CN110408009A - It is a kind of for improving the hole transmission layer and preparation method thereof of perovskite solar cell stability - Google Patents

It is a kind of for improving the hole transmission layer and preparation method thereof of perovskite solar cell stability Download PDF

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CN110408009A
CN110408009A CN201910640111.1A CN201910640111A CN110408009A CN 110408009 A CN110408009 A CN 110408009A CN 201910640111 A CN201910640111 A CN 201910640111A CN 110408009 A CN110408009 A CN 110408009A
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fluorine
layer
fluorenes
dibromo
solar cell
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CN110408009B (en
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李坚
贾正
任强
汪称意
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Changzhou University
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Abstract

The invention belongs to technical field of solar batteries, and in particular to a kind of for improving the hole transmission layer and preparation method thereof of perovskite solar cell stability.The present invention has synthesized fluorine-containing triphenylamine copolymer using Suzuki coupling reaction.Fluorine-containing triphenylamine copolymer obtained is dissolved in chlorobenzene, fluorine-containing triphenylamine copolymer solution is obtained, then as hole mobile material, is spin-coated on the active layer calcium titanium ore bed of solar cell device, obtains hole transmission layer, with a thickness of 1~500nm.Compared to common hole transport layer material, hole transport layer material of the invention can significantly improve the stability of titanium ore solar battery.

Description

It is a kind of for improving the hole transmission layer and its system of perovskite solar cell stability Preparation Method
Technical field
The invention belongs to technical field of solar batteries, and in particular to one kind is stablized for improving perovskite solar battery The hole transmission layer and preparation method thereof of property.
Background technique
Since hybrid inorganic-organic perovskite material in 2009 by for the first time be used for photoelectric field since, be based on this kind of material Perovskite solar battery caused huge concern because perovskite solar battery is at low cost, energy conversion effect Rate is higher, completes the leap that other types solar battery decades could complete.Currently, perovskite solar battery passes through Although the development of last decade, photoelectric conversion efficiency make great progress, but the stability of perovskite solar battery, The moisture stability of especially perovskite material is poor, seriously hinders its commercialized step.Therefore, research can improve calcium titanium The material of mine solar cell stability is of great significance.
In order to improve the stability of perovskite solar battery, MichaelEt al. have studied mixed-cation Perovskite system, uses MA+、FA+And Cs+The Cs of meso-hole structure is prepared by a step spin-coating method for three kinds of cationsx (MA0.17FA0.83)(100-x)Pb(I0.83Br0.17)3Perovskite solar cell obtains 21.1% high efficiency, and surveys in stability In examination find battery remained within after 250 hours 18% or so photoelectric conversion efficiency (Michael S, Taisuke M, Ji-Youn S.Energy&Environmental Science,6(2016):1989-1997.).It is by changing perovskite The method of cation in active layer improves the stability of battery.Kijung Yong et al. uses polytetrafluoroethylene (PTFE) hydrophobic material Perovskite material is protected, made device shows good water stability, and test discovery 30 days after, device Still have the 90% of starting efficiency, still, polytetrafluoroethylene (PTFE) hydrophobic material be used as wherein encapsulating material (Passivation) without It is that its stability is improved as a part of perovskite solar battery, there is no fundamentally solve stability problem. (Hwang I,Jeong I,Lee J.ACS Applied Materials&Interfaces,31(2015):17330- 17336.)。
Summary of the invention
The technical problems to be solved by the invention: it provides a kind of for improving the hole of perovskite solar cell stability Transport layer and preparation method thereof.
Fluorine-containing triphenylamine copolymer has been synthesized using Suzuki coupling reaction, and has been applied in perovskite solar battery In hole transmission layer.The fluorine-containing triphenylamine copolymer hole transmission layer can effectively improve perovskite solar cell stability.
The present invention is realized by the following technical solution:
A kind of material that uses of hole transmission layer improving perovskite solar cell stability is fluorine-containing triphen amine copolymer Object, its structural features are as follows:
R in formulaaSelected from hydrogen atom, C1~C4Saturated alkane or unsaturated alkyl, methoxyl group, ethyoxyl, fluorine atom with And one or more of trifluoromethyl；RbSelected from propionic acid hexafluoro butyl ester base, ten difluoro heptyl ester base of propionic acid, ten trifluoro monooctyl ester of propionic acid Base, methylpropanoic acid trifluoro ethyl ester base, methylpropanoic acid hexafluoro butyl ester base, ten difluoro heptyl ester base of methylpropanoic acid and methylpropanoic acid 13 Fluorine monooctyl ester base；X value is 0.01~0.99, and molecular weight is 1000~100000.
Fluorine-containing triphenylamine copolymer provided by the invention prepares perovskite solar cell device as hole transmission layer, system The perovskite solar cell device structure obtained is followed successively by cathode layer, electron transfer layer, perovskite photoactive layer, sky from bottom to top Cave transport layer and anode layer, structure are as follows:
Anode layer
Hole transmission layer
Perovskite photoactive layer
Electron transfer layer
Cathode layer
Wherein, cathode layer is one of the ito glass, FTO glass, AZO glass etched；Electron transfer layer is densification TiO2Material；Perovskite photoactive layer is CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3One of, using solwution method into Row preparation, technique (Anaraki E H, the Kermanpur A, Steier of calcium titanium ore bed are prepared referring to Anaraki et al. L.Energy&Environmental Science, 10 (2016): 3128-3134.)；Anode is silver, gold or the aluminium of vapor deposition.
Wherein, the material that hole transmission layer uses is fluorine-containing triphenylamine copolymer, with a thickness of 1~500nm, preferably 3~ 20nm。
Further, the preparation of fluorine-containing triphenylamine copolymer sequentially includes the following steps:
(1) preparation of the fluorine-containing fluorenes monomer of dibromo:
In the reactor, 2,7- dibromo fluorenes, phase transfer catalyst and solvent is added, under nitrogen atmosphere, injects alkali soluble Liquid reacts 10~60min, then uses ice-water bath, after system temperature is constant, dropwise addition fluorinated acrylate, reaction 10~ 60min is warming up to 15~40 DEG C, and the reaction was continued 5~for 24 hours.After reaction, reaction solution is poured into separatory funnel, is added appropriate Solvent dilution, cleans organic layer repeatedly to water layer clear with saturated salt solution.With anhydrous MgSO4Dry organic layer, filtering, The organic solution of clear is obtained, solvent is evaporated using revolving instrument, is purified through column chromatography, obtains product.
Above-mentioned, phase transfer catalyst is organic quaternary ammonium salt, is chosen in particular from tetramethyl ammonium chloride, two ammonium acetate of the tetrabutyl, first Triethylammonium chloride, tetraethylammonium bromide, tetraethyl ammonium fluoroborate, 4-propyl bromide, tetrabutylammonium chloride, tetrabutyl sulphur Sour hydrogen ammonium, tetrabutylammonium perchlorate, 4-butyl ammonium fluoroborate, tetrabutyl ammonium fluoride, tetrabutylammonium bromide, benzyl trimethyl chlorination One or more of ammonium, cetyl trimethylammonium bromide or benzyltriethylammoinium chloride.Its dosage is 2,7- dibromo fluorenes weight 0.1~10 times of amount.
Solvent is organic solvent, is chosen in particular from toluene, dimethylbenzene, methylene chloride, dichloroethanes, chloroform, ethyl acetate, vinegar One or more of acid butyl ester, benzene, dosage 2,0.1~50 times of 7- dibromo fluorenes weight.
Aqueous slkali is organic or inorganic aqueous slkali, and it is water-soluble to be chosen in particular from the potassium hydroxide that mass fraction is 10%~90% One or more of liquid, sodium hydrate aqueous solution, barium hydroxide, ammonium hydroxide aqueous solution.Its dosage is 2,7- dibromo fluorenes weight The 1%~500% of amount.
Fluorinated acrylate is selected from hexafluorobutyl acrylate, dodecafluorhe-ptylacrylate, perluorooctyl acrylate, propylene Sour perfluoroalkyl ester, acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, methacrylic acid One or more of ten difluoro heptyl esters, ten trifluoro monooctyl ester of methacrylic acid and perfluoroalkyl methacrylate.Its dosage It is 1~50 times of 2,7- dibromo fluorenes molal quantity.
(2) synthesis of fluorine-containing triphenylamine copolymer:
In the reactor, be added the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivatives, catalyst, ligand, weak base with And solvent is heated to 85~95 DEG C under nitrogen atmosphere, after reaction 12~for 24 hours, phenyl boric acid is added and reacts 2~3h, is eventually adding Bromobenzene reacts 2~3h.After reaction, reaction solution is precipitated with anhydrous methanol, filters, dries, resulting crude product It is purified through column chromatography, the reaction mixture of purification is concentrated with revolving instrument, is precipitated again, filtered, dry product.
Above-mentioned, the fluorine-containing fluorenes monomer of dibromo is selected from bromo- 9,9- bis- (the propionic acid hexafluoro butyl ester base) fluorenes of 2,7- bis-, 2,7- bis- bromo- 9, 9- bis- (ten difluoro heptyl ester base of propionic acid) fluorenes, bromo- 9,9- bis- (ten trifluoro monooctyl ester base of the propionic acid) fluorenes of 2,7- bis-, the bromo- 9,9- bis- of 2,7- bis- (methylpropanoic acid trifluoro ethyl ester base) fluorenes, bromo- 9,9- bis- (the methylpropanoic acid hexafluoro butyl ester base) fluorenes of 2,7- bis-, the bromo- 9,9- bis- of 2,7- bis- One of (ten difluoro heptyl ester base of methylpropanoic acid) fluorenes and bromo- 9,9- bis- (ten trifluoro monooctyl ester base of the methylpropanoic acid) fluorenes of 2,7- bis- or It is several.
Diborate object, structural formula are as follows:
Wherein, R2Selected from hydrogen atom, C1~C8Saturated alkane or unsaturated alkyl, methoxyl group, ethyoxyl, fluorine atom And one or more of trifluoromethyl.
Two bromo-derivatives, structural formula are as follows:
Wherein, R3Selected from hydrogen atom, C1~C8Saturated alkane or unsaturated alkyl, methoxyl group, ethyoxyl, fluorine atom And one or more of trifluoromethyl.
Above-mentioned, the molal quantity ratio of the total mole number and diborate object of the fluorine-containing fluorenes monomer of dibromo and two bromo-derivatives is 0.5: 1~1:1.5.The molar ratio of the fluorine-containing fluorenes monomer of dibromo and two bromo-derivatives is 1:100~100:0.
Above-mentioned, catalyst is palladium catalyst, is selected from Pd (OAc)2、PdCl2(dppf) or Pd (PPh3)4One of or It is several；Its dosage is to be with the ratio of the total moles of the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivative these three substances 0.001:1~0.2:1.
Ligand is selected from tricyclohexyl phosphine borofluoride, tripyrrole alkylphosphines, triphenylphosphine, tri-tert-butylphosphine, thricyclohexyl One or more of phosphine or triethylene diamine；The molar ratio of ligand and catalyst is 0.1:1~50:1.
It is water-soluble that weak base is selected from the tetramethylammonium hydroxide aqueous solution that mass fraction is 5%~50%, tetraethyl ammonium hydroxide Liquid, tetrapropylammonium hydroxide solution, tetrabutylammonium hydroxide aqueous solution, four hexyl ammonium hydroxide aqueous solution, four octyl hydrogen-oxygens Change one or more of aqueous ammonium, wet chemical, aqueous sodium carbonate or acetic acid aqueous solutions of potassium；The molal quantity of weak base The ratio of total mole number with the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivative these three substances is 0.1:1~50:1.
Solvent is toluene, dimethylbenzene, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), dimethyl acetamide (DMAc), one or more of N-Methyl pyrrolidone (NMP).
Phenyl boric acid and bromobenzene, dosage are the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivative these three substances The 0.1~1 of total mole number.
For improve perovskite solar cell stability hole transmission layer the preparation method comprises the following steps: fluorine-containing triphenylamine is total to Polymers is dissolved in chlorobenzene, the fluorine-containing triphenylamine copolymer solution that concentration is 0.1mg/mL~50mg/mL is obtained, then by its spin coating On calcium titanium ore bed, hole transmission layer is obtained, with a thickness of 1~500nm.
The utility model has the advantages that
The hole transmission layer and its preparation side that the present invention provides a kind of for improving perovskite solar cell stability Method.Compared to common hole transmission layer, hole transport layer material of the invention can significantly improve titanium ore solar battery and stablize Property.
Detailed description of the invention
Fig. 1 is poly- [4- tert-butyl triphenylamine-co-9,9- two (propionic acid hexafluoro butyl ester) fluorenes] prepared in embodiment 4 Nuclear-magnetism figure；
Fig. 2 is the stability contrast figure of perovskite solar cell device.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than Limitation of the invention further.
Embodiment 1
Fluorine-containing fluorenes monomer, the preparation of 2,7- bis- bromo- 9,9- bis- (propionic acid hexafluoro butyl ester) fluorenes:
After being placed in magnetic stir bar in the 100mL three-necked flask equipped with thermometer, 3.3g (10.2mmol) is sequentially added 2,7- dibromo fluorenes, 0.25g (0.78mmol) tetrabutylammonium bromide and 25mL toluene vacuumize logical nitrogen, keep nitrogen atmosphere, it The potassium hydroxide aqueous solution that 5mL mass fraction is 50% is slowly added dropwise with syringe afterwards.After magnetic agitation about 30min, ice is used 9.676g (41mmol) hexafluorobutyl acrylate is added dropwise with syringe after temperature of reaction system is constant in water-bath.Drip propylene Continue to stir 1h or so after sour hexafluoro butyl ester, is warming up to 25 DEG C of reaction 6h.After reaction, reaction solution is poured into separatory funnel In, add q. s. toluene to dilute, washes liquid separation repeatedly to water layer clear.With anhydrous MgSO4Dry organic layer, filtering obtain Solvent toluene is evaporated by clear transparent solutions using revolving instrument, is purified that (stationary phase is silica gel, and mobile phase is through column chromatography The mixed solvent of methylene chloride and petroleum ether), after revolving brown color product.Its nuclear-magnetism figure is shown in attached drawing 1, yield 41%.
Embodiment 2
Fluorine-containing fluorenes monomer, the preparation of 2,7- bis- bromo- 9,9- bis- (ten difluoro heptyl ester of propionic acid) fluorenes:
After being placed in magnetic stir bar in the 100mL three-necked flask equipped with thermometer, 3.3g (10.2mmol) is sequentially added 2,7- dibromo fluorenes, 0.16g (0.78mmol) tetraethylammonium bromide and 25mL dichloroethanes vacuumize logical nitrogen, keep nitrogen atmosphere It encloses, the sodium hydrate aqueous solution that 5mL mass fraction is 50% is slowly added dropwise with syringe later.After magnetic agitation about 30min, make 15.832g (41mmol) dodecafluorhe-ptylacrylate is added dropwise with syringe after temperature of reaction system is constant with ice-water bath.Drop It adds dodecafluorhe-ptylacrylate to continue to stir 1h or so later, is warming up to 30 DEG C of reaction 8h.After reaction, reaction solution is fallen Enter in separatory funnel, appropriate dichloroethanes is added to dilute, washes liquid separation repeatedly to water layer clear.With anhydrous MgSO4Drying has Machine layer, filtering, obtains the solution of clear, is evaporated organic solvent dichloroethanes using revolving instrument, is mentioned through column chromatography Pure (stationary phase is silica gel, and mobile phase is the mixed solvent of methylene chloride and petroleum ether), after revolving brown color product.Yield 21%.
Embodiment 3
Fluorine-containing fluorenes monomer, the preparation of 2,7- bis- bromo- 9,9- bis- (ten trifluoro monooctyl ester of propionic acid) fluorenes:
After being placed in magnetic stir bar in the 100mL three-necked flask equipped with thermometer, 3.3g (10.2mmol) is sequentially added 2,7- dibromo fluorenes, 0.21g (0.78mmol) 4-propyl bromide and 25mL chloroform vacuumize logical nitrogen, keep nitrogen atmosphere, it The potassium hydroxide aqueous solution that 5mL mass fraction is 50% is slowly added dropwise with syringe afterwards.After magnetic agitation about 30min, ice is used 17.138g (41mmol) perluorooctyl acrylate is added dropwise with syringe after temperature of reaction system is constant in water-bath.It drips Continue to stir 1h or so after perluorooctyl acrylate, is warming up to 30 DEG C of reaction 10h.After reaction, reaction solution is poured into In separatory funnel, appropriate chloroform is added to dilute, washes liquid separation repeatedly to water layer clear.With anhydrous MgSO4Dry organic layer, mistake Filter, obtains clear transparent solutions, is evaporated solvent chloroform using revolving instrument, is purified that (stationary phase is silica gel, stream through column chromatography Dynamic is mutually the mixed solvent of methylene chloride and petroleum ether), after revolving brown color product.Yield 36%.
Embodiment 4
The preparation of [4- tert-butyl triphenylamine-co-9,9- two (propionic acid hexafluoro butyl ester base) fluorenes] copolymer
After being packed into magnetic stir bar in the 100mL flask with thermometer, 0.2767g (0.5mmol) 4 is sequentially added, 4 '-bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-diyl) -4 "-tert-butyl triphenylamine, 0.3981g (0.5mmol) Bromo- 9,9- bis- (the propionic acid hexafluoro butyl ester base) fluorenes of 2,7- bis-, 0.0034g (0.015mmol) Pd (OAc)2、0.0221g (0.06mmol)P(Cy)3, 8mL mass fraction be 25% TEAOH aqueous solution and 8mL toluene, logical nitrogen is vacuumized, at 90 DEG C For 24 hours, solution has weak blue fluorescence appearance, and system is in rufous for lower reaction.Then 0.061g phenyl boric acid is added, reacts 3h, It adds 62 μ L bromobenzenes later to be blocked, the reaction was continued 3h.After reaction, it is down to room temperature to reacting liquid temperature, uses first Alcohol is precipitated, and is then filtered, and drying, products therefrom is purified (stationary phase is silica gel, and mobile phase is toluene) through column chromatography. Gained filtrate will be chromatographed using revolving instrument to be concentrated, methanol extraction is used again later, filters, and drying obtains blush copolymerization Object.Yield is 76%.Its nuclear-magnetism figure is shown in attached drawing 1.
Embodiment 5
The preparation of [4- tert-butyl triphenylamine-co-9,9- two (ten difluoro heptyl ester of propionic acid) fluorenes] copolymer
0.0551g (0.12mmol) 4 is sequentially added in the 100mL three-necked flask equipped with thermometer and magnetic stir bar, Bis- (4,4,5,5- tetramethyl -1,3,2- dioxa the boron of 4 '-two bromo- 4 "-tert-butyl triphenylamines, 0.3320g (0.6mmol) 4,4 ' - Alkane-diyl) -4 "-tert-butyl triphenylamine, 0.5262g (0.48mmol) the bromo- 9,9- bis- (ten difluoro heptyl ester of propionic acid) of 2,7- bis- Fluorenes, 0.004g (0.018mmol) Pd (OAc)2, 0.0134g (0.12mmol) DABCO, 8mL mass fraction be 25% tetraethyl Ammonium hydroxide aqueous solution, 8mL toluene, stir evenly.Vacuumize logical nitrogen, 90 DEG C of reaction 12h of constant temperature.It is eventually adding 0.0732g The phenyl boric acid of (0.6mmol) reacts 3h, continuously adds the bromobenzene reaction 3h of 0.0942g (0.6mmol).After reaction, will Reaction solution is precipitated with anhydrous methanol, is filtered, is dried, and then by crude product purified by silica gel column Chromatographic purification, it is poly- to obtain blush Close object.Yield is 77%.
Embodiment 6
The preparation of [4- trifluoromethyl triphenylamine-co-9,9- two (propionic acid hexafluoro butyl ester) fluorenes] copolymer
After being packed into magnetic stir bar in the 100mL flask with thermometer, 0.2826g (0.5mmol) 4 is sequentially added, 4 '-bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-diyl) -4 "-trifluoromethyl triphenylamine, 0.3981g Bromo- 9,9- bis- (the propionic acid hexafluoro butyl ester base) fluorenes of (0.5mmol) 2,7- bis-, 0.0034g (0.015mmol) Pd (OAc)2、0.0221g (0.06mmol)P(Cy)3, 8mL mass fraction be 25% TEAOH aqueous solution and 8mL toluene, logical nitrogen is vacuumized, at 90 DEG C Lower reaction is for 24 hours.Then 0.061g phenyl boric acid is added, reacts 3h, adds 62 μ L bromobenzenes later and blocked, the reaction was continued 3h.After reaction, it is down to room temperature to reacting liquid temperature, is precipitated with methanol, then filtered, dried, products therefrom is through column Chromatography is purified (stationary phase is silica gel, and mobile phase is toluene).Gained filtrate will be chromatographed using revolving instrument to be concentrated, later Methanol extraction is used again, is filtered, and drying obtains reddish product.Yield is 68%.
Embodiment 7
The preparation of [4- tert-butyl triphenylamine-co-9,9- two (propionic acid hexafluoro butyl ester base) fluorenes (1%)] copolymer
After being packed into magnetic stir bar in the 100mL flask with thermometer, 0.2767g (0.5mmol) 4 is sequentially added, 4 '-bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-diyl) -4 "-tert-butyl triphenylamine, 0.008g (0.01mmol) Bromo- 9,9- bis- (the propionic acid hexafluoro butyl ester base) fluorenes of 2,7- bis-, the bromo- 4 "-tert-butyl triphenylamine of 0.225g (0.49mmol) 4,4 '-two, 0.0034g(0.015mmol)Pd(OAc)2、0.0221g(0.06mmol)P(Cy)3, 8mL mass fraction be 30% tetramethyl hydrogen Aqueous ammonium and 8mLDMF are aoxidized, logical nitrogen is vacuumized, is reacted at 90 DEG C for 24 hours, solution has weak blue fluorescence appearance, and body System is in rufous.Then 0.061g phenyl boric acid is added, reacts 3h, adds 62 μ L bromobenzenes later and blocked, the reaction was continued 3h.After reaction, it is down to room temperature to reacting liquid temperature, is precipitated with methanol, then filtered, dried, products therefrom is through column Chromatography is purified (stationary phase is silica gel, and mobile phase is toluene).Gained filtrate will be chromatographed using revolving instrument to be concentrated, later Methanol extraction is used again, is filtered, and drying obtains blush copolymer.Yield is 85%.
Embodiment 8
The preparation of [4- tert-butyl triphenylamine-co-9,9- two (ten trifluoro monooctyl ester base of propionic acid) fluorenes] copolymer
After being packed into magnetic stir bar in the 100mL flask with thermometer, 0.2767g (0.5mmol) 4 is sequentially added, 4 '-bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-diyl) -4 "-tert-butyl triphenylamine, 0.5641g (0.5mmol) 2,7- bis- bromo- 9,9- bis- (ten trifluoro monooctyl ester base of propionic acid) fluorenes, 0.0034g (0.015mmol) Pd (OAc)2、0.0221g (0.06mmol)P(Cy)3, 8mL mass fraction be 25% TEAOH aqueous solution and 8mL toluene, logical nitrogen is vacuumized, at 90 DEG C For 24 hours, solution has weak blue fluorescence appearance, and system is in rufous for lower reaction.Then 0.061g phenyl boric acid is added, reacts 3h, It adds 62 μ L bromobenzenes later to be blocked, the reaction was continued 3h.After reaction, it is down to room temperature to reacting liquid temperature, uses first Alcohol is precipitated, and is then filtered, and drying, products therefrom is purified (stationary phase is silica gel, and mobile phase is toluene) through column chromatography. Gained filtrate will be chromatographed using revolving instrument to be concentrated, methanol extraction is used again later, filters, and drying obtains blush copolymerization Object.Yield is 80%.
Comparative example 1
The preparation of poly- (4- tert-butyl triphenylamine)
After being packed into magnetic stir bar in the 100mL flask with thermometer, 0.2767g (0.5mmol) 4 is sequentially added, 4 '-bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-diyl) -4 "-tert-butyl triphenylamine, 0.459g (0.5mmol) 4, 4 '-two bromo- 4 "-tert-butyl triphenylamines, 0.0034g (0.015mmol) Pd (OAc)2、0.0221g(0.06mmol)P(Cy)3、8mL The tetramethylammonium hydroxide aqueous solution and 8mLDMF that mass fraction is 30%, vacuumize logical nitrogen, react at 90 DEG C for 24 hours, molten Liquid has weak blue fluorescence appearance, and system is in rufous.Then 0.061g phenyl boric acid is added, reacts 3h, adds 62 μ later L bromobenzene is blocked, the reaction was continued 3h.After reaction, it is down to room temperature to reacting liquid temperature, is precipitated with methanol, so After filter, dry, products therefrom through column chromatography purified (stationary phase is silica gel, and mobile phase is toluene).It will using revolving instrument Chromatography gained filtrate is concentrated, and is used methanol extraction again later, is filtered, and drying obtains yellow copolymer.Yield is 88%.
Embodiment 9
It is sky with [4- tert-butyl triphenylamine-co-9,9- two (propionic acid hexafluoro butyl ester) fluorenes] copolymer synthesized by embodiment 4 Cave transport layer prepares perovskite solar battery:
The FTO electro-conductive glass of 1.5cm × 2.5cm is successively used into detergent, distilled water, acetone, isopropanol and dehydrated alcohol It is cleaned by ultrasonic 30min respectively, removes the impurity of FTO conductive glass surface.After cleaning finishes, dried up using nitrogen, it 15min is cleaned to FTO conductive glass surface using oxygen plasma cleaning machine afterwards, carries out subsequent operation after being disposed.
The FTO electro-conductive glass cleaned up is immersed to the TiCl of 200mM470 DEG C of reaction 1h in aqueous solution, after reaction Sample is taken out, is rinsed well with deionized water and dehydrated alcohol, the TiO adhered on FTO electro-conductive glass is removed2It is water-soluble Liquid is subsequently placed at 100 DEG C of heating 1h in Muffle furnace and is baked to.Perovskite precursor solution is prepared in advance, is then used The technique of 1000rpm 10s, 6000rpm 20s carry out spin coating, and chlorobenzene promotion perovskite crystalline is added dropwise in 5s before the end.Spin coating is complete Finish, 45min that perovskite thin film is annealed on 100 DEG C of heating base station later obtains the perovskite of black bright and dense uniform Film.
It prepares perovskite solar battery hole transmission layer: weighing a certain amount of [4- tert-butyl triphenylamine-co-9,9- two (propionic acid hexafluoro butyl ester) fluorenes] copolymer is dissolved in chlorobenzene, stirs evenly.Configured [the 4- tert-butyl of spin coating on calcium titanium ore bed Triphenylamine-co-9,9- bis- (propionic acid hexafluoro butyl ester) fluorenes] copolymer solution, spin coating proceeding condition is 3000rpm, and spin-coating time is 30s.Au is deposited on the hole transport layer using thermal evaporation, deposition thickness 80nm, evaporation rate isDevice Effective area is 0.07cm2。
Embodiment 10
It is with [4- tert-butyl triphenylamine-co-9,9- two (ten difluoro heptyl ester of propionic acid) fluorenes] copolymer synthesized by embodiment 5 Hole transmission layer prepares perovskite solar battery:
Other are the same as embodiment 9.
Embodiment 11
With [4- tert-butyl triphenylamine-co-9,9- two (ten trifluoro monooctyl ester base of propionic acid) fluorenes] copolymer synthesized by embodiment 8 Perovskite solar battery is prepared for hole transmission layer:
Other are the same as embodiment 9.
Comparative example 2
It is that hole transmission layer prepares perovskite solar battery with [4- tert-butyl triphenylamine] poly- synthesized by comparative example 1:
The FTO electro-conductive glass of 1.5cm × 2.5cm is successively used into detergent, distilled water, acetone, isopropanol and dehydrated alcohol It is cleaned by ultrasonic 30min respectively, removes the impurity of FTO conductive glass surface.After cleaning finishes, dried up using nitrogen, it 15min is cleaned to FTO conductive glass surface using oxygen plasma cleaning machine afterwards, carries out subsequent operation after being disposed.
The FTO electro-conductive glass cleaned up is immersed to the TiCl of 200mM470 DEG C of reaction 1h in aqueous solution, after reaction Sample is taken out, is rinsed well with deionized water and dehydrated alcohol, the TiO adhered on FTO electro-conductive glass is removed2It is water-soluble Liquid is subsequently placed at 100 DEG C of heating 1h in Muffle furnace and is baked to.Perovskite precursor solution is prepared in advance, is then used The technique of 1000rpm 10s, 6000rpm 20s carry out spin coating, and chlorobenzene promotion perovskite crystalline is added dropwise in 5s before the end.Spin coating is complete Finish, 45min that perovskite thin film is annealed on 100 DEG C of heating base station later obtains the perovskite of black bright and dense uniform Film.
Prepare perovskite solar battery hole transmission layer: weigh a certain amount of poly- [4- tert-butyl triphenylamine] is dissolved in chlorine In benzene, stir evenly.Configured poly- [the 4- tert-butyl triphenylamine] solution of spin coating, spin coating proceeding condition are on calcium titanium ore bed 3000rpm, spin-coating time 30s.Au is deposited on the hole transport layer using thermal evaporation, deposition thickness 80nm, evaporation Rate isDevice effective area is 0.07cm2。
Its performance parameter is shown in Table 1, and stability is shown in Fig. 2.
1 perovskite solar cell properties of table
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications done without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (7)

1. a kind of for improving the hole transmission layer of perovskite solar cell stability, it is characterised in that: the hole transport The material that layer uses is fluorine-containing triphenylamine copolymer；
Wherein, fluorine-containing triphenylamine copolymer structure is as follows:
R in formulaaSelected from hydrogen atom, C1~C4Saturated alkane or unsaturated alkyl, methoxyl group, ethyoxyl, fluorine atom and three One or more of methyl fluoride；RbSelected from propionic acid hexafluoro butyl ester base, ten difluoro heptyl ester base of propionic acid, ten trifluoro monooctyl ester base of propionic acid, Methylpropanoic acid trifluoro ethyl ester base, methylpropanoic acid hexafluoro butyl ester base, ten difluoro heptyl ester base of methylpropanoic acid or ten trifluoro of methylpropanoic acid are pungent Ester group；X value is 0.01~0.99；Molecular weight is 1000~100000.
2. as described in claim 1 for improving the hole transmission layer of perovskite solar cell stability, it is characterised in that: Steps are as follows for the preparation method of the fluorine-containing triphenylamine copolymer:
(1) preparation of the fluorine-containing fluorenes monomer of dibromo:
In the reactor, 2,7- dibromo fluorenes, phase transfer catalyst and solvent is added, under nitrogen atmosphere, injects aqueous slkali, instead 10~60min is answered, ice-water bath is then used, after system temperature is constant, fluorinated acrylate is added dropwise, reacts 10~60min, rises Temperature is to 15~40 DEG C, and the reaction was continued 5~for 24 hours, after reaction, reaction solution is poured into separatory funnel, solubilization dilution agent, with full With saline solution cleaning organic layer to water layer clear, with anhydrous MgSO4Dry organic layer, filtering, obtain clear has Solvent is evaporated using revolving instrument, is purified through column chromatography, obtain product by machine solution；
(2) synthesis of fluorine-containing triphenylamine copolymer:
In the reactor, the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivatives, catalyst, ligand, weak base and molten is added Agent is heated to 85~95 DEG C under nitrogen atmosphere, after reaction 12~for 24 hours, phenyl boric acid is added and reacts 2~3h, is eventually adding bromo Reaction solution is precipitated with anhydrous methanol after reaction, filters, dries, resulting crude product is through column by benzene, 2~3h of reaction Chromatography is purified, and the reaction mixture of purification is concentrated with revolving instrument, is precipitated again, is filtered, and product is dried.
3. as claimed in claim 2 for improving the hole transmission layer of perovskite solar cell stability, it is characterised in that: Step (1) phase transfer catalyst be organic quaternary ammonium salt, dosage 2,0.1~10 times of 7- dibromo fluorenes weight；Solvent is Organic solvent, dosage 2,0.1~50 times of 7- dibromo fluorenes weight；Aqueous slkali is organic or inorganic aqueous slkali, and dosage is The 1%~500% of 2,7- dibromo fluorenes weight；Fluorinated acrylate dosage is 1~50 times of 2,7- dibromo fluorenes molal quantity.
4. as claimed in claim 2 for improving the hole transmission layer of perovskite solar cell stability, it is characterised in that: The molal quantity ratio of the total mole number and diborate object of the fluorine-containing fluorenes monomer of step (2) described dibromo and two bromo-derivatives is 0.5:1 ~1:1.5；The molar ratio of the fluorine-containing fluorenes monomer of dibromo and two bromo-derivatives is 1:100~100:0；Catalyst is palladium catalyst, is used Amount for the ratio of the total moles with the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivative these three substances be 0.001:1~ 0.2:1；Ligand is selected from tricyclohexyl phosphine borofluoride, tripyrrole alkylphosphines, triphenylphosphine, tri-tert-butylphosphine, tricyclohexyl phosphine Or one or more of triethylene diamine；The molar ratio of ligand and catalyst is 0.1:1~50:1；The molal quantity of weak base and two The fluorine-containing fluorenes monomer of bromine, diborate object, two bromo-derivative these three substances the ratio of total mole number be 0.1:1~50:1；Benzene boron Acid and bromobenzene, dosage are the total mole number of the fluorine-containing fluorenes monomer of dibromo, diborate object, two bromo-derivative these three substances 0.1~1.
5. a kind of as described in claim 1 for improving the preparation side of the hole transmission layer of perovskite solar cell stability Method, it is characterised in that: the method are as follows: fluorine-containing triphenylamine copolymer is dissolved in chlorobenzene, obtain concentration be 0.1mg/mL~ The fluorine-containing triphenylamine copolymer solution of 50mg/mL, is then spin-coated on calcium titanium ore bed, obtains hole transmission layer, thickness For 1~500nm.
6. a kind of perovskite solar cell device prepared using hole transmission layer as described in claim 1, feature are existed In: the perovskite solar cell device structure is followed successively by cathode layer, electron transfer layer, perovskite photolytic activity from bottom to top Layer, hole transmission layer and anode layer.
7. perovskite solar cell device as claimed in claim 6, it is characterised in that: the cathode layer is to have etched One of ito glass, FTO glass, AZO glass；Electron transfer layer is TiO2, ZnO, fullerene and its derivant material；Calcium Titanium ore photoactive layer is CH3NH3PbI3、CH3NH3PbCl3、CH3NH3PbBr3One of；Hole transport layer material is fluorine-containing three Aniline, with a thickness of 3~20nm；Anode is silver, gold or the aluminium of vapor deposition.
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CN114507336A (en) * 2022-01-18 2022-05-17 常州大学 Fluorine-containing near-infrared absorption conjugated polymer and preparation method thereof
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