by oxygen and humidity, so that the service life of a solar cell is influenced, and the industrialization of the perovskite solar cell is severely limited.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a perovskite solar cell having a nano titanium dioxide/polyurethane protective layer. The technical problem to be solved by the invention is realized by the following technical scheme:
the embodiment of the invention provides a perovskite solar cell with a nano titanium dioxide/polyurethane protective layer, which comprises:
a conductive glass;
a hole transport layer on the conductive glass;
a perovskite light absorption layer located on the hole transport layer;
a nano titanium dioxide/polyurethane layer located on the perovskite light absorption layer;
the electron transmission layer is positioned on the nano titanium dioxide/polyurethane layer;
a hole blocking layer on the electron transport layer;
and the counter electrode is positioned on the hole blocking layer.
In one embodiment of the present invention, the thickness of the hole transport layer is 10 to 20 nm.
In one embodiment of the invention, the thickness of the perovskite light absorption layer is 100-300 nm.
In one embodiment of the invention, the perovskite light absorbing layer material is ABX3Wherein A is CH3NH3 +、HC(NH2)2 +、CH3(CH2)nNH3 +(n＝1～7)、C6H5(CH2)nNH3 +(n＝1～4)、Cs+B is Pb2 +、Sn2 +、Cu2 +Is one or more of, X is I-、Br-、Cl-One or more of (a).
In one embodiment of the invention, the thickness of the nano titanium dioxide/polyurethane layer is 5-10 nm.
In one embodiment of the present invention, the polyurethane is silicone-modified polyurethane, wherein the mass fraction of silicone in the silicone-modified polyurethane is 10% to 25%.
In one embodiment of the invention, the thickness of the electron transport layer is 20-50 nm.
In one embodiment of the present invention, the thickness of the hole blocking layer is 4 to 10 nm.
In one embodiment of the present invention, the hole blocking layer material comprises one or more of BCP, TPBi, Alq, LiF, DPVBi.
In one embodiment of the present invention, the counter electrode has a thickness of 100 to 300 nm.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the nano titanium dioxide/polyurethane layer is prepared on the perovskite light absorption layer, and the nano titanium dioxide/polyurethane layer has good hydrophobicity and can prevent the perovskite film from contacting with oxygen and water vapor when covering the perovskite light absorption layer, so that the decomposition of perovskite materials is slowed down, the service life of the perovskite solar cell is prolonged, and a foundation is laid for the industrialization of the perovskite solar cell.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite solar cell with a nano titanium dioxide/polyurethane protective layer according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for manufacturing a perovskite solar cell with a nano titanium dioxide/polyurethane protective layer according to an embodiment of the present invention;
FIG. 3 is a voltage-current density graph of a perovskite solar cell with a nano-titania/polyurethane protective layer prepared according to an example of the present invention;
FIG. 4 is a voltage-current density graph of a perovskite solar cell with a nano titanium dioxide/polyurethane protective layer prepared by the embodiment of the invention after being placed in the atmosphere for 7 d.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
Referring to fig. 1, fig. 1 is a schematic structural diagram of a perovskite solar cell having a nano-titania/polyurethane protective layer according to an embodiment of the present invention, where the perovskite solar cell includes: a conductive glass 1; a hole transport layer 2 on the conductive glass 1; a perovskite light absorption layer 3 positioned on the hole transport layer 2; the nano titanium dioxide/polyurethane layer 4 is positioned on the perovskite light absorption layer 3; the electron transport layer 5 is positioned on the nano titanium dioxide/polyurethane 4; a hole blocking layer 6 on the electron transport layer 5, and a counter electrode 7 on the hole blocking layer 6.
According to the embodiment of the invention, the nano titanium dioxide/polyurethane layer is prepared on the perovskite light absorption layer, and the nano titanium dioxide/polyurethane layer has good hydrophobicity and can prevent the perovskite film from contacting with oxygen and water vapor when covering the perovskite light absorption layer, so that the decomposition of the perovskite material is slowed down, the service life of the perovskite solar cell is prolonged, and a foundation is laid for the industrialization of the perovskite solar cell.
In a specific embodiment, the conductive glass 1 is ITO conductive glass or FTO conductive glass; preferably, the conductive glass 1 is ITO conductive glass. ITO is indium oxide (In)2O390% by mass) and tin oxide (SnO)210 percent of the mixture), the range of the Fermi level is 4.5-5.0 eV, and the mixture has higher carrier concentration and lower resistivity; the transmissivity of the ITO conductive glass can reach more than 80% within the wavelength range of 400-1000 nm.
In one embodiment, the thickness of the hole transport layer 2 is 10-20 nm, and the material of the hole transport layer 2 is PEDOT PSS, CuPc, PT, Cu NiOxOne or more of CuI and CuS, preferably, the thickness of the hole transport layer 2 is 12nm, and the material of the hole transport layer 2 is PEDOT: PSS.
In one embodiment, the thickness of the perovskite light absorption layer 3 is 100-300 nm, and the perovskite light absorption layer material 3 is ABX3Wherein A is CH3NH3 +、HC(NH2)2 +、CH3(CH2)nNH3 +(n＝1～7)、C6H5(CH2)nNH3 +(n＝1～4)、Cs+B is Pb2 +、Sn2 +、Cu2 +Is one or more of, X is I-、Br-、Cl-One or more of (a). For example, the perovskite light absorbing layer 3 material may be CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3(CH2)4NH3PbI3、C6H5(CH2)2NH3PbI3Preferably, the thickness of the perovskite light absorption layer 3 is 200nm, and the material of the perovskite light absorption layer 3 is CH3NH3PbI3。
In a specific embodiment, the thickness of the nano titanium dioxide/polyurethane layer 4 is 5-10 nm, wherein the mass ratio of titanium dioxide to polyurethane is 2: 5-5: 1, preferably 3: 5-4: 5; the particle size of the nano titanium dioxide is 15-30 nm, and the preferable particle size is 20 nm; preferably, the polyurethane is organosilicon modified polyurethane, wherein the organosilicon is polysiloxane with a silicon-oxygen bond (-Si-O-Si-) as a framework, the mass fraction of the organosilicon in the organosilicon modified polyurethane is 10-25%, and preferably, the mass fraction of the organosilicon is 15%.
According to the embodiment of the invention, the nano titanium dioxide/organic silicon modified polyurethane layer is prepared on the perovskite light absorption layer to serve as the hydrophobic coating, the nano titanium dioxide serves as the N-type metal oxide, the nano titanium dioxide has good light transmission in a visible light region, and when the electron transmission layer is fullerene, the conduction band of the titanium dioxide is matched with the energy level of the fullerene, so that the extraction and transmission of electrons are facilitated; the organic silicon modified polyurethane has good hydrophobic property, can protect the perovskite film, prevents the perovskite film from being in direct contact with oxygen and water vapor, slows down the decomposition of perovskite materials, improves the stability of devices, and prolongs the service life of perovskite solar cells.
The titanium dioxide/polyurethane layer of the embodiment of the invention adopts the thickness of 5-10 nm, not only plays a role of protecting the perovskite film, but also ensures the transmission performance of electrons, thereby improving the efficiency of the device; the titanium dioxide and polyurethane with the mass ratio of 3: 5-4: 5 ensure the transmission performance of electrons, so that the titanium dioxide/polyurethane layer fully plays the role of a hydrophobic layer and plays a role in protecting perovskite; the organic silicon modified polyurethane with the mass fraction of 15% is adopted, and the titanium dioxide/polyurethane layer has super-hydrophobicity and strongest protective effect on the perovskite material.
In one embodiment, the thickness of the electron transport layer 5 is 20-50 nm, and the material of the electron transport layer 5 is fullerene, ZnO, Al2O3One or more of (a).
In one embodiment, the thickness of the hole blocking layer 6 is 4-10 nm, and the material of the hole blocking layer 6 comprises one or more of BCP, TPBi, Alq, LiF and DPVBi; preferably, the hole blocking layer material adopts BCP and has the thickness of 6 nm.
According to the embodiment of the invention, the hole blocking layer is prepared on the electron transport layer 5, so that the hole blocking layer has the capability of blocking or slowing down holes, the hole leakage current is reduced, the current carriers in the solar cell are balanced, and the efficiency of the cell is improved; meanwhile, blocked holes are accumulated on the interface of the hole blocking layer, so that the electric field distribution in the device is influenced, and the efficiency of the device is improved.
In one embodiment, the counter electrode 7 has a thickness of 100 to 300 nm; the counter electrode 7 is usually made of metal with lower work function as cathode to improve the electron injection and collection, such as Al, Ga, Mg, Ag, etc., preferably, the cathode material is Ag with a thickness of 120 nm.
According to the embodiment of the invention, the nano titanium dioxide/organic silicon modified polyurethane is used as the hydrophobic coating, so that the extraction and transmission capability of electrons in the device are improved, the stability of the device is improved, and the service life of the perovskite solar cell is prolonged.
Referring to fig. 2, fig. 2 is a schematic flow chart of a method for manufacturing a perovskite solar cell having a nano titanium dioxide/polyurethane protective layer according to an embodiment of the present invention, including the steps of:
s1, cleaning the ITO conductive glass 1: firstly, performing acoustic treatment on ITO conductive glass in tap water, a potassium hydroxide solution, deionized water, alcohol, acetone and isopropanol for 15min in sequence, then drying the ITO conductive glass, and treating the dried conductive glass for 5-10 min under the ultraviolet-ozone condition.
S2, preparing a hole transport layer 2: firstly, preparing a PEDOT/PSS aqueous solution, wherein the volume ratio of the PEDOT to the PSS to water is 1:3, and performing sonication on the PEDOT/PSS aqueous solution for 2 hours to uniformly disperse the PEDOT to the PSS; then 0.5ml of PEDOT is dripped on the ITO conductive glass treated by ozone, PSS aqueous solution is spin-coated, the spin-coating rotating speed is 2000rpm, and the spin-coating time is 15-35 s; then, the substrate is heated for 15-20 min at 120 ℃.
S3, preparing a perovskite light absorption layer 3: putting the substrate in an evaporation machine for evaporation coating of 100-150 nm PbI2The evaporation rate is 0.2nm/s; preparing CH of 40mg/ml in isopropanol3NH3I precursor solution, 200 mul precursor solution is dripped in PbI2Standing for 10s on the film, and spin-coating to obtain CH3NH3I precursor solution and PbI2Fully contacting, wherein the spin-coating speed is 3000rpm, and the spin-coating time is 20 s; annealing the substrate at 60 deg.C for 2h after the spin coating to obtain CH3NH3I and PbI2Fully reacting and fully volatilizing the isopropanol.
S4, preparing a nano titanium dioxide/polyurethane layer 4: preparing isopropanol dispersion liquid of titanium dioxide and organic silicon modified polyurethane, and performing ultrasonic treatment for 30-50 min to uniformly disperse the titanium dioxide and the organic silicon modified polyurethane, wherein the mass ratio of the titanium dioxide to the organic silicon modified polyurethane is 3: 5-4: 5, and w (TiO) in the dispersion liquid2+ PU) is 10 percent, and the content of the organic silicon in the organic silicon modified polyurethane is 15 percent; then, 300 mul of dispersion liquid is dripped on the perovskite light absorption layer for spin coating, the spin coating rotating speed is 4000rpm, and the spin coating time is 30 s; and annealing the substrate at 50 ℃ for 30min after the spin coating is finished, and then annealing at 90 ℃ for 1h to ensure that the titanium dioxide and the organic silicon modified polyurethane fully react and are cured.
S5, preparing an electron transport layer 5: putting the substrate in an evaporator to evaporate 30nm of C60The deposition rate was 0.1 nm/s.
S6, preparing a hole blocking layer 6: c60After the evaporation is finished, closing the evaporator C60And opening the BCP baffle, and continuing to evaporate the BCP with the thickness of 6nm at the evaporation rate of 0.05 nm/s.
S7, preparing the counter electrode 7: the substrate is placed in an evaporation machine for evaporation of 120nm of Ag, and the evaporation rate is 0.2 nm/s.
In the perovskite solar cell preparation method provided by the embodiment of the invention, the adopted thicknesses among the hole transmission layer, the perovskite light absorption layer, the nano titanium dioxide/polyurethane layer, the electron transmission layer and the hole blocking layer enable the energy level matching among the materials to reach a better level, so that current carriers can be transmitted more effectively, and the efficiency of the cell is improved to a certain extent.
The prepared solar cell device is taken out of the vacuum chamber, and the structural schematic diagram thereof is shown in fig. 1.
The voltage-current density of the solar cell device prepared by testing in the atmospheric environment is shown in fig. 3, which is a voltage-current density curve diagram of the perovskite solar cell with the nano titanium dioxide/polyurethane protective layer prepared by the embodiment of the invention, wherein the energy conversion efficiency is 9.1%, the open-circuit voltage is 9.92V, and the short-circuit current is 15.23mA/cm3The fill factor is 64.9%; after the perovskite solar cell is placed in the atmosphere for 7 days, the voltage-current density of the prepared solar cell device is tested in the atmosphere environment, please refer to fig. 4, which is a voltage-current density curve diagram of the perovskite solar cell with the nano titanium dioxide/polyurethane protective layer prepared by the embodiment of the invention in the atmosphere for 7 days, wherein the energy conversion efficiency is 8.9%, the open-circuit voltage is 0.92V, and the short-circuit current is 14.53mA/cm3The filling factor is 67.30%, and the comparison shows that the efficiency is only reduced by 2%, and the nano titanium dioxide/polyurethane layer plays a role in protecting the perovskite film.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A perovskite solar cell having a nano-titania/polyurethane protective layer, comprising:
a conductive glass;
a hole transport layer on the conductive glass;
a perovskite light absorption layer located on the hole transport layer;
a nano titanium dioxide/polyurethane layer located on the perovskite light absorption layer;
the electron transmission layer is positioned on the nano titanium dioxide/polyurethane layer;
a hole blocking layer on the electron transport layer;
and the counter electrode is positioned on the hole blocking layer.
2. The perovskite solar cell with the nano titanium dioxide/polyurethane protective layer according to claim 1, wherein the hole transport layer has a thickness of 10 to 20 nm.
3. The perovskite solar cell with the nano-titania/polyurethane protective layer of claim 1, wherein the thickness of the perovskite light absorption layer is 100-300 nm.
4. The perovskite solar cell with the nano-titania/polyurethane protective layer of claim 1, wherein the perovskite light absorption layer material is ABX3Wherein A is CH3NH3 +、HC(NH2)2 +、CH3(CH2)nNH3 +(n＝1～7)、C6H5(CH2)nNH3 +(n＝1～4)、Cs+B is Pb2 +、Sn2 +、Cu2 +Is one or more of, X is I-、Br-、Cl-One or more of (a).
5. The perovskite solar cell with the nano titanium dioxide/polyurethane protective layer according to claim 1, wherein the thickness of the nano titanium dioxide/polyurethane layer is 5-10 nm.
6. The perovskite solar cell with the nano titanium dioxide/polyurethane protective layer according to claim 1, wherein the polyurethane is an organosilicon-modified polyurethane, wherein the mass fraction of organosilicon in the organosilicon-modified polyurethane is 10% to 25%.
7. The perovskite solar cell with the nano titanium dioxide/polyurethane protective layer according to claim 1, wherein the thickness of the electron transport layer is 20-50 nm.
8. The perovskite solar cell with the nano titanium dioxide/polyurethane protective layer according to claim 1, wherein the hole blocking layer has a thickness of 4 to 10 nm.
9. The perovskite solar cell with the nano-titania/polyurethane protective layer of claim 1, wherein the hole blocking layer material comprises one or more of BCP, TPBi, Alq, LiF, DPVBi.
10. The perovskite solar cell with the nano titanium dioxide/polyurethane protective layer according to claim 1, wherein the counter electrode has a thickness of 100 to 300 nm.
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