CN105199083B - A kind of optical activity layer of polymer solar cell longwave absorption copolymer donor material - Google Patents
A kind of optical activity layer of polymer solar cell longwave absorption copolymer donor material Download PDFInfo
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- CN105199083B CN105199083B CN201510578172.1A CN201510578172A CN105199083B CN 105199083 B CN105199083 B CN 105199083B CN 201510578172 A CN201510578172 A CN 201510578172A CN 105199083 B CN105199083 B CN 105199083B
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- 0 CCCCCCCCC(*C(c([s]c(-c1cc([n](c2c3[s]c(-c([s]c(-c4c(CCCCCCCC)c(C)c(*)[s]4)c4[*+])c4OCCCCCC)c2)-c2cc(*)c(*)c(*)c2)c3[s]1)c1OCCCCCC)c1OCCCCCC)=S1)=C1Br Chemical compound CCCCCCCCC(*C(c([s]c(-c1cc([n](c2c3[s]c(-c([s]c(-c4c(CCCCCCCC)c(C)c(*)[s]4)c4[*+])c4OCCCCCC)c2)-c2cc(*)c(*)c(*)c2)c3[s]1)c1OCCCCCC)c1OCCCCCC)=S1)=C1Br 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E10/549—Organic PV cells
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Abstract
The present invention relates to a kind of optical activity layer of polymer solar cell copolymer donor material and preparation method thereof.The structural formula of the compound is：
Description
Technical field
The present invention relates to a kind of optical activity layer of polymer solar cell copolymer donor material and preparation method thereof.
Background technology
As the mankind are continuously increased to energy demand, one of major issue that energy problem faces as today's society.
Due to a large amount of environmental pollutions that the non-recyclability of conventional fossil fuel and people are caused using fossil fuel, exploitation is a kind of new
The rechargeable energy of type turns into the emphasis and focus of research.People always search for the energy substitution fossil of renewable cleaning
Deng non-regeneration energy.Solar energy accounts for earth gross energy more than 99%, is typically regarded as inexhaustible, and
And it is pollution-free, thus as scientists from all over the world's competitively one of research object of development and utilization.Based on photovoltaic effect too
Positive energy battery is to develop the maximally efficient method of solar energy.
For many Land use systems of solar energy, directly the solar cell that solar radiant energy is converted into electric energy is considered as
It is one of best Land use systems.The solar cell of research is inorganic material solar energy battery earliest, early in the fifties in 19th century,
Bell laboratories begin to develop crystal silicon solar energy battery, and energy conversion efficiency at that time reaches 6% or so.At present, the sun
Energy battery research work is concentrated mainly on silica-based solar cell, and highest transformation efficiency reaches 24%, already close to the theoretical upper limit
30%.Although annual all rapid growths of inorganic solar cell yield at present, its total amount account for the ratio of total power consumption according to
It is so not high.This mainly due to inorganic solar cell cost of manufacture is high, the reason such as preparation condition is harsh, while inorganic solar-electricity
The shortcomings of pond carries inconvenient, non-flexible and non-easy processing limits its large-scale application.Organic polymer solar cell,
Due to its have the advantages that material source extensively, light weight, preparation process is simple, can large area prepare, device flexibility cause people
Extensive concern, from 1986, first organic photovoltaic cell came out till now, and the energy of organic polymer solar cell turns
Change efficiency and reach more than 8%.
The key for determining PSCs performances quality is PSCs photoactive layer donor materials.At present, most hot photolytic activity is studied
Layer donor material includes polystyrene support class, polythiophene class and narrow band gap to-receptor type (D-A) copolymer analog.Wherein, polyphenyl second
It is its own limited light absorpting ability that alkene supports class and the topmost shortcoming of polythiophene class donor material, and is difficult to be commercialized.
And narrow band gap D-A copolymers donor material is taken seriously because it has and preferably absorb light ability in visible region.In addition, should
Donor material also possesses relatively low band gap and stronger Intramolecular electron transfer (ICT) ability, but its to there is also synthesis condition severe
The shortcomings of quarter, low conjugated degree and poor solubility property.Synthesize absorption wide for this, the good low band gap polymer of dissolubility has important
Meaning.
The content of the invention
It is an object of the invention to provide a kind of polymer solar cell device photoactive layer D-A type copolymer donor
Material.And present invention also offers the preparation method of the polymeric material.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of polymer solar cell device photoactive layer D-A type copolymer donor material material, it is characterised in that
The structural formula of the polymer is：
Wherein：R1 is C4~C12 alkyl, and R2 is C2~C8 alkyl, and R3 is C4~C10 alkyl.N=8~100.
Above-mentioned polymer solar cell device photoactive layer is as follows with the preparation method of D-A type copolymer material：
(1) the double Thienopyrroles monomers of double (2- trimethylstannyls the bithiophene)-N- tri-alkoxy phenyls of precise and
Two bromo- benzo [1,2-C；4,5-C] double [1,2,5]-thiadiazoles monomers, are dissolved in polar solvent and pour into microwave reaction bottle,
Catalyst is added, indifferent gas is blasted to microwave reaction bottle, rapid capping moves into microwave reactor, and microwave gathers under certain condition
Close, reaction terminates, after cooling, pour into a large amount of methyl alcohol, suction filtration, be vacuum dried to obtain polymer as solar cell device photolytic activity
Layer D-A type copolymer donor material.
(2) reaction raw materials addition is：The double thieno pyrroles of double (2- trimethylstannyls bithiophene)-N- tri-alkoxy phenyls
Cough up monomer (0.2~2mmol), two bromo- benzos [1,2-C；4,5-C] double [1,2,5]-thiadiazoles monomers (0.2~2mmol) are single
Body ratio is 1：1.
(3) polar solvent used by is toluene, chlorobenzene, methyl alcohol, a kind of solvent in DMF or two kinds it is mixed
Bonding solvent, mixture ratio is 1:10~20:1.
(4) used catalyst is two (three-tert-butyl phosphine) palladiums, tetra-triphenylphosphine palladium, 1,1'- double (diphenylphosphines) two cyclopentadienyl
Iron palladium, bi triphenyl phosphorus palladium chloride, the ammonium of palladium tetrachloride two, the one kind in two (acetylacetone,2,4-pentanedione) triphenylphosphine palladiums, addition is
0.1~2mol% of reactant.
(5) inert gas is blasted for nitrogen or argon gas, blasts the time for 10~30min.
(6) Microwave Emulsifier-Free Polymerization reaction condition used by be 100~200 DEG C at a temperature of, 10~80min of microwave reaction.
The copolymer donor material prepared using the above method is characterized through gel permeation chromatography, and weight average molecular weight is
4100~40000, molecular weight distribution 1.1~5.5；Polymer band gap is narrower, and band gap is in 1.2~2.8eV；Ultraviolet and excitation spectrum
Polymer absorption optical range is measured between 300~1100nm, with absorption optical range wider；Polymer has excellent molten
Solution performance and film forming.
The present invention is coupling in conjugated main chain to introduce and possesses big conjugate rigid plane structure using gentle Stiller
Double Thienopyrroles donor monomers and benzo [1,2-C；4,5-C] double [1,2,5]-thiadiazoles receptor units, and taken with alkyl
It is that electric charge transmits bridge for bithiophene, this is effectively improved intermolecular π-π heaps in the conjugated degree of copolymer and solid-state structure
Product, while being also grafted alkyl chain on double Thienopyrroles unit side chains, strengthens the solubility property of copolymer donor material and adds
Work performance.Therefore, this material has the characteristic of low band gaps conjugated degree high.The copolymer so as to prepared by is a kind of with wide
The optical activity layer of polymer solar cell material of prospect.
Specific embodiment
With reference to embodiment, the present invention is described in detail：
Embodiment one：
(1) the double Thienopyrroles of double bromine (bithiophene)-N- tri-alkoxy phenyls
Double double Thienopyrroles of (bithiophene)-N- tri-alkoxy phenyls are added in the round-bottomed flask of 250mL
(2.0mmol), chloroform (60mL) and acetic acid (12mL), add N- bromo-succinimides (NBS, 2.1mmol), reactant mixture
3h is stirred at room temperature.Then to dichloromethane (100mL) is added in reactant mixture, by using anhydrous magnesium sulfate after water washing
Dry organic layer.Removal of solvent under reduced pressure, the brown solid for obtaining as target product, yield is 95%.
(2) the double Thienopyrroles of double (2- tin trimethyls bithiophene)-N- tri-alkoxy phenyls
The double Thienopyrroles (1.22mmol) of double bromines (bithiophene)-N- tri-alkoxy phenyls are dissolved in tetrahydrofuran
In (150mL), reaction system is cooled to -78 DEG C, is added dropwise over adding n-BuLi (2.68mmol), stirs 1h, is warming up to room temperature
After be stirred for 2h, -78 DEG C are cooled to again, be added dropwise over Me3Room temperature is gradually heating to after SnCl (5.7mmol), 1h is stirred.Plus
Water quenching is gone out reaction, and is extracted with dichloromethane, and anhydrous magnesium sulfate is dried, and be concentrated under reduced pressure removal volatile materials.Obtain faint yellow
Grease be target product, yield is 81%.
(3) the bromo- 5-2,6- dinitros -2,1,3- diazosulfides of 4,7- bis-
Trifluoromethane sulfonic acid (4.0mmol) is added in two mouthfuls of flasks, is placed in ice-water bath, by concentrated nitric acid
(0.952mmol) is slowly dropped in flask.Water insoluble white mixed acid CF is obtained3SO3H/HNO3.4,7- bis- is bromo-
2,1,3- diazosulfides (0.34mmol) are added in mixed acid, and 50 DEG C are stirred overnight.Then the mixture that will be obtained is slow
Pour into frozen water, add sodium hydroxide solution in and excess acid.It is precipitated, filtering precipitation, and is cleaned with clear water.Recrystallization is pure
Change obtains pale yellow crystals and is the bromo- 5-2 of 4,7- bis- twice, 6- dinitro -2, and 1,3- diazosulfide, yield is 85%.
(4) the bromo- 5-2,6- diaminourea -2,1,3- diazosulfides of 4,7- bis-
The bromo- 5-2 of 4,7- bis-, 6- dinitro -2,1,3- diazosulfide (2mmol) are dissolved in acetic acid, iron filings are added
(24.4mmol).Reactant mixture is heated to 100 DEG C of reaction 2h,.NaOH (10mL, 10%) is subsequently adding, ether is used
Extract.Organic phase anhydrous sodium sulfate drying, removal of solvent under reduced pressure obtains brown solid and is the bromo- 5-2 of 4,7- bis-, 6- diaminos
Base -2,1,3- diazosulfide, yield is 90%.
(5) two bromo- benzo [1,2-C；4,5-C] double [1,2,5]-thiadiazoles
The bromo- 5-2 of 4,7- bis-, 6- diaminourea -2,1,3- diazosulfide (2mmol), PHNSO (4mmol) and trimethyl
Chlorosilane (0.6mL) is added in round-bottomed flask.Add anhydrous pyridine (20mL), 70 DEG C of stirring 24h.Then cool down, use water
Solid is collected by filtration.Obtain solid and washed with water and methyl alcohol repeatedly to obtain solid as 4,7- bis- (thiophene -2- bases) benzo [1,2-
C；4,5-C] double [1,2,5]-thiadiazoles, yield is 49%.
(6) synthesis of polymer
Double Thienopyrroles monomer (0.30mmol) of double (2- tin trimethyls the bithiophene)-N- tri-alkoxy phenyls of precise
Benzo [1,2-C bromo- with two；4,5-C] double [1,2,5]-thiadiazoles) monomer (0.30mmol).It is dissolved in toluene (5mL) and DMF
In the mixed solvent of (3mL).Add Pd (PPh3)4(0.5%).Continue air-blowing 10min, rapid capping moves into microwave reactor,
Under the conditions of 150 DEG C, Microwave Emulsifier-Free Polymerization 30min.After reaction terminates, a large amount of methyl alcohol are cooled and poured into, suction filtration, be vacuum dried and must be polymerized
Thing, yield is 67%.
Characterized through gel permeation chromatography, weight average molecular weight is 9100, molecular weight distribution 1.8；Copolymer donor material
Band gap is narrower, and band gap is in 1.1eV；Ultraviolet and excitation spectrum measure copolymer donor material absorb optical range 500~900nm it
Between, with absorption optical range wider；Copolymer donor material has excellent solubility property and film forming.
Embodiment two：
(1) the double Thienopyrroles of double bromine (bithiophene)-N- tri-alkoxy phenyls
In the round-bottomed flask of 250mL plus the double Thienopyrroles (2.0mmol) of double (bithiophene)-N- tri-alkoxy phenyls,
Chloroform (60mL) and acetic acid (16mL), add N- bromo-succinimides (NBS, 2.2mmol), and reactant mixture is stirred at room temperature
Mix 0.5h.Then it is organic by being dried with anhydrous magnesium sulfate after water washing to dichloromethane (180mL) is added in reactant mixture
Layer.Removal of solvent under reduced pressure, obtains solid as target product, and yield is 91%.
(2) the double Thienopyrroles of double (2- tin trimethyls bithiophene)-N- tri-alkoxy phenyls
The double Thienopyrroles (1.22mmol) of double bromines (bithiophene)-N- tri-alkoxy phenyls are dissolved in tetrahydrofuran
In (100mL), reaction system is cooled to -78 DEG C, is added dropwise over adding the hexane solution of n-BuLi (2.65mmol), stirring
0.5h, 2h is stirred for after being to slowly warm up to room temperature, and -78 DEG C are cooled to again, is added dropwise over Me3SnCl (5.5mmol) heats up afterwards
To room temperature, 1h is stirred.Add water and reaction is quenched, and extracted with dichloromethane, anhydrous magnesium sulfate is dried, be concentrated under reduced pressure removal volatility
Material.Purified through column chromatography, obtain flaxen grease as target product, yield is 85%.
(3) synthesis of polymer
The double Thienopyrroles monomers of double (2- tin trimethyls the bithiophene)-N- tri-alkoxy phenyls of precise are (about
0.30mmol) with two bromo- benzo [1,2-C；4,5-C] double [1,2,5]-thiadiazoles) monomer (0.30mmol).It is dissolved in toluene
In the mixed solvent of (1.5mL) and DMF (0.5mL).Add Pd (PPh3)4(0.5%).Continue air-blowing 10min, rapid capping is moved
Enter microwave reactor, the Microwave Emulsifier-Free Polymerization under the conditions of 120 DEG C of 50min.After reaction terminates, a large amount of methyl alcohol are cooled and poured into, it is suction filtration, true
Empty dry polymer, yield is 60%.
Characterized through gel permeation chromatography, weight average molecular weight is 12000, molecular weight distribution 1.6；Copolymer donor material
Band gap is narrower, and band gap is in 1.3eV；Ultraviolet and excitation spectrum measure copolymer donor material absorb optical range 400~800nm it
Between, with absorption optical range wider；Copolymer donor material has excellent solubility property and film forming.
Embodiment three：
(1) the double Thienopyrroles of double bromine (bithiophene)-N- tri-alkoxy phenyls
Double double Thienopyrroles of (bithiophene)-N- tri-alkoxy phenyls are added in the round-bottomed flask of 250mL
(2.0mmol), chloroform (60mL) and acetic acid (10mL), add N- bromo-succinimides (NBS, 2.1mmol), reactant mixture
2h is stirred at room temperature.Then to dichloromethane (100mL) is added in reactant mixture, by using anhydrous magnesium sulfate after water washing
Dry organic layer.Removal of solvent under reduced pressure, the brown solid for obtaining as target product, yield is 90%.
(2) the double Thienopyrroles of double (2- tin trimethyls bithiophene)-N- tri-alkoxy phenyls
The double Thienopyrroles (1.22mmol) of double bromines (bithiophene)-N- tri-alkoxy phenyls are dissolved in tetrahydrofuran
In (150mL), reaction system is cooled to -78 DEG C, is added dropwise over adding n-BuLi (2.7mmol), 1h is stirred, after being warming up to room temperature
2h is stirred for, -78 DEG C are cooled to again, be added dropwise over Me3Room temperature is gradually heating to after SnCl (5.6mmol), 1h is stirred.Add water
Reaction is quenched, and is extracted with dichloromethane, anhydrous magnesium sulfate is dried, be concentrated under reduced pressure removal volatile materials.Obtain grease i.e.
It is target product, yield is 80%.
(3) synthesis of polymer
Double Thienopyrroles monomer (0.30mmol) of double (2- tin trimethyls the bithiophene)-N- tri-alkoxy phenyls of precise
Benzo [1,2-C bromo- with two；4,5-C] double [1,2,5]-thiadiazoles) monomer (0.30mmol).It is dissolved in toluene (8mL) and DMF
In the mixed solvent of (2mL).Add Pd (PPh3)4(0.5%).Continue air-blowing 20min, rapid capping moves into microwave reactor,
Under the conditions of 160 DEG C, Microwave Emulsifier-Free Polymerization 20min.After reaction terminates, a large amount of methyl alcohol are cooled and poured into, suction filtration, be vacuum dried and must be polymerized
Thing, yield is 60%.
Characterized through gel permeation chromatography, weight average molecular weight is 14000, molecular weight distribution 1.9；Copolymer donor material
Band gap is narrower, and band gap is in 1.3eV；Ultraviolet and excitation spectrum measure copolymer donor material absorb optical range 500~900nm it
Between, with absorption optical range wider；Copolymer donor material has excellent solubility property and film forming.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (1)
1. a kind of polymer solar cell device photoactive layer D-A type copolymer donor material, it is characterised in that the polymerization
The structural formula of thing is：
Wherein：R1It is C4~C12 alkyl, R2It is C2~C8 alkyl, R3It is C4~C10 alkyl, n=8~100.
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| CN107141451B (en) * | 2017-04-11 | 2018-07-20 | 中国石油大学(华东) | A kind of polymer solar cell device photoactive layer D-A type copolymer donor material |
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| CN102762630A (en) * | 2009-05-26 | 2012-10-31 | 佛罗里达大学研究基金会公司 | Green soluble conjugated polymers with high charge carrier mobilities |
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| CN102762630A (en) * | 2009-05-26 | 2012-10-31 | 佛罗里达大学研究基金会公司 | Green soluble conjugated polymers with high charge carrier mobilities |
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| Title |
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| Ambipolarity in Benzobisthiadiazole-Based Donor–Acceptor Conjugated P;Jonathan D. Yuen et al;《Adv. Mater.》;20111231;第23卷;第3780–3785页 * |
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