A preparation method and battery of multifunctional TCO

Abstract

The present invention provides a method for preparing a multifunctional TCO, comprising: preparing FTO by chemical vapor deposition; using the residual heat in the process of preparing FTO to prepare a nickel oxide layer on the surface of FTO using a nickel source precursor solution; and / or; using the residual heat in the process of preparing FTO to prepare a tin oxide layer on the surface of FTO using a tin source precursor solution. After the present invention adopts the method of preparing FTO in situ, the residual heat in the process of preparing FTO in situ is converted into a heat source for forming a tin oxide / nickel oxide coating by spraying a precursor solution of a tin source or a nickel source, and no separate heating link is set in the process of spraying the precursor solution of the tin source or the nickel source. The photoelectric conversion efficiency of the perovskite solar cell prepared by the multifunctional TCO prepared by the present invention is high, and the photoelectric conversion efficiency of the TCO containing nickel oxide reaches 15%. The present invention provides a battery.

Description

Technical Field

[0001] The invention belongs to the technical field of solar cells, and in particular relates to a preparation method and a battery of a multifunctional TCO. Background Art

[0002] Currently, commonly used photovoltaic substrates are generally made on the basis of transparent electrodes such as FTO through scraping, spraying and other methods. However, in the process of preparing tin oxide or nickel oxide, the existing technology requires separate high-temperature heating, which has high energy consumption, causes energy waste, and prolongs the energy recovery cycle of the entire component. Summary of the invention

[0003] In view of this, an object of the present invention is to provide a method for preparing a multifunctional TCO. The method provided by the present invention has a simple preparation process and low energy consumption, and the prepared multifunctional TCO has good performance.

[0004] The present invention provides a method for preparing a multifunctional TCO, comprising:

[0005] FTO was prepared by chemical vapor deposition;

[0006] Using the waste heat in the process of preparing FTO to prepare a nickel oxide layer on the surface of FTO using a nickel source precursor solution; and / or;

[0007] The residual heat in the process of preparing FTO is used to prepare a tin oxide layer on the surface of FTO using a tin source precursor solution.

[0008] Preferably, the tin source precursor solution comprises: a tin source and a solvent;

[0009] The tin source is selected from one or more of SnCl2, SnCl4, C4H9SnCl3 and SnCl4·5H2O;

[0010] The solvent is selected from one or more of water, ethanol, methanol, n-butanol and isopropanol.

[0011] Preferably, the concentration of the tin source in the tin source precursor solution is 0.01 to 5 mol / L.

[0012] Preferably, the tin source precursor solution also includes doping metal ions;

[0013] The doping metal ion is selected from Li + Mg 2+ 、Al 3+ , Y 3+ , Sb 3+ and Nb 5+ One or more of the .

[0014] Preferably, the concentration of the doping metal ions in the tin source precursor solution is 0.001-0.1 mol / L.

[0015] Preferably, the nickel source precursor solution comprises: a nickel source and a solvent;

[0016] The nickel source is selected from one or more of NiNO3·6H2O, nickel acetate, NiCl2 and NiCl;

[0017] The solvent is selected from one or more of water, ethanol, methanol, n-butanol, isopropanol and ethylene glycol methyl ether.

[0018] Preferably, the concentration of the nickel source in the nickel source precursor solution is 0.01 to 5 mol / L.

[0019] Preferably, the nickel source precursor solution further includes a doping substance, and the doping substance is selected from one or more of cations and non-metals;

[0020] The cation is selected from one or more of alkaline cations and transition metal cations;

[0021] The alkaline cation is selected from K + Mg + , Li + and Na + One or more of the following;

[0022] The transition metal cation is selected from Zn 2+ , Cu + 、Co 2+ 、Al 3+ and Ag + One or more of the following;

[0023] The non-metal is selected from guanidine nitrate.

[0024] Preferably, the concentration of the doping substance in the nickel source precursor solution is 0.001-0.1 mol / L.

[0025] Preferably, the thickness of the nickel oxide layer and the tin oxide layer are independently 5 to 100 nm.

[0026] The present invention provides a battery, comprising: a multifunctional TCO prepared by the method described in the above technical solution.

[0027] The present invention provides a method for preparing a multifunctional TCO. After preparing FTO (fluorine-doped tin oxide) by an in-situ preparation method, a precursor solution of a tin source or a nickel source is sprayed, and residual heat in the in-situ preparation process of the FTO is converted into a heat source for forming a tin oxide / nickel oxide coating. In the process of spraying the precursor solution of the tin source or the nickel source, a separate heating link is no longer provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 These are the transmittance test results of the multifunctional TCO films prepared in Examples 1 to 4 of the present invention. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] The present invention provides a method for preparing a multifunctional TCO (transparent conductive oxide), comprising:

[0031] FTO (fluorine-doped SnO2 conductive glass) was prepared by chemical vapor deposition;

[0032] Using the waste heat in the process of preparing FTO to prepare a nickel oxide layer on the surface of FTO using a nickel source precursor solution; and / or;

[0033] The residual heat in the process of preparing FTO is used to prepare a tin oxide layer on the surface of FTO using a tin source precursor solution.

[0034] In the present invention, the method for preparing FTO by chemical vapor deposition preferably comprises:

[0035] Monobutyltin trichloride is used as a precursor, trifluoroacetic acid is used as a dopant, and air and water are used as the oxidant and catalyst for the reaction. After entering the evaporator, it is vaporized, and then enters the gas mixing chamber for mixing and is sprayed on the surface of the glass through the coater. The mixed gas reacts at the gas-solid interface and is deposited to form a dense FTO solid film.

[0036] In the present invention, the purity of the monobutyltin trichloride is preferably 93-97%, more preferably 94-96%, and most preferably 95%.

[0037] In the present invention, the purity of the trifluoroacetic acid is preferably 98.5-99.5%, more preferably 99%.

[0038] In the present invention, the molar ratio of monobutyltin trichloride, trifluoroacetic acid and water is preferably (1.4-1.8):(0.85-0.95):(4.5-5.5), more preferably (1.5-1.7):(0.86-0.9):(4.6-5), and most preferably 1.6:0.88:4.8.

[0039] In the present invention, the air pressure is preferably 1*10 5 Pa.

[0040] In the present invention, nitrogen is preferably used as a carrier gas to allow the gasified monobutyltin trichloride, trifluoroacetic acid and water to enter the gas mixing chamber for mixing.

[0041] In the present invention, the gasification temperature is preferably 170-180°C, more preferably 173-177°C, and most preferably 175°C.

[0042] In the present invention, the temperature of the glass is preferably 670-680°C, more preferably 673-677°C, and most preferably 675°C.

[0043] In the present invention, the method of utilizing waste heat in the process of preparing FTO preferably comprises:

[0044] The nickel oxide layer and / or the tin oxide layer are prepared on the FTO surface with a certain temperature obtained in the process of preparing FTO.

[0045] In the present invention, it is preferred to use the residual heat of the FTO which has just been prepared and still has a certain temperature to prepare the nickel oxide layer and / or the tin oxide layer.

[0046] In the present invention, the temperature of the FTO having a certain temperature is preferably 540-560°C, more preferably 545-555°C, and most preferably 550°C.

[0047] In the present invention, the temperature of the residual heat (waste heat) is preferably 450 to 650°C, more preferably 500 to 600°C, and most preferably 550°C.

[0048] In the present invention, the temperature for preparing the tin oxide layer and / or the nickel oxide layer is preferably 300-500°C, more preferably 350-450°C, and most preferably 400°C.

[0049] In the present invention, the method for preparing the nickel oxide layer and / or the tin oxide layer preferably comprises: coating, spraying and / or inkjet printing.

[0050] In the present invention, the thickness of the spray coating is preferably 5 to 100 nm, more preferably 10 to 80 nm, more preferably 20 to 60 nm, more preferably 30 to 50 nm, more preferably 40 nm, and most preferably 20 to 30 nm.

[0051] In the present invention, the method for preparing a nickel oxide layer on the FTO surface using a nickel source precursor solution preferably comprises:

[0052] A nickel source precursor solution is used for coating, with nitrogen and oxygen as carrier gases. After entering the evaporator, it is vaporized, then enters the gas mixing chamber for mixing, and is sprayed on the FTO surface with residual heat obtained during the FTO preparation process (just completed) through a coating device.

[0053] In the present invention, the coating is preferably carried out in an oxygen-rich environment; the purity of the nitrogen is preferably 99.5-99.9%, more preferably 99.9%; the purity of the oxygen is preferably 98.5-99.5%, more preferably 99%; the flow ratio of the nitrogen to oxygen is preferably (3-12):1, more preferably (5-11):1, and most preferably 10:1.

[0054] In the present invention, the gasification temperature is preferably 170-180°C, more preferably 173-177°C, and most preferably 175°C.

[0055] In the present invention, the temperature of the FTO with residual heat is preferably 450-550°C, more preferably 480-520°C, and most preferably 500°C.

[0056] In the present invention, the method of preparing a tin oxide layer on the FTO surface using a tin source precursor solution is consistent with the method of preparing a nickel oxide layer on the FTO surface using a nickel source precursor solution described in the above technical solution, the difference being that the nickel source precursor solution is replaced by a tin source precursor solution.

[0057] In the present invention, the tin source precursor solution preferably includes: a tin source and a solvent.

[0058] In the present invention, the tin source is preferably selected from one or more of SnCl2, SnCl4, C4H9SnCl3 and SnCl4·5H2O.

[0059] In the present invention, the solvent is preferably selected from one or more of water, ethanol, methanol, n-butanol and isopropanol.

[0060] In the present invention, the concentration of the tin source in the tin source precursor solution is preferably 0.01-5 mol / L, more preferably 0.05-4 mol / L, more preferably 0.1-3 mol / L, more preferably 0.5-2 mol / L, and most preferably 1-1.5 mol / L.

[0061] In the present invention, the tin source precursor solution preferably further comprises doping metal ions, the doping metal ions are preferably present in the form of hydrochloride and / or nitrate of the doping metal ions, and the doping metal ions are preferably selected from Li + Mg 2+ 、Al 3+ , Y 3+ , Sb 3+ and Nb 5+ One or more of the above; the doped metal ions can perform doping modification on the tin source.

[0062] In the present invention, the tin source precursor solution preferably also includes hydrochloride and / or nitrate doped with metal ions, more preferably Zn(NO3)2.

[0063] In the present invention, the concentration of the doped metal ions in the tin source coating is preferably 0.001-0.1 mol / L, more preferably 0.005-0.08 mol / L, more preferably 0.01-0.06 mol / L, more preferably 0.02-0.05 mol / L, and most preferably 0.03-0.04 mol / L.

[0064] In the present invention, the nickel source precursor solution preferably includes: a nickel source and a solvent.

[0065] In the present invention, the nickel source is preferably selected from one or more of NiNO3·6H2O, nickel acetate (C4H6NiO4), NiCl2 and NiCl.

[0066] In the present invention, the solvent is preferably selected from one or more of water, ethanol, methanol, n-butanol, isopropanol and ethylene glycol methyl ether.

[0067] In the present invention, the concentration of the nickel source in the nickel source precursor solution is preferably 0.01-5 mol / L, more preferably 0.05-4 mol / L, more preferably 0.1-3 mol / L, more preferably 0.5-2 mol / L, and most preferably 1-1.5 mol / L.

[0068] In the present invention, the nickel source precursor solution preferably also includes a doping substance to dope and modify the nickel source. The doping substance is preferably selected from one or more of cations and non-metals; the cation is preferably selected from one or more of alkaline cations and transition metal cations; the alkaline cation is preferably selected from K + Mg + , Li + and Na + One or more of; the transition metal cation is preferably selected from Zn 2+ , Cu + 、Co 2+、Al 3+ and Ag + One or more of; the non-metal is preferably selected from guanidine nitrate.

[0069] In the present invention, the cation preferably exists in the form of cationic nitrate and / or hydrochloride; the nickel source precursor solution preferably also includes cationic nitrate and / or hydrochloride, more preferably one or more selected from KCl, KNO3, NaCl, NaNO3, Zn(NO3)2 and Cu(NO3)2.

[0070] In the present invention, the concentration of the doping substance in the nickel source precursor solution is preferably 0.001-0.1 mol / L, more preferably 0.005-0.08 mol / L, more preferably 0.01-0.06 mol / L, more preferably 0.02-0.05 mol / L, and most preferably 0.03-0.04 mol / L.

[0071] In the present invention, the thickness of the nickel oxide layer and the tin oxide layer is preferably independently 5 to 100 nm, more preferably 10 to 80 nm, more preferably 20 to 60 nm, more preferably 30 to 50 nm, and most preferably 40 nm.

[0072] In the present invention, a nickel oxide layer can be prepared on the FTO surface using a nickel source precursor solution alone, or a tin oxide layer can be prepared on the FTO surface using a tin source precursor solution alone; a nickel oxide layer can be first prepared on the FTO surface using a nickel source precursor solution, and then a tin oxide layer can be prepared on the surface of the nickel oxide layer using a tin source precursor solution; a tin oxide layer can be prepared on the FTO surface using a tin source precursor solution, and then a nickel oxide layer can be prepared on the surface of the tin oxide layer using a nickel source precursor solution.

[0073] The present invention provides a multifunctional TCO prepared by the method described in the above technical solution, wherein the structure of the multifunctional TCO comprises:

[0074] FTO transparent electrode;

[0075] A tin oxide layer and / or a nickel oxide layer is arranged on the surface of the FTO transparent electrode.

[0076] In the present invention, the thickness of the FTO transparent electrode is preferably 400-600 nm, more preferably 450-550 nm, and most preferably 500 nm.

[0077] In the present invention, the thickness of the tin oxide layer is preferably 10 to 50 nm, more preferably 20 to 40 nm, more preferably 25 to 35 nm, and most preferably 30 nm.

[0078] In the present invention, the thickness of the nickel oxide (NiOx nickel oxide is a self-doping compound, x is 2.2 to 3) layer is preferably 10 to 50 nm, more preferably 20 to 40 nm, more preferably 25 to 35 nm, and most preferably 30 nm.

[0079] In the present invention, a nickel oxide layer can be separately provided on the surface of the FTO transparent electrode; a tin oxide layer can also be separately provided on the surface of the FTO transparent electrode; a nickel oxide layer can also be provided on the surface of the FTO transparent electrode, and a tin oxide layer can be provided on the surface of the nickel oxide layer; a tin oxide layer can also be provided on the surface of the FTO transparent electrode, and a nickel oxide layer can be provided on the surface of the tin oxide layer.

[0080] The present invention provides a battery, comprising: a multifunctional TCO prepared by the method described in the above technical solution.

[0081] In the present invention, the battery preferably comprises:

[0082] The multifunctional TCO prepared by the method described in the above technical solution;

[0083] A perovskite light absorbing layer disposed on the surface of the multifunctional TCO;

[0084] An electron transport layer disposed on the surface of the perovskite light absorbing layer;

[0085] An electrode layer is arranged on the surface of the electron transport layer.

[0086] In the present invention, the multifunctional TCO is consistent with the multifunctional TCO described in the above technical solution.

[0087] In the present invention, the structure of the perovskite light-absorbing layer is preferably MAPbI3.

[0088] In the present invention, the thickness of the perovskite light-absorbing layer is preferably 300-600 nm, more preferably 400-500 nm, and most preferably 450 nm.

[0089] In the present invention, the method for preparing the perovskite light absorbing layer preferably comprises:

[0090] preparing a lead film on the surface of the multifunctional TCO;

[0091] The lead film is placed in CVD (chemical vapor deposition), MAI (methylamine iodide) is placed 3 to 10 cm in front of the lead film origin, and I ions are introduced by ventilation, and the gas source pressure is (0.05 to 0.3)*10 5 Pa, and obtain the perovskite light-absorbing layer.

[0092] In the present invention, the thickness of the lead film is preferably 10 to 200 nm, more preferably 30 to 150 nm, more preferably 50 to 100 nm, and most preferably 60 to 80 nm.

[0093] In the present invention, the lead film is preferably prepared by evaporation.

[0094] In the present invention, the temperature during the CVD process is preferably 30-120°C, more preferably 50-100°C, and most preferably 70-80°C; preferably 5-8 cm in front; the gas source pressure is preferably (0.06-0.2)*10 5 Pa, most preferably (0.08~0.1)*10 5 Pa.

[0095] In the present invention, the material of the electron transport layer is preferably C60.

[0096] In the present invention, the thickness of the electron transport layer is preferably 40 to 50 nm, more preferably 42 to 48 nm, and most preferably 44 to 46 nm.

[0097] In the present invention, the electron transport layer is preferably prepared by evaporation; the speed during the evaporation is preferably 0.1-0.5 A / s, more preferably 0.2-0.4 A / s, and most preferably 0.3 A / s.

[0098] In the present invention, the material of the electrode layer is preferably copper, more preferably high-purity copper.

[0099] In the present invention, the thickness of the electrode layer is preferably 80 to 120 nm, more preferably 90 to 110 nm, and most preferably 100 nm.

[0100] In the present invention, the electrode layer is preferably prepared by evaporation; the speed during the evaporation is preferably 0.1 to 1.5 A / s, more preferably 0.3 to 1 A / s, and most preferably 0.3 to 0.5 A / s.

[0101] The multifunctional TCO prepared by the method provided by the present invention has a transparent conductive layer and an N-type / P-type functional layer, which achieves energy level matching with the perovskite core layer and is conducive to large-scale preparation. The prior art uses FTO to directly prepare the perovskite layer, but the energy level is not matched, so that the photoelectric conversion efficiency of the prepared battery is only 3%; the photoelectric conversion efficiency of the perovskite solar cell prepared by the multifunctional TCO prepared by the present invention is relatively high, and the photoelectric conversion efficiency of the TCO containing nickel oxide reaches 15%.

[0102] Example 1

[0103] A multi-channel coater was inserted into the narrow section of the tin bath of the float glass production line. Monobutyltin trichloride (C4H9SnCl3, MBTC) with a purity of 95% (mass fraction, the same below) was used as a precursor, trifluoroacetic acid (CF3COOH, TFA) with a purity of 99% was used as a dopant, and air and water were used as the oxidant and catalyst for the reaction. MBTC, TFA, water and N2 were used as carrier gases. The molar ratio of MBTC, TFA and water was 1.6:0.88:4.8. The air pressure was 1*10 5 Pa; after entering the evaporator, it is vaporized at 175℃; after vaporization, it enters the gas mixing chamber for mixing and is sprayed on the surface of the glass at a temperature of 675℃ through the coater. The mixed gas reacts at the gas-solid phase interface and is deposited to form a dense FTO solid film.

[0104] A 99% pure nickel nitrate isopropanol solution (Ni(NO3)2·6H2O) is used as a precursor solution (1 mol / L), and 99.5% zinc nitrate (Zn(NO3)2) is used as a dopant (the molar ratio of (Zn(NO3)2):(Ni(NO3)2·6H2O) is 100:5). Coating is carried out in an oxygen-rich environment: 99.9% pure N2 and 99% O2 are used as carrier gases at a flow ratio of 10:1. After entering the evaporator, they are vaporized at 175°C. After vaporization, they enter the gas mixing chamber for mixing and are sprayed on the surface of FTO glass (the FTO glass with residual heat obtained in the above preparation process) at a temperature of 450°C through a coater. The mixed gas reacts at the gas-solid interface and is deposited to form a dense nickel oxide solid film.

[0105] The multifunctional TCO prepared in Example 1 of the present invention includes: a FTO solid film with a thickness of 500 nm, and a Zn-doped nickel oxide film with a thickness of 25 nm disposed on the surface of the FTO solid film.

[0106] Example 2

[0107] A multi-channel coater was inserted into the narrow section of the tin bath of the float glass production line. Monobutyltin trichloride (C4H9SnCl3, MBTC) with a purity of 95% (mass fraction, the same below) was used as a precursor, trifluoroacetic acid (CF3COOH, TFA) with a purity of 99% was used as a dopant, and air and water were used as the oxidant and catalyst for the reaction. MBTC, TFA, water and N2 were used as carrier gases. The molar ratio of MBTC, TFA and water was 1.6:0.88:4.8. The air pressure was 1*10 5 Pa; after entering the evaporator, it is vaporized at 175℃; after vaporization, it enters the gas mixing chamber for mixing and is sprayed on the surface of the glass at a temperature of 675℃ through the coater. The mixed gas reacts at the gas-solid phase interface and is deposited to form a dense FTO solid film.

[0108] A 99% pure nickel nitrate isopropanol solution (Ni(NO3)2·6H2O) is used as a precursor solution (1 mol / L) and a 99.5% copper nitrate ((Cu(NO3)2):(Ni(NO3)2·6H2O) molar ratio of 100:5) is used as a dopant, and coating is carried out in an oxygen-rich environment: 99.9% pure N2 and 99% O2 are used as carrier gases at a flow ratio of 5:1, and are vaporized at 175°C after entering the evaporator; after vaporization, they enter the gas mixing chamber for mixing and are sprayed on the surface of FTO glass (the FTO glass with residual heat obtained in the above preparation process) at a temperature of 450°C through a coater, and the mixed gas reacts at the gas-solid interface to deposit and form a dense nickel oxide solid film.

[0109] The multifunctional TCO prepared in Example 2 of the present invention includes: a FTO solid film with a thickness of 500 nm, and a copper-doped nickel oxide film with a thickness of 25 nm disposed on the surface of the FTO solid film.

[0110] Example 3

[0111] A multi-channel coater was inserted into the narrow section of the tin bath of the float glass production line. Monobutyltin trichloride (C4H9SnCl3, MBTC) with a purity of 95% (mass fraction, the same below) was used as a precursor, trifluoroacetic acid (CF3COOH, TFA) with a purity of 99% was used as a dopant, and air and water were used as the oxidant and catalyst for the reaction. MBTC, TFA, water and N2 were used as carrier gases. The molar ratio of MBTC, TFA and water was 1.6:0.88:4.8. The air pressure was 1*10 5 Pa; after entering the evaporator, it is vaporized at 175℃; after vaporization, it enters the gas mixing chamber for mixing and is sprayed on the surface of the glass at a temperature of 675℃ through the coater. The mixed gas reacts at the gas-solid phase interface and is deposited to form a dense FTO solid film.

[0112] The isopropanol solution of nickel nitrate with a purity of 99% (Ni(NO3)2·6H2O) was used as the precursor solution (1 mol / L), and 99.5% copper nitrate ((Cu(NO3)2):(Ni(NO3)2·6H2O) with a molar ratio of 100:5) was used as the dopant, and the coating was carried out in an oxygen-rich environment. 99.9% pure N2 and 99% O2 were used as carrier gases at a flow ratio of 5:1. After entering the evaporator, they were vaporized at 175°C, and then entered the gas mixing chamber for mixing and sprayed on the surface of FTO glass at a temperature of 300°C through the coating device. The mixed gas reacted at the gas-solid interface and deposited to form a dense nickel oxide solid film.

[0113] The multifunctional TCO prepared in Example 3 of the present invention includes: a FTO solid film with a thickness of 500 nm, and a copper-doped nickel oxide film with a thickness of 30 nm disposed on the surface of the FTO solid film.

[0114] Example 4

[0115] A multi-channel coater was inserted into the narrow section of the tin bath of the float glass production line. Monobutyltin trichloride (C4H9SnCl3, MBTC) with a purity of 95% (mass fraction, the same below) was used as a precursor, trifluoroacetic acid (CF3COOH, TFA) with a purity of 99% was used as a dopant, and air and water were used as the oxidant and catalyst for the reaction. MBTC, TFA, water and N2 were used as carrier gases. The molar ratio of MBTC, TFA and water was 1.6:0.88:4.8. The air pressure was 1*10 5 Pa; after entering the evaporator, it is vaporized at 175℃; after vaporization, it enters the gas mixing chamber for mixing and is sprayed on the surface of the glass at a temperature of 675℃ through the coater. The mixed gas reacts at the gas-solid phase interface and is deposited to form a dense FTO solid film.

[0116] The isopropanol solution of nickel nitrate (Ni(NO3)2·6H2O) with a purity of 99% was used as the precursor solution (1mol / L), and zinc nitrate (Zn(NO3)2) with a molar ratio of (Zn(NO3)2): (Ni(NO3)2·6H2O) was 99.5% as the dopant ((Zn(NO3)2): (Ni(NO3)2·6H2O) was 100:5), and the coating was carried out in an oxygen-rich environment. 99.9% pure N2 and 99% O2 were used as carrier gases at a flow ratio of 3:1. After entering the evaporator, they were vaporized at 175°C, and then entered the gas mixing chamber for mixing and sprayed on the surface of FTO glass at a temperature of 450°C through the coating device. The mixed gas reacted at the gas-solid interface and deposited to form a dense nickel oxide solid film.

[0117] The multifunctional TCO prepared in Example 4 of the present invention includes: a FTO solid film with a thickness of 500 nm, and a zinc-doped nickel oxide film with a thickness of 30 nm disposed on the surface of the FTO solid film.

[0118] Example 5

[0119] A perovskite light-absorbing layer was prepared on the surface of the product prepared in Example 1 (Zn-doped nickel oxide film surface): a lead film (thickness of 60 nm) was prepared on the surface of the Zn-doped nickel oxide prepared in Example 1 by evaporation; the prepared lead film was placed in a glass vessel required for CVD, the preparation temperature was 70°C, MAI was placed 5 cm in front of the origin of the Pb film substrate, I ions were introduced by ventilation, and the gas source pressure was 0.08*10 5 Pa, the thickness of the obtained perovskite light-absorbing layer is about 500nm, and the structure is MAPbI3.

[0120] The electron transport layer is prepared by thermal evaporation on the perovskite light-absorbing layer. The material is C60; the evaporation rate is 0.3A / s; and the thickness is about 45nm.

[0121] A metal counter electrode layer is evaporated on the electron transport layer, the material of which is high-purity copper (>99.99%); the evaporation rate is 0.3A / s; the copper film thickness is 100nm, and a battery is obtained.

[0122] Example 6

[0123] A battery was prepared according to the method of Example 5, which differs from Example 5 in that the product prepared in Example 2 was used to replace the product prepared in Example 1.

[0124] Example 7

[0125] A battery was prepared according to the method of Example 5, which differs from Example 5 in that the product prepared in Example 1 was replaced by the product prepared in Example 3.

[0126] Example 8

[0127] A battery was prepared according to the method of Example 5, which differs from Example 5 in that the product prepared in Example 4 was used to replace the product prepared in Example 1.

[0128] Performance Testing

[0129] The optical properties of the multifunctional TCO prepared in Examples 1 to 4 were tested using an Agilent CARY100 UV-Vis spectrophotometer. The test results are as follows: Figure 1 As shown, Figure 1 is the light transmission curve of the multifunctional TCO prepared in the embodiment of the present invention, Figure 1 It can be seen that when the doping method in nickel oxide is changed from Zn doping to Cu doping, the light transmittance in the 300-700nm band has a significant decrease. Therefore, the short-circuit current of the battery prepared by using the TCO prepared under the parameters of Example 2 as the substrate will be restricted. By comparing Example 1 with Example 3, it can be seen that when the temperature is changed, due to the low temperature, the oxidation and phase change temperature are incomplete, so the light transmittance is significantly reduced. By comparing Example 1 with Example 4, it can be seen that due to the excessive oxygen content, part of the nickel oxide layer has been completely oxidized, so its transmittance is significantly reduced.

[0130] The cells prepared in Examples 5 to 8 were placed in simulated standard sunlight (AM 1.5G, 100 mW / cm 2 ), the light intensity was calibrated with a standard reference cell certified by NREL, and the efficiency of the cell was tested using the GB / T 6495.1-1996 standard. The test results are as follows:

[0131] Example 5 Example 6 Example 7 Example 8 Battery efficiency 15％ 13％ 11.8％ 6.4％

[0132] It can be seen from the above embodiments that the present invention provides a method for preparing a multifunctional TCO. After preparing FTO (fluorine-doped tin oxide) by an in-situ preparation method, a precursor solution of a tin source or a nickel source is sprayed, and the residual heat in the in-situ preparation of FTO is converted into a heat source for forming a tin oxide / nickel oxide coating. In the process of spraying the precursor solution of the tin source or the nickel source, a separate heating step is no longer provided.

[0133] Although the present invention has been described and illustrated with reference to specific embodiments of the present invention, these descriptions and illustrations do not limit the present invention. It will be clearly understood by those skilled in the art that various changes may be made without departing from the true spirit and scope of the present invention as defined by the appended claims, so that specific circumstances, materials, material compositions, materials, methods or processes are suitable for the goals, spirit and scope of the present application. All such modifications are intended to be within the scope of the appended claims. Although the methods disclosed herein have been described with reference to specific operations performed in a specific order, it should be understood that these operations may be combined, subdivided or reordered to form equivalent methods without departing from the teachings of the present invention. Therefore, unless specifically indicated herein, the order and grouping of operations are not limitations of the present application.

Claims

1. A method for preparing a multifunctional TCO, comprising: FTO was prepared by chemical vapor deposition; Using the waste heat in the process of preparing FTO, a nickel oxide layer is prepared on the surface of FTO using a nickel source precursor solution; and / or; Using the waste heat in the process of preparing FTO, a tin oxide layer is prepared on the surface of FTO using a tin source precursor solution; The method for preparing FTO by chemical vapor deposition comprises: Monobutyltin trichloride is used as a precursor, trifluoroacetic acid is used as a dopant, and air and water are used as the oxidant and catalyst for the reaction. The film is then vaporized in the evaporator, mixed in the gas mixing chamber, and sprayed on the surface of the glass through the coating device. The mixed gas reacts at the gas-solid interface and is deposited to form a dense FTO solid film. The temperature of the waste heat is 450-650°C.

2. The method according to claim 1, characterized in that The tin source precursor solution comprises: a tin source and a solvent; The tin source is selected from one or more of SnCl2, SnCl4, C4H9SnCl3 and SnCl4·5H2O; The solvent is selected from one or more of water, ethanol, methanol, n-butanol and isopropanol.

3. The method according to claim 2, characterized in that The concentration of the tin source in the tin source precursor solution is 0.01-5 mol / L.

4. The method according to claim 2, characterized in that: The tin source precursor solution also includes doping metal ions; The doping metal ion is selected from Li + Mg 2+ 、Al 3+ , Y 3+ , Sb 3+ and Nb 5+ One or more of the .

5. The method according to claim 4, characterized in that The concentration of the doped metal ions in the tin source precursor solution is 0.001-0.1 mol / L.

6. The method according to claim 1, characterized in that The nickel source precursor solution comprises: a nickel source and a solvent; The nickel source is selected from one or more of NiNO3·6H2O, nickel acetate, NiCl2 and NiCl; The solvent is selected from one or more of water, ethanol, methanol, n-butanol, isopropanol and ethylene glycol methyl ether.

7. The method according to claim 6, characterized in that The concentration of the nickel source in the nickel source precursor solution is 0.01-5 mol / L.

8. The method according to claim 7, characterized in that The nickel source precursor solution also includes a doping substance, and the doping substance is selected from one or more of cations and non-metals; The cation is selected from one or more of alkaline cations and transition metal cations; The alkaline cation is selected from K + Mg + , Li + and Na + One or more of the following; The transition metal cation is selected from Zn 2+ , Cu + 、Co 2+ 、Al 3+ and Ag + One or more of the following; The non-metal is selected from guanidine nitrate.

9. The method according to claim 8, characterized in that The concentration of the doping substance in the nickel source precursor solution is 0.001-0.1 mol / L.

10. A battery comprising: The multifunctional TCO prepared by the method according to claim 1.

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