CN105895808A - Nanometer aluminum oxide sol coating solution of perovskite solar cell and preparation method - Google Patents

Abstract

The invention relates to a nanometer aluminum oxide sol coating solution of a perovskite solar cell, wherein nanometer Al203 particles with an adjustable particle size are taken as a chief constituent of the sol; the sol is blended with rare earth yttrium and the europium element; an organic silicon coupling agent is applied to further strengthen adhesive form of a film layer; the formed film layer can be firmly adhered on a substrate material without processing of high temperature sintering; ultraviolet light in the solar spectrum can be transformed into visual light; and the particle size of the nanometer Al203 particles is adjusted by that urea in the sol gets resolved slowly to change a solution pH value. A nanometer Al203 blended framework film formed by the invention has a high light transmittance rate and high chemical stability and is an ideal nanometer framework material for a perovskite light-absorption layer.

Description

A kind of perovskite solar cell nanometer alumina sol coating liquid and preparation method

Technical field

The present invention relates to a kind of perovskite solar cell nanometer alumina sol coating liquid and preparation method, particularly a kind of Perovskite solar cell light absorption layer rare-earth yttrium and europium doping nano alumina sol coating liquid and preparation method, the light of formation Absorbed layer framework film requires no high temperature sintering and just can be firmly attached on backing material, it is possible to by the ultraviolet in solar spectrum Light is converted to visible ray, belongs to new forms of energy and field of new.

Technical background

Perovskite solar cell be typically by transparent conducting glass, compacted zone, perovskite light absorbing zone, hole transmission layer, Metal back electrode five part forms.Perovskite light absorbing zone is by perovskite light absorbing material with as the porous nanometer material of skeleton Film is constituted, and the thickness of perovskite light absorbing zone is generally 200-600nm, and Main Function is to absorb sunlight and produce electronics-sky Cave pair, and can high efficiency of transmission electron-hole pair.Although also with or without the perovskite solar cell of framework film, but its opto-electronic conversion effect Rate usually less than has the perovskite solar cell of framework film.Skeleton nano material is except the support bone as perovskite light absorbing material Outside frame, it is also possible to transmission electronics, improve light absorbing material crystalline texture and increase perovskite light absorbing material surface area, thus carrying Rising the photoelectric transformation efficiency of perovskite light absorbing zone, the effect of framework film is studied thoroughly the most completely.Conventional skeleton Film nano material includes nano-TiO₂、Al₂O₃、ZrO₂、SiO₂、ZnO、SnO₂、WO₃、ReO、BaSnO₃、SrTiO₃Deng, wherein, Conventional is nano-TiO₂。

Nano-TiO₂Framework film preparation method mainly has high-temperature sintering process and sol-gel process.High-temperature sintering process is first will Nano-TiO₂Slurry or colloid are coated on matrix, work as nano-TiO₂When particle diameter is relatively big or film layer is thicker, during drying and forming-film often Peeling and film layer obscission occur, needs to process under 500 DEG C of high temperature to make it be sintered to fix on matrix.High-temperature sintering process adds Work cost is high, can not use, limit its range of application on flexible high molecular material substrate.Sol-gel process is to receive Rice TiO₂Colloid is coated on matrix, nano-TiO₂Molecular separating force or binding agent is relied on to be securely attached on matrix surface, can be Film-forming under lower temperature, advantage is to select matrix material relatively flexibly, easily to realize industrialization.

United States Patent (USP) US 2015129034(2015-05-14) and US2015249170(2015-09-03) in use nanometer Al₂O₃Replace nano-TiO₂As the framework film of perovskite light absorbing material, by nanometer Al₂O₃The annealing temperature of framework film It is reduced to less than 150 DEG C.Because nanometer Al₂O₃Replace nano-TiO₂Prevent nano-TiO₂Organic calcium titanium ore light is absorbed material The photocatalysis Decomposition of material, so that light absorbing zone photoelectric transformation efficiency maintains higher level, without high temperature sintering processing procedure, Make it apply on flexible macromolecule substrate perovskite solar cell to be possibly realized, make nanometer Al₂O₃Perforated membrane causes extensively pass Note.

Consider from practical application angle, market demand photoelectric transformation efficiency and stability higher perovskite solar cell light Absorbed layer, especially while can absorb the perovskite solar cell light of the ultraviolet light in solar spectrum and infrared light swing absorption Layer.

Changzhou University's patent of invention CN104538192 (2015-04-22) uses at nano-TiO₂Colloidal sol mixes rare earth Up-conversion erbium (Er) and ytterbium (Yb), prepare rare earth doped nano-TiO₂Framework material, is coated with the most thereon Perovskite light absorbing material, converts infrared light to the function of visible ray because framework material has, and can expand perovskite light and absorb The light absorption range of layer and raising photoelectric transformation efficiency.

Nanometer Al₂O₃Refractive index close with optical glass refractive index, formed framework film light transmittance compare nano-TiO₂Film is saturating Light rate is high, is suitable as perovskite light absorbing zone nano bone frame material.Rare earth mixing with nano Al₂O₃Average particle size 10- 200nm, can realize size tunable by colloidal sol pH and regulate, and the porosity of formation framework film, up to 70%, is that perovskite light absorbs The nano bone frame material that layer is more satisfactory.Use nanometer Al₂O₃Framework material is to improve perovskite light absorbing zone stability and realization Ultraviolet light swing absorption, improves the new way of the photoelectric transformation efficiency of assembled battery.

Summary of the invention

It is an object of the present invention to provide a kind of perovskite solar cell nanometer alumina sol coating liquid, use particle diameter scalable Nanometer Al₂O₃Particle is as colloidal sol key component, rare earth doped yttrium and europium element, and introduces organo-silicon coupling agent and increase further Strong film adhesion is strong, makes the film layer of formation require no high temperature sintering and just can be firmly attached on backing material, it is possible to will Ultraviolet light in solar spectrum is converted to visible ray.

Colloidal sol that perovskite solar battery nano alumina sol of the present invention is hydrolyzed to form by nanometer aluminum isopropylate., rare-earth yttrium and Colloidal sol, organo-silicon coupling agent and the deionized water composition that europium hydrolyzes to form, in colloidal sol, mass percent shared by each component is as follows:

Aluminum isopropylate. 12%-20%

Yttrium trinitrate 0.1%-0.5%

Europium nitrate 0.02%-0.1%

Nitric acid 0.02%-1%

Carbamide 0.4%-1%

Ammonium nitrate 0.1%-0.5%

Organo-silicon coupling agent 0.3%-1%

Deionized water surplus.

Aluminum isopropylate. is as nanometer Al₂O₃Colloidal sol raw material, hydrolysis generates nanometer Al in acid condition₂O₃Colloidal sol, its particle diameter Can be regulated by acid-base value.Nanometer Al that hydrolysis generates₂O₃Colloidal sol is more stable when pH is 3-4, particle diameter at 10-20nm, by In small particle nanometer Al in the basic conditions₂O₃Particle is easily reunited and is grown up, it is possible to slowly decomposed change solution by carbamide The mode of pH controls nanometer Al₂O₃Particle growth, regulating pH value of solution after appropriate particle size to be achieved again is that 3-4 stabilizes it and particle diameter No longer grow up.

Rare-earth yttrium and europium change sensitizer as rare earth light, are entrained in nanometer Al by hydrothermal treatment process₂O₃In particle Form composite Nano colloidal sol；Rare-earth yttrium and europium Nano sol can also be coated with nanometer Al₂O₃Particle, blocks its cohesion and forms colloidal sol Group, thus improve nanometer Al₂O₃Collosol stability.

Organo-silicon coupling agent includes MTES, dimethyldiethoxysilane, organo-silicon coupling agent KH550, organo-silicon coupling agent KH560, organo-silicon coupling agent KH570 or its mixture, it is coated on nanometer as viscosifier Al₂O₃On particle, strengthen nanometer Al₂O₃The particle adhesive force to substrate surface.

Nitric acid is aluminum isopropylate. and organo-silicon coupling agent hydrolyst and colloidal sol acidity regulator.

Carbamide is colloidal sol acidity regulator and nanometer Al₂O₃Size controlling agent.

The salinity that ammonium nitrate produces when being and decompose and regulate hydrosol acidity with carbamide.

Deionized water, as solvent, has the moderate advantage with low cost of volatility.

Raw material aluminum isopropylate., organo-silicon coupling agent MTES, dimethyldiethoxysilane, organosilicon are even Connection agent KH550, organo-silicon coupling agent KH560, organo-silicon coupling agent KH570, nitric acid, carbamide are commercially available chemical reagent.

It is a further object of the present invention to provide the preparation side of a kind of perovskite solar cell nanometer alumina sol coating liquid Method, the technical scheme taked includes nanometer Al₂O₃Prepared by colloidal sol, rare-earth yttrium and europium particle dopen Nano Al₂O₃Prepared by colloidal sol, contain Coupling agent dopen Nano Al₂O₃Prepared by colloidal sol, nanometer Al₂O₃Colloidal sol film, nanometer Al₂O₃Dissolved glue film layer last handling process, specifically Implementing step is:

(1) being separately added into deionized water and nitric acid in glass reactor, making pH value of solution is 1-3, is heated to 70-90 in water-bath ℃；Aluminum isopropylate. is completely dissolved in ethanol, is added drop-wise in solution under being stirred continuously, make aluminum isopropylate. disperse in the solution Be hydrolyzed reaction 8-12h, controls material molar ratio and is: aluminum isopropylate.: deionized water: nitric acid=1:40-80:0.05-0.2, Until aluminum isopropylate. is completely dissolved forms the transparent nano Al that mean diameter is 10nm₂O₃Colloidal sol；

(2) rare earth Yttrium trinitrate and europium nitrate are dissolved in deionized water, be added drop-wise to nanometer Al₂O₃In colloidal sol, stir and make Rare Earth Y³⁺And Eu³⁺Ionic adsorption is in nanometer Al₂O₃Sol particles surface, adds aqueous solution of urea, controls material molar ratio and is: Al₂O₃: Y³⁺: Eu³⁺: carbamide=1: 0.01-0.2: 0.002-0.02: 0.1-0.5, at a reflux temperature hydrothermal treatment consists 8-24h, makes Rare Earth Y³⁺And Eu³⁺Ion enters nanometer Al₂O₃In lattice, make colloidal sol pH rise a height of 5-7 owing to carbamide decomposes, make to receive Rice Al₂O₃Particle constantly condenses and grows up, until colloidal sol produce blue-opalescent be to, obtain rare-earth yttrium that mean diameter is 50nm with Europium dopen Nano Al₂O₃Colloidal sol；

(3) with nitric acid regulation rare-earth yttrium and europium dopen Nano Al₂O₃Colloidal sol pH is 2-3, adds organo-silicon coupling agent at room temperature Being hydrolyzed and polyreaction 8-12 h, controlling material molar ratio is: Al₂O₃: organo-silicon coupling agent: nitric acid=1: 0.01- 0.05: 0.001-0.01, reaction generates the dopen Nano Al containing coupling agent₂O₃Colloidal sol；

(4) with dropper by the dopen Nano Al containing coupling agent₂O₃Colloidal sol drops in the 100mm 100mm fluorine doped dioxy of compacted zone Changing in stannum Conducting Glass, with the coating of bar spreader uniformly, control wet-film thickness 3000-5000 nm, solvent volatilization is dried Rear thicknesses of layers is 200-600nm, cleans film layer with deionized water, then with 110-150 DEG C of hot air drying 30 minutes, makes colloidal sol complete All solidstate, forms surface uniform dopen Nano Al₂O₃Framework film, framework film porosity 40%-70%, attached to substrate material surface Putting forth effort one-level, after being coated in fluorine-doped tin dioxide Conducting Glass, the Uv and visible light of 250-800nm wave-length coverage is saturating The rate of mistake is 81%-85%.

Beneficial effects of the present invention is embodied in:

(1) the dopen Nano Al that the present invention is formed₂O₃Light absorbing zone framework film adhesive force is strong, and requiring no high temperature sintering just can jail Admittedly be attached on backing material；

(2) dopen Nano Al of the present invention₂O₃Ultraviolet light in solar spectrum can be converted to visible ray by framework film, can improve group The photoelectric transformation efficiency of dress perovskite solar cell；

(3) the dopen Nano Al that the present invention uses₂O₃Framework film light transmittance and chemical stability are high, are that preferable perovskite light is inhaled Receive layer nano bone frame material.

Detailed description of the invention

Embodiment 1

It is separately added into deionized water 108g(6mol in the 500mL glass reactor of band stirring) and mass percentage concentration 10% Nitric acid 6.3g(0.01mol), making pH value of solution is 2, is heated to 70-90 DEG C in water-bath；By aluminum isopropylate. 20.4g(0.1mol) complete CL in ethanol, is added drop-wise in solution under being stirred continuously, and makes aluminum isopropylate. dispersion be hydrolyzed in the solution and reacts 8- 12h, until aluminum isopropylate. is completely dissolved forms the transparent nano Al that mean diameter is 10nm₂O₃Colloidal sol.

By rare earth Yttrium trinitrate 3.83g(0.01mol) and europium nitrate 1.69g(0.005mol) dissolve in deionized water, drip It is added to nanometer Al₂O₃In colloidal sol, stir and make Rare Earth Y³⁺And Eu³⁺Ionic adsorption is in nanometer Al₂O₃Sol particles surface, adds Carbamide 2.4g(0.04mol) aqueous solution, hydrothermal treatment consists 8-24h at a reflux temperature, make Rare Earth Y³⁺And Eu³⁺Ion enters and receives Rice Al₂O₃In lattice, make colloidal sol pH rise a height of 6.5 owing to carbamide decomposes, make nanometer Al₂O₃Particle constantly condenses and grows up, until molten Glue produce blue-opalescent be to, obtain rare-earth yttrium and europium dopen Nano Al that mean diameter is 50nm₂O₃Colloidal sol.

With nitric acid regulation rare-earth yttrium and europium dopen Nano Al₂O₃Colloidal sol pH is 3, adds organo-silicon coupling agent methyl three ethoxy Base silane 1.78g(0.01mol) at room temperature it is hydrolyzed and polyreaction 8-12 h, the doping that reaction generates containing coupling agent is received Rice Al₂O₃Colloidal sol.

With dropper by the dopen Nano Al containing coupling agent₂O₃Colloidal sol drops in the 100mm 100mm fluorine doped dioxy of compacted zone Changing in stannum Conducting Glass, with the coating of bar spreader uniformly, control wet-film thickness 3000-5000 nm, solvent volatilization is dried Rear thicknesses of layers is 600nm, cleans film layer with deionized water, then with 110-150 DEG C of hot air drying 30 minutes, makes colloidal sol the most solid Change, form surface uniform dopen Nano Al₂O₃Framework film, framework film porosity 55%, to substrate material surface adhesive force one-level, After being coated in fluorine-doped tin dioxide Conducting Glass, the Uv and visible light transmitance of 250-800nm wave-length coverage is 82%。

Embodiment 2

By PbI₂Reagent 46.1g(100mmol) and CH₃NH₃I reagent 15.9g(100mmol) add 200g dimethylformamide molten In agent, under 60-70 DEG C at stir 12 h, obtain CH₃NH₃PbI₃Light absorbing zone coating fluid.With needle tubing by light absorbing zone coating fluid Drop in nanometer Al of embodiment 1 preparation₂O₃On framework film, with the coating of stainless steel wire rod coating device uniformly, it is placed on vacuum glove box In make solvent volatilization dry, light absorbing zone thickness reaches 500-600nm, and finally with 90-110 DEG C of hot air drying 30 minutes, light is inhaled Receiving layer sheet resistance to reduce rapidly, color is become black by rufous rapidly, forms surface and smooths and cover uniform black calcium Titanium ore light absorbing zone.

Claims (3)

1. a perovskite solar cell nanometer alumina sol coating liquid, is characterized by use adjustable nanometer Al of particle diameter₂O₃ Particle as colloidal sol key component, rare earth doped yttrium and europium element, and introduce organo-silicon coupling agent further enhance film layer attachment Power, makes the film layer of formation require no high temperature sintering and just can be firmly attached on backing material, it is possible to by solar spectrum Ultraviolet light is converted to visible ray, adjustable nanometer Al of described particle diameter₂O₃The particle diameter of particle is slowly to be divided by carbamide in colloidal sol The mode of solution change pH value of solution is carried out, and in colloidal sol, mass percent shared by each component is as follows:

Aluminum isopropylate. 12%-20%

Yttrium trinitrate 0.1%-0.5%

Europium nitrate 0.02%-0.1%

Nitric acid 0.02%-1%

Carbamide 0.4%-1%

Ammonium nitrate 0.1%-0.5%

Organo-silicon coupling agent 0.3%-1%

Deionized water surplus.

2. perovskite solar cell nanometer alumina sol coating liquid as claimed in claim 1, is characterized by that rare-earth yttrium and europium are made Change sensitizer for rare earth light, be entrained in nanometer Al by hydrothermal treatment process₂O₃Particle is formed composite Nano colloidal sol, rare earth Yttrium and europium Nano sol can also be coated with nanometer Al₂O₃Particle, blocks its cohesion and forms colloidal sol group, thus improve nanometer Al₂O₃Molten Glue stability.

3. a preparation method for perovskite solar cell nanometer alumina sol coating liquid, is characterized by the technical scheme taked Including nanometer Al₂O₃Prepared by colloidal sol, rare-earth yttrium and europium dopen Nano Al₂O₃Prepared by colloidal sol, containing coupling agent dopen Nano Al₂O₃Colloidal sol Preparation, nanometer Al₂O₃Colloidal sol film, nanometer Al₂O₃Dissolved glue film layer last handling process, being embodied as step is:

(1) being separately added into deionized water and nitric acid in glass reactor, making pH value of solution is 1-3, is heated to 70-90 in water-bath ℃；Aluminum isopropylate. is completely dissolved in ethanol, is added drop-wise in solution under being stirred continuously, make aluminum isopropylate. disperse in the solution Be hydrolyzed reaction 8-12h, controls material molar ratio and is: aluminum isopropylate.: deionized water: nitric acid=1:40-80:0.05-0.2, Until aluminum isopropylate. is completely dissolved forms the transparent nano Al that mean diameter is 10nm₂O₃Colloidal sol；

(2) rare earth Yttrium trinitrate and europium nitrate are dissolved in deionized water, be added drop-wise to nanometer Al₂O₃In colloidal sol, stirring, it is dilute to make Soil Y³⁺And Eu³⁺Ionic adsorption is in nanometer Al₂O₃Sol particles surface, adds aqueous solution of urea, controls material molar ratio and is: Al₂O₃: Y³⁺: Eu³⁺: carbamide=1: 0.01-0.2: 0.002-0.02: 0.1-0.5, at a reflux temperature hydrothermal treatment consists 8-24h, makes Rare Earth Y³⁺And Eu³⁺Ion enters nanometer Al₂O₃In lattice, make colloidal sol pH rise a height of 5-7 owing to carbamide decomposes, make to receive Rice Al₂O₃Particle constantly condenses and grows up, until colloidal sol produce blue-opalescent be to, obtain rare-earth yttrium that mean diameter is 50nm with Europium dopen Nano Al₂O₃Colloidal sol；

(3) with nitric acid regulation rare-earth yttrium and europium dopen Nano Al₂O₃Colloidal sol pH is 2-3, adds organo-silicon coupling agent and at room temperature enters Row hydrolysis and polyreaction 8-12 h, controlling material molar ratio is: Al₂O₃: organo-silicon coupling agent: nitric acid=1: 0.01-0.05 : 0.001-0.01, reaction generates the dopen Nano Al containing coupling agent₂O₃Colloidal sol；

(4) with dropper by the dopen Nano Al containing coupling agent₂O₃Colloidal sol drops in the 100mm 100mm fluorine doped dioxy of compacted zone Changing in stannum Conducting Glass, with the coating of bar spreader uniformly, control wet-film thickness 3000-5000 nm, solvent volatilization is dried Rear thicknesses of layers is 200-600nm, cleans film layer with deionized water, then with 110-150 DEG C of hot air drying 30 minutes, makes colloidal sol complete All solidstate, forms surface uniform dopen Nano Al₂O₃Framework film, framework film porosity 40%-70%, attached to substrate material surface Putting forth effort one-level, after being coated in fluorine-doped tin dioxide Conducting Glass, the Uv and visible light of 250-800nm wave-length coverage is saturating The rate of mistake is 81%-85%.