CN108461633A - A kind of hybrid and preparation method thereof for perovskite solar cell electron transfer layer - Google Patents
A kind of hybrid and preparation method thereof for perovskite solar cell electron transfer layer Download PDFInfo
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- CN108461633A CN108461633A CN201810203763.4A CN201810203763A CN108461633A CN 108461633 A CN108461633 A CN 108461633A CN 201810203763 A CN201810203763 A CN 201810203763A CN 108461633 A CN108461633 A CN 108461633A
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- solar cell
- electron transfer
- transfer layer
- acid
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Classifications
-
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Abstract
The present invention relates to a kind of perovskite solar cell electron transfer layer and preparation method thereof can be used for low temperature preparation, the present invention prepares nano titania dispersion liquid using solvent-thermal method, and by TiO2Nano dispersion fluid and Alcohol-soluble conjugate polymer are compound, prepare conjugated polymer/TiO2Hybrid material finally uses spin-coating method by conjugated polymer/TiO2Hybrid material is spin-coated in the ito glass substrate of plasma treated mistake, and conjugated polymer/TiO is made2Hybrid film, as electron transfer layer.The beneficial effects of the invention are as follows：Side chain provided by the present invention contains the preparation method of carboxyl or sulfonic alcohol/soluble conjugated polymer；And provide one kind can low temperature preparation (≤100 DEG C) the hybrid material and preparation method thereof for perovskite solar cell electron transfer layer.
Description
Technical field
The present invention relates to technical field of solar batteries, more particularly to it is a kind of can low temperature preparation perovskite solar cell
Electron transfer layer and preparation method thereof.
Background technology
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 cell caused huge concern because perovskite solar cell is at low cost, energy conversion effect
Rate is higher.Perovskite solar cell is divided into two kinds of structures, respectively mesoscopic structure and plane heterojunction structure.Earliest calcium titanium
Mine solar battery structure be mesoscopic structure, later research find perovskite material have longer carrier diffusion length and compared with
Long carrier lifetime, thus perovskite material can be used in the perovskite solar cell of planar heterojunction structure.Study table
It is bright, with TiO2Planar heterojunction perovskite solar cell as cathode buffer layer is easier to prepare, and can also obtain higher
Energy conversion efficiency (PCE).But the fine and close Detitanium-ore-type TiO of high quality2Layer needs the high-temperature process by 450 DEG C or more,
In terms of so extreme treatment conditions can limit the flexibility of the development in perovskite solar cell future, especially device.Cause
This, the method that high performance calcium titanium ore solar cell is prepared in exploration under cryogenic is most important.
Patent CN106384784A and patent CN106299141A describes a kind of calcium titanium of composite electron transport layer structure
Mine solar cell and its manufacturing method, in preparation process, the spin coating SnO on conductive glass layer2Compacted zone, then in Muffle furnace
In 180 DEG C calcining 1h, be compared to 400 DEG C of N-type metal oxide forming temperature and decrease, but consume energy it is still very high, it is unfavorable
In commercialization.Patent CN106449982A describe it is a kind of using chromium oxide as the perovskite solar cell of electron transfer layer and its
Preparation method, in preparation process, the first electron transfer layer of first spin coating, then hot evaporation or sputtering the second electron transfer layer of chromium oxide,
Although preparation process can reach 150 DEG C hereinafter, but still energy consumption is high, and complex steps.Patent CN106449988A describes one
The perovskite solar cell of kind of super-thin electronic transport layer structure, in preparation process, electron transfer layer is using dip coating by FTO
Glass is immersed in prepared titanium tetrachloride aqueous solution, and environment temperature needs to control, at 70 DEG C, to be also needed to later 150
It is dried at DEG C, required condition is harsh, and complex steps.Patent CN106711333A describes a kind of perovskite solar cell gradually
The preparation method for becoming hetero-junctions electron transfer layer, in preparation process, successively the tin source precursor solution at 70 DEG C and titanium source forerunner
40min is respectively reacted in liquid solution, 30min is finally calcined at 500 DEG C, and this method condition is harsh, and step is quite cumbersome, and calcines
Temperature is high.
The present invention prepares nano titania dispersion liquid using solvent-thermal method, and by TiO2Nano dispersion fluid is total with alcohol-soluble
Conjugated polymer is compound, prepares conjugated polymer/TiO2Hybrid material finally uses spin-coating method by conjugated polymer/TiO2Hydridization
Material is spin-coated in the ito glass substrate of plasma treated mistake, and conjugated polymer/TiO is made2Hybrid film, as electronics
Transport layer.This method with it has been reported that method compared with, the electron transfer layer of perovskite solar cell can be realized in low temperature
Preparation under the conditions of (≤100 DEG C), and operating method is simple.
Invention content
The technical problems to be solved by the invention：It provides a kind of for low temperature preparation perovskite solar cell electron-transport
Layer and preparation method thereof.
The present invention is realized by the following technical solution：
One kind being used for perovskite solar cell electron transfer layer hybrid, it is characterised in that：It is poly- by alcohol/soluble conjugated
Close object and nano-TiO2The hybrid material of formation.
Wherein, conjugated polymer structural formula is as follows：
R in formulaaFor hydrogen atom or C1~C12Saturated alkane or unsaturated alkyl；RbSelected from propionyloxy, methylpropanoic acid
Base or 3- propyl amides -2- methyl propane sulfonic acid sodium；X values are 0.00~0.99.
Wherein, conjugated polymer and TiO2Mass ratio is 1:100~100:1.
A kind of alcohol/soluble conjugated polymer/TiO2Hybrid material film, preparation method includes the following steps：
(1) synthesis of water/Alcohol-soluble conjugate polymer：
In the reactor, dibromo fluorenes monomer, the diborate object of A1, two bromo-derivatives of A2, catalyst, ligand, weak is added
Alkali and solvent are heated to 85~95 DEG C under nitrogen atmosphere, after reaction 12~for 24 hours, phenyl boric acid are added and reacts 2~3h, finally
Bromobenzene is added, reacts 2~3h.After reaction, by reaction solution pour into acidification after deionized water in precipitate, filtering,
Drying, the product of gained are purified through column chromatography, the reaction mixture of purification are concentrated with revolving instrument, is precipitated again, mistake
Product is dried in filter.
Further, dibromo fluorenes monomer is selected from bis- (propionyloxy) fluorenes of 2,7-, bis- bromo- 9,9-, bis- (the 2- first of 2,7-, bis- bromo- 9,9-
Base -3- propionyloxies) fluorenes, one or more of 2,7- bis- bromo- 9,9- bis- (3- propyl amides -2- methyl propane sulfonic acids sodium) fluorenes.
Further, A1 is diborate object, and structural formula is：
Wherein, R2For hydrogen atom or C1~C12Saturated alkane or unsaturated alkyl.
Further, A2 is two bromo-derivatives, and structural formula is：
Wherein, R2For hydrogen atom or C1~C12Saturated alkane or unsaturated alkyl.
Further, the mole ratio of the diborate object of the total mole number and A1 of two bromo-derivatives of dibromo fluorenes monomer and A2
Example is 0.5:1~1:1.5.The ratio of two bromo-derivatives of dibromo fluorenes monomer and A2 is 1:100~100:1.
Further, catalyst is palladium catalyst, is selected from Pd (OAc)2、PdCl2(dppf) or Pd (PPh3)4In one
Kind is several；Its molal quantity and dibromo fluorenes monomer, the diborate object of A1, A2 two bromo-derivative these three substances total moles
Ratio is 0.001:1~0.06:1.
Further, ligand be selected from tricyclohexyl phosphine borofluoride, tripyrrole alkylphosphines, triphenylphosphine, tri-tert-butylphosphine,
One or more of tricyclohexyl phosphine or triethylene diamine；The molar ratio of ligand and catalyst is 1:1~12:1.
Further, weak base is selected from tetramethylammonium hydroxide aqueous solution, the tetraethyl hydrogen-oxygen that mass fraction is 5%~50%
Change aqueous ammonium, tetrapropylammonium hydroxide solution, tetrabutylammonium hydroxide aqueous solution, four hexyl ammonium hydroxide aqueous solution, four
One or more of octyl ammonium hydroxide aqueous solution, wet chemical, aqueous sodium carbonate or acetic acid aqueous solutions of potassium；Weak base
Molal quantity and dibromo fluorenes monomer, the diborate object of A1, A2 the ratios of total mole number of two bromo-derivative these three substances be
1:1~12:1.
Further, solvent is toluene, dimethylbenzene, dimethyl sulfoxide (DMSO) (DMSO), n,N-Dimethylformamide (DMF), two
One or more of methylacetamide (DMAc), N-Methyl pyrrolidone (NMP).
Further, phenyl boric acid and bromobenzene, dosage are two bromos of dibromo fluorenes monomer, the diborate object of A1, A2
The 0.5~1 of the total mole number of these three substances of object.
(2)TiO2The preparation of nano dispersion fluid：
Solvent S, titanate esters and suitable acid are mixed in beaker, solution A is obtained after 10~20min of magnetic agitation.Separately
It takes solvent S and deionized water to be mixed in beaker, obtains solution B.Solution B is slowly dropped under conditions of magnetic agitation molten
In liquid A, continue 20~30min of stirring after being added dropwise, obtains translucent TiO2Colloidal sol.Finally by TiO2In colloidal sol pours into
In the stainless steel cauldron of lining teflon, 5~8h of reaction in 140~160 DEG C of baking oven is put into after reaction kettle is sealed, instead
It is cooled to room temperature after answering to get to translucent TiO2Nano dispersion fluid, average grain diameter≤150nm.
Further, solvent S be selected from methanol, ethyl alcohol, ethylene glycol, propylene glycol, glycerine, isopropanol, butanol, amylalcohol and
One or more of hexanol；
Further, titanate esters are selected from tetraethyl titanate, butyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, metatitanic acid
One or more of four different monooctyl esters and metatitanic acid four (octadecyl) ester；
Further, acid is selected from one or more of glacial acetic acid, hydrochloric acid, sulfuric acid, nitric acid and carbonic acid；
Further, the volume ratio of the acid used in solution A and solution B and titanate esters is 1:1~1:20；Acid and water
Volume ratio is 1:1~1:5；
Further, prepared TiO2A concentration of 3mg/mL~40mg/mL of nano dispersion fluid.
(3) conjugated polymer/TiO2The preparation of hybrid electron transport layer：
TiO prepared by step (2)2Nano dispersion fluid is placed on filter filtering in vial.Then weigh step
(1) alcohol/soluble conjugated polymer prepared is dissolved in solvent, is filtered with filter after object to be polymerized dissolving completely, and by filtrate
With TiO2Nano dispersion fluid is mixed, and stable, translucent conjugation is obtained after the sonicated 10~15min of blended liquid
Polymer/TiO2Hydridization dispersion liquid.By obtained conjugated polymer/TiO2Hydridization dispersion liquid be spin-coated on it is plasma treated after
Substrate of glass on, obtain conjugated polymer/TiO2Hybrid material film, it is finally that hybridized film is dry in 100 DEG C of baking oven
.
Further, conjugated polymer and TiO2Mass ratio is 1:100~100:1；
Further, organic solvent is selected from methanol, ethyl alcohol, ethylene glycol, propylene glycol, glycerine, isopropanol, butanol, the third two
One or more of alcohol methyl ether and ethylene glycol monomethyl ether.
One kind is by above-mentioned conjugated polymer/TiO2The perovskite solar cell device that hybrid material is prepared, it is described
Perovskite solar cell device structure is followed successively by cathode layer, electron transfer layer, perovskite active layer, hole transport from down to up
Layer and anode layer, structural representation are as follows：
| Ag |
| Hole transmission layer |
| MAPbI3 |
| Electron transfer layer |
| Ito glass |
Wherein, cathode layer is the ito glass etched or FTO glass.
Wherein, electron transfer layer is conjugated polymer/TiO2Hybrid material film.
Wherein, using rotation successive soln sedimentation, (air humidity is less than perovskite photoactive layer in air environment
40%) it is prepared.
Wherein, hole transmission layer be poly- 3- hexyl thiophenes (P3HT) or thiophene derivants or small molecule containing thiophene, it is poly-
The homopolymer or copolymerization of the homopolymer or copolymer or triphen amine derivant of triphenylamine or small molecule, polycarbazole containing triphenylamine
Object or carbazole analog derivative or the small molecule containing carbazole, spiro-OMeTAD, phthalocyanine-like compound.
Wherein, anode is silver, gold or the aluminium of vapor deposition.
The present invention has the following advantages and beneficial effects：
Side chain provided by the present invention contains the preparation method of carboxyl or sulfonic alcohol/soluble conjugated polymer；And
And provide one kind can low temperature preparation (≤100 DEG C) for perovskite solar cell electron transfer layer hybrid material and its
Preparation method.
Specific implementation mode
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：
The preparation of conjugated polymer poly- [bis- (propionyloxy) fluorenes of 9,9- dioctyl fluorenes-co-9,9-]：
0.2808g (0.6mmol) 2,7- is sequentially added in the 100mL three-necked flasks equipped with thermometer and magnetic stirrer
Bis- (propionyloxy) fluorenes of two bromo- 9,9-, the bis- (4,4,5,5- tetramethyl -1,3,2- dioxaborinates-of 0.3852g (0.6mmol) 2,7-
Diyl) -9,9- dioctyl fluorenes, 0.004g (0.018mmol) Pd (OAc)2, 0.0134g (0.12mmol) DABCO, 8mL mass
Tetraethyl ammonium hydroxide aqueous solution, 5mL DMSO and 5mL toluene of the score for 25%, stir evenly, heat under nitrogen atmosphere
To 90 DEG C of reaction 12h.0.0732g (0.6mmol) phenyl boric acid is added later and reacts 3h, adds 0.0942g (0.6 mmol) bromine
3h is reacted for benzene.After reaction, reaction solution is poured into the deionized water after 200mL is acidified and is precipitated, filtered, dry,
The product of gained is purified (stationary phase is neutral alumina, mobile phase THF) through column chromatography, is finally obtained containing 50% carboxylic acid
The yellow polymer of fluorene structural units, yield 45%.Its nuclear-magnetism figure is shown in attached drawing 1, and poly- [9,9- dioctyl fluorene-co-9,9- are bis-
(propionyloxy) fluorenes] nuclear-magnetism figure.By gpc analysis, it is 19600 to measure its number-average molecular weight, weight average molecular weight 35000, point
Son amount is distributed as 1.79.
Embodiment 2：
The preparation of conjugated polymer poly- [bis- (2- methyl -3- propionyloxies) fluorenes of 9,9- dihexyl fluorenes-co-9,9-]：
0.2371g (0.48mmol) 2 is sequentially added in the 100mL three-necked flasks equipped with thermometer and magnetic stirrer,
Bis- (2- methyl -3- propionyloxies) fluorenes of bis- bromo- 9,9- of 7-, bis- bromo- 9,9- dihexyls fluorenes of 0.0588g (0.12mmol) 2,7-,
Bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-the diyl) -9,9- dihexyls fluorenes of 0.3518g (0.6 mmol) 2,7-,
0.004g(0.018mmol) Pd(OAc)2, 0.0134g (0.12mmol) DABCO, 8mL mass fraction be 25% tetraethyl hydrogen
Aqueous ammonium, 5mL DMSO and 5mL toluene are aoxidized, is stirred evenly, is heated to 90 DEG C of reaction 12h under nitrogen atmosphere.Later plus
Enter 0.0732 g (0.6mmol) phenyl boric acid reaction 3h, adds 0.0942g (0.6mmol) bromobenzene reaction 3h.Reaction terminates
Afterwards, will be precipitated in deionized water that reaction solution pours into after 200mL acidifications, filter, dry, the product of gained through column chromatography into
Row purification (stationary phase is neutral alumina, mobile phase THF), finally obtains the polymer containing 40% carboxylic acid fluorene structural units.
Embodiment 3：
The preparation of conjugated polymer poly- [bis- (2- methyl -3- propionyloxies) fluorenes of 9,9- dioctyl fluorenes-co-9,9-]：
0.1778g (0.36mmol) 2 is sequentially added in the 100mL three-necked flasks equipped with thermometer and magnetic stirrer,
Bis- (2- methyl -3- propionyloxies) fluorenes of bis- bromo- 9,9- of 7-, bis- bromo- 9,9- dioctyl fluorenes of 0.1316g (0.24mmol) 2,7-,
Bis- (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-the diyl) -9,9- dioctyl fluorenes of 0.3852g (0.6 mmol) 2,7-,
0.004g(0.018mmol) Pd(OAc)2, 0.0134g (0.12mmol) DABCO, 8mL mass fraction be 25% tetraethyl hydrogen
Aqueous ammonium, 5mL DMSO and 5mL toluene are aoxidized, is stirred evenly, is heated to 90 DEG C of reaction 12h under nitrogen atmosphere.Later plus
Enter 0.0732 g (0.6mmol) phenyl boric acid reaction 3h, adds 0.0942g (0.6mmol) bromobenzene reaction 3h.Reaction terminates
Afterwards, will be precipitated in deionized water that reaction solution pours into after 200mL acidifications, filter, dry, the product of gained through column chromatography into
Row purification (stationary phase is neutral alumina, mobile phase THF), finally obtains the polymer containing 30% carboxylic acid fluorene structural units.
Embodiment 4：
Content is the TiO of 3mg/mL2The preparation of nano dispersion fluid：
Nano titania dispersion liquid is prepared using solvent-thermal method.25mL anhydrous isopropyl alcohols, 0.5mL metatitanic acids are taken at room temperature
Orthocarbonate and 0.05mL nitric acid mix in the beaker of 50mL, and solution A is obtained after magnetic agitation 10min.Separately take the anhydrous isopropyls of 5mL
Alcohol and 0.15mL deionized waters mix in the beaker of 10mL, and solution B is obtained after being ultrasonically treated 5min.In the condition of magnetic agitation
It is lower that solution B is slowly dropped in solution A, continue to stir 20min after being added dropwise, obtains translucent TiO2Colloidal sol.Most
Afterwards by TiO2Colloidal sol pours into the stainless steel cauldron of inner liner polytetrafluoroethylene, and 150 DEG C of baking oven is put into after reaction kettle is sealed
Middle reaction 6h is cooled to room temperature after reaction to get to translucent TiO2Nano dispersion fluid.By the test of solid content,
TiO in dispersion liquid2Content be 3mg/mL.It is detected by laser particle analyzer, average grain diameter 71nm, particle diameter distribution is
0.258。
Embodiment 5：
Content is the TiO of 30mg/mL2The preparation of nano dispersion fluid：
Nano titania dispersion liquid is prepared using solvent-thermal method.25mL absolute methanols, four fourth of 4mL metatitanic acids are taken at room temperature
Ester and 0.4mL glacial acetic acid mix in the beaker of 50mL, and solution A is obtained after magnetic agitation 10min.It is another take 5mL absolute methanols and
1.3mL deionized waters mix in the beaker of 10mL, and solution B is obtained after being ultrasonically treated 5min.It will under conditions of magnetic agitation
Solution B is slowly dropped in solution A, is continued to stir 20min after being added dropwise, is obtained translucent TiO2Colloidal sol.Finally will
TiO2Colloidal sol pours into the stainless steel cauldron of inner liner polytetrafluoroethylene, is put into after reaction kettle is sealed in 150 DEG C of baking oven anti-
6h is answered, is cooled to room temperature after reaction to get to translucent TiO2Nano dispersion fluid.Pass through the test of solid content, dispersion
TiO in liquid2Content be 30mg/mL.It is detected by laser particle analyzer, average grain diameter 49nm, particle diameter distribution 0.246.
Embodiment 6：
Content is the TiO of 40mg/mL2The preparation of nano dispersion fluid：
Nano titania dispersion liquid is prepared using solvent-thermal method.25mL absolute ethyl alcohols, 6mL metatitanic acid tetrems are taken at room temperature
Ester and 0.6mL hydrochloric acid mix in the beaker of 50mL, and solution A is obtained after magnetic agitation 10min.Separately take 5mL absolute ethyl alcohols and 2mL
Deionized water mixes in the beaker of 10mL, and solution B is obtained after being ultrasonically treated 5min.By solution B under conditions of magnetic agitation
It is slowly dropped in solution A, continues to stir 20min after being added dropwise, obtain translucent TiO2Colloidal sol.Finally by TiO2It is molten
Glue pours into the stainless steel cauldron of inner liner polytetrafluoroethylene, is put into after reaction kettle is sealed in 150 DEG C of baking oven and reacts 6h, instead
It is cooled to room temperature after answering to get to translucent TiO2Nano dispersion fluid.By the test of solid content, TiO in dispersion liquid2
Content be 40mg/mL.It is detected by laser particle analyzer, average grain diameter 47nm, particle diameter distribution 0.224.
Embodiment 7：
Conjugated polymer/TiO2The preparation of hybrid electron transport layer：
It is poly- [bis- (propionyloxy) fluorenes of 9,9- dioctyl fluorenes-co-9,9-] with the conjugated polymer prepared by embodiment 1
(PF8COOH) and the TiO prepared by embodiment 52Nanometer alcohol dispersion liquid prepares electron transfer layer.
Take TiO2Nano dispersion fluid 2mL is placed on 0.45 μm of filter filtering in the vial of 10mL.Then weigh 6
The PF8COOH of mg is dissolved in the THF solution of 2mL, is filtered with 0.45 μm of filter after object to be polymerized dissolving completely, and by filtrate and
TiO2Nano dispersion fluid is blended, and stable, translucent PF8COOH/ is obtained after the sonicated 10min of blended liquid
TiO2Dispersion liquid.By obtained PF8COOH/TiO2Dispersion liquid with the rotating speed of 4000rpm be spin-coated on it is plasma treated after glass
In glass substrate, spin-coating time 30s, it is TiO to obtain conjugated polymer content2The PF8COOH/TiO of quality 10%2Hybrid material
Film, it is finally that hybridized film is dry in 100 DEG C of baking oven.
Embodiment 8：
With the PF8COOH/TiO prepared by embodiment 72Hybrid material prepares perovskite solar cell：
The ITO electro-conductive glass of 5cm × 5cm is etched and cuts into 1.25 × 1.25cm2Size.It then will be after cutting
ITO electro-conductive glass is cleaned by ultrasonic with detergent, distilled water, acetone and isopropanol successively, and it is dry that vacuum is put into after cleaning
Dry case drying.Glass surface is handled with plasma washing machine after the drying of ITO electro-conductive glass, after being carried out after being disposed
Continuous operation.PF8COOH is dissolved in THF, TiO is added2Nano dispersion fluid prepares PF8COOH/TiO2Dispersion liquid will then divide
Dispersion liquid is spin-coated on the ITO conductive glass surfaces anticipated, then 100 DEG C of thermal anneal process 10min.Further, it will be rotary with
PF8COOH/TiO2The ito glass substrate of hybridized film is heated on 70 DEG C of warm table, later by 70 DEG C of PbI2/DMF
Solution (550mg/mL) is spun on conjugated polymer/TiO2Surface obtains PbI2Film, by PbI2Film 100 DEG C of heat in air
Anneal 1min.Wait for PbI2In its a small amount of isopropanol of surface spin coating (IPA) solution with to PbI after film cooling to room temperature2Film carries out
It pre-wets.Then in PbI2Surface spin coating MAI/IPA solution (70mg/mL), later by perovskite photoactive layer in vacuum drying oven
In 100 DEG C annealing 2h.Polymer P 3HT is configured to the solution of a concentration of 20mg/mL in advance, solvent is chloroform.Later by P3HT
Solution is spin-coated on perovskite thin film MAPbI3Surface, wiping part P3HT films with cotton swab after spin coating makes ITO electrode reveal
Go out.It is through metal mask that deposition of silver is true at the surfaces P3HT, thermal evaporation using the method for thermal evaporation using silver as anode material
Reciprocal of duty cycle is 1.5 × 10-3Pa, deposition rate areDeposition thickness is 200nm.Final perovskite solar cell device
Effective area is 0.09cm2。
Its performance parameter is shown in Table 1, and the J-V curve graphs of device are shown in Fig. 2, PF8COOH/TiO2Polymer content is not in hybridized film
The J-V curves of device simultaneously.
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,
Equivalent substitute mode is should be, is included within the scope of the present invention.
1 PF8COOH/TiO of table2The asynchronous solar cell properties of polymer content in hybridized film
Description of the drawings
The nuclear-magnetism figure of Fig. 1 poly- [bis- (propionyloxy) fluorenes of 9,9- dioctyl fluorenes-co-9,9-]
Fig. 2 PF8COOH/TiO2In hybridized film when polymer content difference device J-V curves.
Claims (9)
1. one kind being used for perovskite solar cell electron transfer layer hybrid, it is characterised in that：By alcohol/soluble conjugated polymerization
Object and nano-TiO2The hybrid material of formation, wherein conjugated polymer structural formula is：
R in formulaaFor hydrogen atom or the saturated alkane or unsaturated alkyl of C1~C12；RbSelected from propionyloxy, methyl-prop acidic group or
3- propyl amides -2- methyl propane sulfonic acid sodium；X values are 0.00~0.99；Conjugated polymer and TiO2Mass ratio is 1:100~100:
1。
2. a kind of preparation method for perovskite solar cell electron transfer layer hybrid according to claim 1,
It is characterized in that including the following steps：
(1) in the four round flask equipped with magneton and thermometer, dibromo fluorenes monomer, the diborate object of A1, A2 is added
Two bromo-derivatives, catalyst, ligand, weak base and solvent are 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, after reaction solution being poured into acidification
It is precipitated in deionized water, filters, dries, the product of gained is purified through column chromatography, is precipitated again, is filtered, drying；
(2) it takes solvent S, titanate esters and suitable acid to be mixed in beaker at room temperature, is obtained after 10~20min of magnetic agitation molten
Liquid A.Separately solvent S and deionized water is taken to be mixed in beaker, obtains solution B.Solution B is slowly dripped under conditions of magnetic agitation
It is added in solution A, continues 20~30min of stirring after being added dropwise, obtain translucent TiO2Colloidal sol.Finally by TiO2Colloidal sol
It pours into the stainless steel cauldron of inner liner polytetrafluoroethylene, is put into after reaction kettle is sealed in 140~160 DEG C of baking oven and reacts 5
~8h is cooled to room temperature after reaction to get to translucent TiO2Nano dispersion fluid, average grain diameter≤150nm；
(3) TiO for preparing step (2)2Nano dispersion fluid is placed on filter filtering in vial.Then weigh step (1)
Alcohol/soluble conjugated polymer of preparation is dissolved in solvent, is filtered with filter after object to be polymerized dissolving completely, and by filtrate with
TiO2Nano dispersion fluid is mixed, and it is poly- that stable, translucent conjugation is obtained after the sonicated 10~15min of blended liquid
Close object/TiO2Hydridization dispersion liquid.By obtained conjugated polymer/TiO2Hydridization dispersion liquid be spin-coated on it is plasma treated after
In substrate of glass, conjugated polymer/TiO is obtained2Hybrid material film, it is finally that hybridized film is dry in 100 DEG C of baking oven.
3. a kind of preparation method for perovskite solar cell electron transfer layer hybrid according to claim 2,
It is characterized in that：Dibromo fluorenes monomer is that bis- (propionyloxy) fluorenes of bis- bromo- 9,9- of 2,7-, bis- bromo- 9,9- of 2,7- are bis- in the step (1)
One kind or several in (2- methyl -3- propionyloxies) fluorenes, 2,7- bis- bromo- 9,9- bis- (3- propyl amides -2- methyl propane sulfonic acids sodium) fluorenes
Kind；The structural formula of the diborate object of A1 is：R in formula2For hydrogen atom or C1~C12Saturated alkane or
Person's unsaturated alkyl；The structural formula of two bromo-derivatives of A2 is：R in formula2For hydrogen atom or C1~C12's
Saturated alkane or unsaturated alkyl.
4. a kind of preparation side for perovskite solar cell electron transfer layer hybrid material according to claim 2
Method, it is characterized in that：The diborate object of the total mole number and A1 of two bromo-derivatives of dibromo fluorenes monomer and A2 in the step (1)
Molal quantity ratio be 0.5:1~1:1.5.The ratio of two bromo-derivatives of dibromo fluorenes monomer and A2 is 1:100~100:1.
5. a kind of preparation side for perovskite solar cell electron transfer layer hybrid material according to claim 2
Method, it is characterized in that：Catalyst is palladium catalyst in the step (1), is selected from Pd (OAc)2、PdCl2(dppf) or Pd
(PPh3)4One or more of；Its molal quantity and dibromo fluorenes monomer, the diborate object of A1, two bromo-derivatives of A2 these three objects
The ratio of the total mole number of matter is 0.001:1~0.6:1；In the step (1) ligand be selected from tricyclohexyl phosphine borofluoride,
The one or more of tripyrrole alkylphosphines, triphenylphosphine, tri-tert-butylphosphine, tricyclohexyl phosphine or triethylene diamine；Ligand with urge
The molar ratio of agent is 1:1~12:1.
6. a kind of preparation side for perovskite solar cell electron transfer layer hybrid material according to claim 2
Method, it is characterized in that：In the step (1) weak base be selected from mass fraction be 5%~50% tetramethylammonium hydroxide aqueous solution,
Tetraethyl ammonium hydroxide aqueous solution, tetrapropylammonium hydroxide solution, tetrabutylammonium hydroxide aqueous solution, four hexyl ammonium hydroxide
Aqueous solution, four octyl ammonium hydroxide aqueous solutions, wet chemical, aqueous sodium carbonate or one kind in acetic acid aqueous solutions of potassium or
It is several；The molal quantity of weak base and dibromo fluorenes monomer, the diborate object of A1, A2 two bromo-derivative these three substances total mole number
Ratio be 1:1~12:1；Solvent is selected from toluene, dimethylbenzene, dimethyl sulfoxide (DMSO) (DMSO), N, N- bis- in the step (1)
One or more of methylformamide (DMF), dimethylacetylamide (DMAc), N-Methyl pyrrolidone (NMP).
7. a kind of preparation side for perovskite solar cell electron transfer layer hybrid material according to claim 2
Method, it is characterized in that：Solvent S is selected from methanol, ethyl alcohol, ethylene glycol, propylene glycol, glycerine, isopropanol, fourth in the step (2)
One or more of alcohol, amylalcohol and hexanol；In the step (2) titanate esters be selected from tetraethyl titanate, butyl titanate,
One or more of metatitanic acid orthocarbonate, tetraisopropyl titanate, four different monooctyl ester of metatitanic acid and metatitanic acid four (octadecyl) ester；It is described
The step of (2) in acid one or more of selected from glacial acetic acid, hydrochloric acid, sulfuric acid, nitric acid and carbonic acid.
8. a kind of preparation side for perovskite solar cell electron transfer layer hybrid material according to claim 2
Method, it is characterized in that：The volume ratio of acid and titanate esters is 1 in the step (2):1~1:20；The volume ratio of acid and water is 1:1
~1:5；TiO2A concentration of 3mg/mL~40mg/mL of nano dispersion fluid.
9. a kind of preparation side for perovskite solar cell electron transfer layer hybrid material according to claim 2
Method, it is characterized in that：In the step (3) organic solvent be selected from methanol, ethyl alcohol, ethylene glycol, propylene glycol, glycerine, isopropanol,
One or more of butanol, propylene glycol monomethyl ether and ethylene glycol monomethyl ether；Conjugated polymer and TiO2Mass ratio is 100:1~1:
100。
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| CN112670420A (en) * | 2020-12-23 | 2021-04-16 | 江苏集萃分子工程研究院有限公司 | Perovskite thin film battery and preparation method thereof |
| CN113416213A (en) * | 2021-06-22 | 2021-09-21 | 重庆大学 | Application of organic phosphonium salt molecule in perovskite solar cell and preparation method of device thereof |
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| CN113416213A (en) * | 2021-06-22 | 2021-09-21 | 重庆大学 | Application of organic phosphonium salt molecule in perovskite solar cell and preparation method of device thereof |
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