CN107141451B - A kind of polymer solar cell device photoactive layer D-A type copolymer donor material - Google Patents

A kind of polymer solar cell device photoactive layer D-A type copolymer donor material Download PDF

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CN107141451B
CN107141451B CN201710233437.3A CN201710233437A CN107141451B CN 107141451 B CN107141451 B CN 107141451B CN 201710233437 A CN201710233437 A CN 201710233437A CN 107141451 B CN107141451 B CN 107141451B
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solar cell
polymer solar
alkyl
donor material
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CN107141451A (en
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朱丽君
霍添
夏道宏
周玉路
项玉芝
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Qingdao Zhiyong New Material Technology Co ltd
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Abstract

The present invention relates to a kind of polymer solar cell device photoactive layer D A type copolymer donor materials.The structural formula of the compound is：Wherein：R1For C4~C12Alkyl, R2For C2~C8Alkyl, R3For C4~C10Alkyl.M, n=8~50.The method of the present invention synthesis step is simply mild, and synthesis raw material is cheap, and manufacturing cost is cheap；Gained copolymer has good thermal stability (half decomposition temperature is more than 280 DEG C), preferable solubility property and filming performance, is suitable as polymer solar battery active layer material；With lower band gap (1.2~2.8eV), the absorption optical range of the material is increased while reducing electronic transition energy (within the scope of 300~1100nm)；The material has larger rigid conjugated structure and coplanarity, intermolecular π pi accumulations in solid-state structure are increased while enhancing Intramolecular electron transfer (ICT) intensity, are a kind of optical activity layer of polymer solar cell materials with bright prospects.

Description

A kind of polymer solar cell device photoactive layer D-A type copolymer donor Material
Technical field
The present invention relates to a kind of polymer solar cell device photoactive layer D-A type copolymer donor material and its systems Preparation Method.
Background technology
As the mankind are continuously increased energy demand, energy problem becomes one of the major issue that today's society faces. Since the non-recyclability of conventional fossil fuel and people use a large amount of environmental pollutions caused by fossil fuel, develop a kind of new The rechargeable energy of type becomes the emphasis and hot spot of research.People always search for renewable, clean energy substitution fossil Equal non-regeneration energies.Solar energy accounts for 99% or more earth gross energy, is generally regarded as inexhaustible, and And one of research object that is pollution-free, thus competitively being developed and utilized as scientists from all over the world.Too based on photovoltaic effect Positive energy battery is to develop and use the maximally efficient method of solar energy.
For many Land use systems of solar energy, directly converting solar radiant energy in the solar cell of electric energy is considered It is one of best Land use systems.The solar cell studied earliest is inorganic material solar energy battery, early in the fifties in 19th century, The laboratories Bell begin to develop crystal silicon solar energy battery, and energy conversion efficiency at that time reaches 6% or so.Currently, 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 current inorganic solar cell yield all rapid growth every year, its total amount account for the ratio of total power consumption according to It is so not high.This is mainly due to reasons such as inorganic solar cell cost of manufacture height, preparation condition harshnesses, while inorganic solar-electricity Pond is inconvenient to carry, non-flexible property and it is not easy to be processed the shortcomings of limit its and large-scale apply.Organic polymer solar cell, Due to its have many advantages, such as material source extensively, light weight, preparation process it is simple, can prepare by large area, device is flexible causes people Extensive concern, from 1986, first organic photovoltaic cell came out till now, and the energy of organic polymer solar cell turns It changes efficiency and has reached 8% or more.
Determine that the key of PSCs performance quality is PSCs photoactive layer donor materials.Currently, the photolytic activity that research is most hot Layer donor material includes polystyrene support class, polythiophene class and narrow band gap to-receptor type (D-A) copolymer analog.Wherein, polyphenyl second Alkene supports class and the most important disadvantage of polythiophene class donor material is its own limited light absorpting ability, and is difficult to be commercialized. And narrow band gap D-A copolymers donor material is taken seriously because of it due to there is preferable absorption light ability in visible light region.In addition, should Donor material also possesses lower band gap and stronger Intramolecular electron transfer (ICT) ability, but its that there is also synthesis conditions is severe It carves, the shortcomings of conjugated degree is low and solubility property is poor.Synthesis is wide thus absorbs, and the good low band gap polymer of dissolubility has important Meaning.
Invention content
The purpose of the present invention is to provide a kind of polymer solar cell device photoactive layer D-A type copolymer donors Material.And the present invention also provides the preparation methods of the polymer material.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of polymer solar cell device photoactive layer D-A type copolymer donor material, it is characterised in that this is poly- Close object structural formula be：
Wherein：R1For C4~C12Alkyl, R2For C2~C8Alkyl, R3For C4~C10Alkyl.M, n=8~50.
Above-mentioned polymer solar cell device photoactive layer is as follows with the preparation method of D-A type copolymer material：
(1) precise bis- (2- trimethylstannyls bithiophenes)-is to the double Thienopyrroles lists of two-N- dialkoxies phenyl Body and two bromo- benzo [1,2-C；4,5-C] bis- [1,2,5]-thiadiazoles monomers, are dissolved in polar solvent and pour into microwave reaction bottle In, catalyst is added, indifferent gas is blasted to microwave reaction bottle, it is rapid to cover, microwave reactor is moved into, under certain condition microwave Polymerization, reaction terminates, and after cooling, pours into a large amount of methanol, filter, be dried in vacuo polymer is that solar cell device light is lived Property layer D-A type copolymer donor material, synthetic route are as follows.
(2) reaction raw materials addition is：Bis- (2- trimethylstannyls bithiophenes)-are to the double thiophenes of two-N- dialkoxies phenyl Pheno and pyrrole monomer monomer (0.2~2mmol), two bromo- benzos [1,2-C；4,5-C] bis- [1,2,5]-thiadiazoles monomers (0.2~ 2mmol), monomer ratio 1：1.
(3) polar solvent used in is toluene, chlorobenzene, methanol, a kind of solvent in n,N-Dimethylformamide or two kinds it is mixed Bonding solvent, mixture ratio 1:10~20:1.
(4) used catalyst is two (three-tert-butyl phosphines) palladiums, tetra-triphenylphosphine palladium, 1,1'- bis- (diphenylphosphines) two cyclopentadienyl Iron palladium, bi triphenyl phosphorus palladium chloride, palladium tetrachloride diammonium, one kind in two (acetylacetone,2,4-pentanedione) triphenylphosphine palladiums, additive amount are 0.1~2mol% of reactant.
(5) it is nitrogen or argon gas to blast inert gas, and it is 10~30min to blast the time.
(6) at a temperature of Microwave Emulsifier-Free Polymerization reaction condition used in is 100~200 DEG C, 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 relatively narrow, and band gap is in 1.2~2.8eV；Ultraviolet and visible spectrum Polymer absorption optical range is measured between 300~1100nm, there is wider absorption optical range；Polymer has excellent molten Solve performance and film forming.
The present invention is coupled to introduce in conjugated main chain using mild Stiller possesses big conjugate rigid plane structure Double Thienopyrroles donor monomers and benzo [1,2-C；4,5-C] bis- [1,2,5]-thiadiazoles receptor units, and taken with alkyl It is that charge transmits bridge for bithiophene, this is effectively improved intermolecular π-π heaps in the conjugated degree and solid-state structure of copolymer Product, while being also grafted alkyl chain on double Thienopyrroles unit side chains, enhance the solubility property of copolymer donor material and adding Work performance.Therefore, this material has the characteristic of the high conjugated degree of low band gaps.To prepared copolymer be it is a kind of have it is wide The optical activity layer of polymer solar cell material of foreground.
Specific implementation mode
The following describes the present invention in detail with reference to examples：
Embodiment one：
(1) bis- (2- trimethylstannyls bithiophenes)-are to the double Thienopyrroles monomers of two-N- dialkoxies phenyl
Bis- (bithiophenes)-is added in the round-bottomed flask of 250mL to the double Thienopyrroles of two-N- dialkoxies phenyl N- bromo-succinimides (NBS, 2.1mmol), reaction mixture is added in (2.0mmol), chloroform (60mL) and acetic acid (12mL) 3h is stirred at room temperature.Then dichloromethane (100mL) is added into reaction mixture, and anhydrous magnesium sulfate is used after water washing Dry organic layer.Solvent is removed under reduced pressure, obtained brown solid is target product, yield 95%.
(2) bis- (2- trimethylstannyls bithiophenes)-are to the double Thienopyrroles of two-N- dialkoxies phenyl
Double bromine bithiophenes-are dissolved in tetrahydrofuran to the double Thienopyrroles (1.22mmol) of two-N- dialkoxies phenyl In (150mL), reaction system is cooled to -78 DEG C, is added dropwise and n-BuLi (2.68mmol) is added, and stirs 1h, is warming up to room temperature After be stirred for 2h, be cooled to -78 DEG C again, Me be added dropwise3It is gradually heating to room temperature after SnCl (5.7mmol), stirs 1h.Add Water quenching is gone out reaction, and dichloromethane is used in combination to extract, and removal volatile materials is concentrated under reduced pressure in anhydrous magnesium sulfate drying.It obtains faint yellow Grease be target product, yield 81%.
(3) bis- bromo- 5-2,6- dinitros -2,1,3- diazosulfides of 4,7-
Trifluoromethane sulfonic acid (4.0mmol) is added in two mouth flask, is placed in ice-water bath, by concentrated nitric acid (0.952mmol) is slowly dropped in flask.White mixed acid CF not soluble in water 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 obtained mixture is slow Pour into ice water, be added sodium hydroxide solution in and excess acid.It is precipitated, filtering precipitation is used in combination clear water to clean.It recrystallizes pure It is 4,7-, bis- bromo- 5-2,6- dinitros -2,1,3- diazosulfides, yield 85% that change obtains pale yellow crystals twice.
(4) bis- bromo- 5-2,6- diamino -2,1,3- diazosulfides of 4,7-
4,7-, bis- bromo- 5-2,6- dinitros -2,1,3- diazosulfides (2mmol) are dissolved in acetic acid, and iron filings are added (24.4mmol).Reaction mixture is heated to 100 DEG C of reaction 2h,.Then sodium hydroxide (10mL, 10%) is added, uses ether Extraction.Organic phase is dried with anhydrous sodium sulfate, and it is 4,7-, bis- bromo- 5-2,6- diaminos that solvent, which is removed under reduced pressure, and obtains brown solid Base -2,1,3- diazosulfides, yield 90%.
(5) two bromo- benzo [1,2-C；4,5-C] bis- [1,2,5]-thiadiazoles
4,7-, bis- bromo- 5-2,6- diamino -2,1,3- diazosulfides (2mmol), PHNSO (4mmol) and trimethyl Chlorosilane (0.6mL) is added in round-bottomed flask.Anhydrous pyridine (20mL) is added, 70 DEG C of stirrings are for 24 hours.Then it cools down, uses water Solid is collected by filtration.It obtains solid water and methanol washs that repeatedly to obtain solid be 4,7- bis- (thiophene -2- bases) benzo [1,2- C；4,5-C] bis- [1,2,5]-thiadiazoles, yield 49%.
(6) synthesis of polymer
Precise bis- (2- trimethylstannyls bithiophenes)-is to the double Thienopyrroles monomers of two-N- dialkoxies phenyl (0.30mmol) and two bromo- benzo [1,2-C；4,5-C] bis- [1,2,5]-thiadiazoles) monomer (0.30mmol).It is dissolved in toluene The in the mixed solvent of (5mL) and DMF (3mL).Pd (PPh are added3)4(0.5%).Continue air-blowing 10min, it is rapid to cover, it moves into micro- Wave reactor, under the conditions of 150 DEG C, Microwave Emulsifier-Free Polymerization 30min.After reaction, a large amount of methanol are cooled and poured into, are filtered, vacuum Dry polymer, yield 67%.
It is characterized through gel permeation chromatography, weight average molecular weight 8200, molecular weight distribution 1.8；Copolymer donor material Band gap is relatively narrow, and band gap is in 1.1eV；Ultraviolet and visible spectrum measures copolymer donor material and absorbs optical range in 600~1000nm Between, there is wider absorption optical range；Copolymer donor material has excellent solubility property and film forming.
Embodiment two：
(1) bis- (2- trimethylstannyls bithiophenes)-are to the double Thienopyrroles monomers of two-N- dialkoxies phenyl
In the round-bottomed flask of 250mL plus bis- (bithiophenes)-are to the double Thienopyrroles of two-N- dialkoxies phenyl N- bromo-succinimides (NBS, 2.2mmol), reaction mixture is added in (2.0mmol), chloroform (60mL) and acetic acid (16mL) 0.5h is stirred at room temperature.Then dichloromethane (180mL) is added into reaction mixture, and anhydrous slufuric acid is used after water washing Magnesium dries organic layer.Solvent is removed under reduced pressure, it is target product, yield 91% to obtain solid.
(2) bis- (2- trimethylstannyls bithiophenes)-are to the double Thienopyrroles of two-N- dialkoxies phenyl
Double bromine bithiophenes-are dissolved in tetrahydrofuran to the double Thienopyrroles (1.22mmol) of two-N- dialkoxies phenyl In (100mL), reaction system is cooled to -78 DEG C, and the hexane solution that n-BuLi (2.65mmol) is added, stirring is added dropwise 0.5h is stirred for 2h after being to slowly warm up to room temperature, is cooled to -78 DEG C again, Me is added dropwise3SnCl (5.5mmol) heats up afterwards To room temperature, 1h is stirred.Add water quenching to go out reaction, dichloromethane is used in combination to extract, removal volatility is concentrated under reduced pressure in anhydrous magnesium sulfate drying Substance.It is purified through column chromatography, it is target product, yield 85% to obtain flaxen grease.
(3) synthesis of polymer
Precise bis- (2- trimethylstannyls bithiophenes)-is to the double Thienopyrroles monomers of two-N- dialkoxies phenyl (about 0.30mmol) and two bromo- benzo [1,2-C；4,5-C] bis- [1,2,5]-thiadiazoles) monomer (0.30mmol).It is dissolved in first The in the mixed solvent of benzene (1.5mL) and DMF (0.5mL).Pd (PPh are added3)4(0.5%).Continue air-blowing 10min, it is rapid to cover, Move into microwave reactor, Microwave Emulsifier-Free Polymerization under the conditions of 120 DEG C of 50min.After reaction, a large amount of methanol are cooled and poured into, filter, It is dried in vacuo to obtain polymer, yield 60%.
It is characterized through gel permeation chromatography, weight average molecular weight 11000, molecular weight distribution 1.6；Copolymer donor material Band gap is relatively narrow, and band gap is in 1.3eV；Ultraviolet and visible spectrum measure copolymer donor material absorb optical range 600~900nm it Between, there is wider absorption optical range；Copolymer donor material has excellent solubility property and film forming.

Claims (2)

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 object is：
Wherein：R1For C4~C12Alkyl, R2For C2~C8Alkyl, R3For C4~C10Alkyl.M, n=8~50.
2. D-A type copolymer material according to claim 1, which is characterized in that there is the polymer long wavelength to absorb energy Power, absorption spectrum ranges are between 300~1100nm.
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CN103865038A (en) * 2012-12-12 2014-06-18 海洋王照明科技股份有限公司 Conjugated polymer containing diketopyrrolopyrrole-dibenzothiophenebenzodithiophene and preparation method and application thereof
CN104311800A (en) * 2014-10-22 2015-01-28 上海大学 Copolymer donor material for optically active layer of polymer solar cell (PSC) and preparation method of copolymer donor material
EP2927257A1 (en) * 2012-11-30 2015-10-07 Ocean's King Lighting Science&Technology Co., Ltd. Benzodithiophene based copolymer containing pyridino [2,1,3]thiadiazole units and preparing method and applications thereof
CN105199083A (en) * 2015-09-11 2015-12-30 中国石油大学(华东) Long-wave absorption copolymer donor material for polymer solar cell light active layer and preparation method of long-wave absorption copolymer donor material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP2927257A1 (en) * 2012-11-30 2015-10-07 Ocean's King Lighting Science&Technology Co., Ltd. Benzodithiophene based copolymer containing pyridino [2,1,3]thiadiazole units and preparing method and applications thereof
CN103865038A (en) * 2012-12-12 2014-06-18 海洋王照明科技股份有限公司 Conjugated polymer containing diketopyrrolopyrrole-dibenzothiophenebenzodithiophene and preparation method and application thereof
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