CN108912139A - A kind of organic solar batteries electron acceptor material and the preparation method and application thereof - Google Patents
A kind of organic solar batteries electron acceptor material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of organic solar batteries electron acceptor materials and the preparation method and application thereof, with three thiophene core of benzo, by the thiophene unit bridge for introducing different number, then strong electron-withdrawing group group is introduced in end to realize the regulation of its photoelectric property, to construct high performance organic solar batteries electron acceptor material.Organic solar batteries electron acceptor material of the invention shows excellent exciton dissociation ability, have good thermal stability, electrical stability and solution processability energy, and it is convieniently synthesized, be easy to purify, it is low in cost, be the potential replacer of fullerene electron acceptor.Non- fullerene electron acceptor material is suitable for be widely used in preparing high-performance organic solar batteries device.
Description
Technical field
The invention belongs to photoelectric materials and applied technical field, and in particular to a kind of organic photoelectrical material, more specifically one
Kind organic solar batteries electron acceptor material and the preparation method and application thereof.
Background technique
Organic solar batteries are a kind of convert light into as the novel thin film solar battery technology of electricity.With traditional silicon substrate light
Volt battery is compared, with low in cost, light, environmental pollution is small, it is easy to accomplish the advantages such as large area and flexibility, in recent years
To have become one of the research hotspot of academia and industrial circle.By the rapid development of last decade, incident photon-to-electron conversion efficiency is
Through breaking through 14%.Nevertheless, the distance commercialization of its efficiency still has biggish gap (20%), its performance how is improved
Remain the key problem of its development.
It is attracted wide attention currently based on conjugated polymer/non-fullerene to receptor bulk heterojunction solar cells
And research.Between the past several years, the non-fullerene electron acceptor material of high-performance emerges one after another, by the effect of organic solar batteries
Rate has been increased to 14% or more.Non- fullerene electron acceptor material has huge compared to traditional fullerene electron acceptor material
Big advantage：Firstly, non-fullerene electron acceptor material is stronger for the absorbability of light, this makes photolytic activity from performance
Layer is higher for the capture ability of photon, this will improve the photoelectric current of device, to improve its incident photon-to-electron conversion efficiency；Secondly,
Although fullerene derivate has good electron mobility (~10-3cm2V-1s-1), however nowadays developed numerous high migrations
Rate electron acceptor material is equally matched even higher in contrast.Thus in high-performance polymer solar battery, light
Electron-hole is compound caused by the unbalanced carrier transport of active layer is addressed, and is that its performance further increases
Key factor.Second, from processing technology, non-fullerene electron acceptor material is mutually separated with polymer-electronics donor material
Situation and film morphology can regulate and control improved from the skeleton of non-fullerene molecule, so that processing technology is simpler, avoid
Film aftertreatment technology, including thermal annealing, solvent anneal, solvent additive using extremely complex harshness etc. improve
The mutually separation situation at electron donor-acceptor (EDA) interface；In addition, the filming performance of non-fullerene electron acceptor material is preferable, improve indirectly
The solution processability energy of optical activity layer film, be conducive to reduce the performance of large area organic polymer solar cell with
The difference of small area battery efficiency, this largely pushes the commercial applications of organic polymer solar cell.Finally,
From cost, the preparation cost of non-fullerene electron acceptor material wants much lower compared to fullerene electron acceptor material, more
Be conducive to the cost effective and applied generalization of organic solar batteries technology.To sum up, further developing novel high-performance
Non- fullerene electron acceptor material has realization organic polymer solar cell performance to commercialized development very important
Meaning.
The present invention proposes a kind of non-fullerene electron acceptor material technical solution of novel high-performance, efficient, cheap to building,
The organic solar batteries device of long-life has important scientific meaning and practical value.
Summary of the invention
Goal of the invention：In order to overcome the deficiencies in the prior art, the present invention provides a kind of organic solar batteries electricity
Sub- acceptor material and the preparation method and application thereof, specifically one kind are using three thiophene of benzo as core, by introducing different number
Thiophene unit bridge, then introduce strong electron-withdrawing group group in end to realize the regulation of its photoelectric property, it is high performance to construct
Organic solar batteries electron acceptor material.
Technical solution：To achieve the above object, the technical solution adopted by the present invention is：
A kind of organic solar batteries electron acceptor material, the material is using three thiophene of benzo as core, by introducing different numbers
Then the thiophene unit bridge of amount introduces strong electron-withdrawing group group in end to realize the regulation of its photoelectric property, to construct high-performance
Organic solar batteries electron acceptor material；With the general structure as shown in following formula 1：
It is integer that wherein n, which is the quantity of thiophene unit, 0≤n≤10, and n,；R1、R2Independent is hydrogen atom, C1~
C30Alkyl chain, C1~C30Oxyalkyl chain, C5~C30Naphthenic base or C2~C30One of miscellaneous alkyl chain；
End group A is selected from one of following group A1-A16：
Wherein, * is link position；C is carbon atom；H is hydrogen atom；O is oxygen atom；N is nitrogen-atoms；F is fluorine atom.
Further, the n is the quantity of thiophene unit, can be preferably n=1,2 or 3；The R1、R2Respectively
It is independently hydrogen atom, C1~C10Alkyl chain, C1~C10Oxyalkyl chain, C5~C10One of naphthenic base chain.
More specifically, the R1、R2Independent is hydrogen atom, C1~C10Straight chained alkyl or C1~C10Branch
One of alkyl.
Such as take n=1, R1、R2Independent is hydrogen atom, C1~C10Straight chained alkyl or C1~C10In branched alkyl
One kind；It can be with one of flowering structure：
Present invention simultaneously provides the preparation method of the organic solar batteries electron acceptor material, this method includes following step
Suddenly：
It is carried out among Borneo camphor Wen Gaier (Knoevenagel) condensation reaction generation using end group and the thiophene aldehyde radical with bromine
Then the tin reagent of intermediate and core is carried out Stille coupling reaction and generates final product by body.
More specifically, this approach includes the following steps：
Step 1：End group and bromo alkyl thiophene aldehyde are dissolved in chloroform, bromo alkyl thiophene aldehyde molar equivalent number is instilled
0.1% triethylamine stirring one hour of room temperature reaction, after extracting and washing, drying, filtering and concentrating, column Chromatographic purification is obtained
Intermediate B rRTCN；
Step 2：Intermediate and three thiophene tin reagent of benzo are added to inside microwave tube, chlorobenzene dissolution substrate simultaneously uses nitrogen
It is bubbled deoxygenation, the tetra-triphenylphosphine palladium of three thiophene molar equivalent number 3% of benzo is then added, microwave tube is finally placed on microwave
It is reacted 15 minutes for 150 DEG C inside reactor.After extracting and washing, drying, filtering and concentrating, column Chromatographic purification obtains final product
BTTCN。
The material can be used as electron acceptor material for binary or polynary organic solar batteries device.
Beneficial effect：A kind of organic solar batteries electron acceptor material provided by the invention and preparation method thereof with answer
With characterizing compound by nuclear magnetic resonance (NMR), ground substance assistant laser Dissociation time flight mass spectrum (MALDI-TOF-MS)
Structure, ultra-violet absorption spectrum (UV-vis), cyclic voltammetry characterize the basic spectrum of material and electrochemical properties, differential thermal point
The basic physical property that analysis tests material has the advantage that compared with prior art：
(1) photoelectric property is adjustable, that is, uses the thiophene unit bridge of different length, can simply realize material photo electric
The regulation of matter；
(2) end group modification of strong electron-withdrawing ability is to match high performance donor material energy band and absorption spectrum；
(3) there is certain crystal property, materials synthesis is easy, is easy to purify, is low in cost；
(4) material acts not only as electron acceptor use in organic solar batteries, can also be used as tertiary blending
Organic solar batteries are used to the added material that/acceptor interface regulates and controls.
Detailed description of the invention
The nuclear magnetic resoance spectrum of Fig. 1 (a), (b) acceptor material BTTCN.
The mass spectrogram of Fig. 2 acceptor material BTTCN.
The film absorption spectrogram of Fig. 3 acceptor material BTTCN.
Fig. 4 acceptor material BTTCN electrochemistry cyclic voltammogram.
The DSC differential scanning calorimetry of Fig. 5 acceptor material BTTCN analyzes result.
The mass spectrogram of Fig. 6 acceptor material BTTIC.
Fig. 7 acceptor material BTTCN is applied to binary, ternary machine photovoltaic device and the tradition using identical donor material
The voltage-current curve of fullerene organic solar batteries.
Fig. 8 acceptor material BTTIC is applied to binary, ternary machine photovoltaic device and the tradition using identical donor material
The voltage-current curve of fullerene organic solar batteries.
Specific embodiment
The present invention will be further explained with reference to the accompanying drawings and examples.
End group A is selected from one of following group A1-A16：
When end group A is selected from group A1 or A8, the synthesis of some materials synthesis：
Embodiment 1：The synthesis of BTTCN
When end group A is selected from group A1, reaction route 1：
Prepare the synthesis step of BTTCN intermediate B rRTCN：By malononitrile (52.3mg, 0.79mmol) and BrRTCHO
(200mg, 0.66mmol) is added in 20mL chloroform.Then the triethylamine stirring of 0.1mL room temperature reaction 10 minutes is added.Ice
Then water quenching reaction uses methylene chloride and water to distinguish extracting and washing three times, with anhydrous magnesium sulfate drying, filtering and concentrating.It uses
Petroleum ether and methylene chloride mixed solvent carry out column Chromatographic purification, obtain BrRTCN (211.5mg, 91.3%).1H NMR
(400MHz,CDCl3):δ7.71(s,1H),7.38(s,1H),2.54-2.53(d,2H),1.61-1.58 (m,1H),1.32-
1.24(m,8H),0.90-0.86(m,6H).13C NMR(100MHz,CDCl3):δ150.17, 143.93,139.56,
134.75,124.64,113.78,113.03,39.85,33.37,32.38,28.71,25.58,22.98, 14.10,10.75,
0.97.MALDI-TOF-MS(m/z):Calcd for C32H32N4S3,Exact Mass:M+568.18； Found:567.97[M+].
BTTCN synthesis:By BrRTCN (430.38mg, 1.23mmol) and (tin trimethyl) benzo of 2,5,8- tri- [1,2-B:
3,4-B':5,6-B "] three thiophene (200mg, 0.27mmol) are dissolved in inside the microwave tube equipped with 4ml chlorobenzene, are then added
The tetra-triphenylphosphine palladium of 10mg, which is placed on inside microwave reactor, to react 15 minutes for 150 DEG C.Then ice water quenching reaction uses dichloromethane
Alkane and water distinguish extracting and washing three times, with anhydrous magnesium sulfate drying, filtering and concentrating.It is mixed using petroleum ether and methylene chloride molten
Agent carries out column Chromatographic purification, obtains red solid BTTCN (230.9mg, 80.2%)1H NMR(400MHz,CDCl3):δ7.83
(s,3H),7.80(s,3H),7.58(s, 3H),2.93-2.91(d,6H),1.75-1.69(m,3H),1.40-1.28(m,
24H),0.90-0.85(m,18H).13C NMR(100MHz,CDCl3):δ150.09,142.55,142.16,141.62,
134.23,133.73,133.57, 131.33,122.99,113.96,113.17,40.25,33.47,32.57,28.76,
25.78,23.00,14.09,10.76, 1.02.MALDI-TOF-MS(m/z):Calcd for C32H32N4S3,Exact
Mass:M+568.18；Found: 567.97[M+]。
The nuclear magnetic resoance spectrum of acceptor material BTTCN as shown in Figure 1, mass spectrogram as shown in Fig. 2, film absorption spectrogram such as
Shown in Fig. 3, electrochemistry cyclic voltammogram is as shown in figure 4, DSC differential scanning calorimetry analysis result is as shown in Figure 5.
Embodiment 2：The synthesis of BTTIC：
When end group A is selected from group A8, reaction route 2：
Prepare the intermediate of BTTIC：
The synthesis step of BrRTIC：By BrRTCHO (200mg, 0.66mmol) and (3- oxo -2,3- dihydro -1H- indenes -
1- subunit) malononitrile (154.2mg, 0.79mmol) is added in 20mL chloroform.Then the triethylamine teeter chamber of 0.1mL is added
Temperature one hour of reaction.Then ice water quenching reaction uses methylene chloride and water to distinguish extracting and washing three times, dry with anhydrous magnesium sulfate
Dry, filtering and concentrating.Carry out column Chromatographic purification using petroleum ether and methylene chloride mixed solvent, obtain BrRTIC (256.9mg,
81.2%).1H NMR(400MHz,CDCl3):δ7.71(s,1H),7.69(s,3H),7.68(t, 3H),7.52(s,3H),
7.33(t,3H),7.38(s,1H),2.54-2.53(d,2H),1.61-1.58(m,1H),1.32-1.24 (m,8H),0.90-
0.86(m,6H).13C NMR(100MHz,CDCl3):δ161.61,161.01,159.53,158.31, 157.66,157.01,
156.54,155.21,154.01,153.11,150.17,143.93,139.56,134.75,124.64, 113.78,
113.03,39.85,33.37,32.38,28.71,25.58,22.98,14.10,10.75,0.97. MALDI-TOF-MS(m/
z):Calcd for C25H23BrN2OS,Exact Mass:M+478.07；Found:478.2 [M+].
The synthesis of BTTIC:By BrRTIC (589.17mg, 1.23mmol) and (tin trimethyl) benzo of 2,5,8- tri- [1,2-
B:3,4-B':5,6-B "] three thiophene (200mg, 0.27mmol) are dissolved in inside the microwave tube equipped with 4ml chlorobenzene, are then added
The tetra-triphenylphosphine palladium of 10mg, which is placed on inside microwave reactor, to react 15 minutes for 150 DEG C.Then ice water quenching reaction uses dichloromethane
Alkane and water distinguish extracting and washing three times, with anhydrous magnesium sulfate drying, filtering and concentrating.It is mixed using petroleum ether and methylene chloride molten
Agent carries out column Chromatographic purification, obtains black solid BTTIC (230.8mg, 80.2%)1H NMR(400MHz,CDCl3):δ7.83
(s,3H),7.80(s,3H),7.72(t, 3H),7.57(s,3H),7.36(t,3H),7.35(t,3H),7.32(t,3H),
2.94-2.90(d,6H),1.74-1.68 (m,3H),1.41-1.27(m,24H),0.91-0.86(m,18H).13C NMR
(100MHz,CDCl3):δ 162.21,161,33,160.25,159.66,159.01,158.33,157.89,158.11,
157.66,157.01, 156.66,156.04,155.47,150.09,142.45,142.26,141.52,134.27,
133.75,133.51, 131.32,122.94,113.92,113.18,40.22,33.41,32.55,28.73,25.72,
23.10,14.03,10.71, 1.05.MALDI-TOF-MS(m/z):Calcd for C87H72N6N3S6,Exact Mass:M+
1440.40； Found:1440.88[M+]。
The mass spectrogram of acceptor material BTTIC is as shown in Figure 6.
Embodiment 3：Product BTTCN in embodiment 1 is applied to organic photovoltaic devices, device construction method and its property
Energy parameter is as follows：
Device 1：Target product BTTCN in embodiment 1 is blended with commercialized polymer donor material PTB7-Th, with
Chloroform is solvent, and preparing device architecture is ITO/ZnO/PTB7-th:BTTCN(1:1.5)/MoO3The organic photovoltaic devices of/Ag,
The thickness of its active layer is about 90nm.
Device 2：By the target product BTTCN and commercialized PTB7-Th and fullerene electron acceptor in embodiment 1
Material PC71BM is blended, and with chlorobenzene/1,8- diiodo-octane as solvent, preparing device architecture is ITO/ZnO/PTB7- th:
PC71BM:BTTCN(1:1.5:0.03)/MoO3The organic photovoltaic devices of/Ag, the thickness of active layer are about 100nm.
Reference device preparation：By commercialized polymer donor material PTB7-Th and PC71BM is blended, with chlorobenzene/1,8-
For diiodo-octane as solvent, preparing device architecture is ITO/ZnO/PTB7-th:PC71BM(1:1.5)/MoO3Organic light of/Ag
Device is lied prostrate, the thickness of active layer is about 100nm.The voltage-current curve of these three organic solar batteries is shown in Fig. 7.
We are it can be found that based on product BTTCN obtained in embodiment 1 in its light of duel cell from experimental result
Electrotransformation efficiency has reached 3.1%.In addition, more importantly the open-circuit voltage of the duel cell based on BTTCN is up to
1.03V very high open-circuit voltage.In addition, we add in traditional activated layer medium in such a way that ternary material is blended
After adding minimal amount of BTTCN (3%w/w), which, which plays, provides new transmission for electronics to/acceptor interface regulating and controlling effect
Device photoelectric transfer efficiency has successfully been increased to 9.9% from the efficiency (8.5%) of fullerene reference device, shown by channel
The multiple use that the material regulates and controls in organic solar batteries with electron acceptor and interface.
Embodiment 4：Product BTTIC in embodiment 2 is applied to organic photovoltaic devices, device architecture and embodiment 3 are same
Prepared by the method for reason, the voltage-current curve of three kinds of organic solar batteries is shown in Fig. 8.Its performance parameter is as follows：
We are it can be found that based on product BTTIC obtained in embodiment 2 in its light of duel cell from experimental result
Electrotransformation efficiency has reached 6.8%.In addition, more importantly the open-circuit voltage of the duel cell based on BTTIC is up to
1.06V high open-circuit voltage.In addition, we are in such a way that ternary material is blended, in traditional activated layer medium
After BTTIC (3%w/w), successfully device photoelectric transfer efficiency is increased to from the efficiency (8.4%) of fullerene reference device
10.2%, show the multiple use that the material regulates and controls in organic solar batteries with electron acceptor and interface.
Organic solar batteries electron acceptor material of the invention shows excellent exciton dissociation ability, has good
Thermal stability, electrical stability and solution processability energy, and it is convieniently synthesized, be easy to purify, it is low in cost, be fullerene
The potential replacer of electron acceptor.Be suitable for non-fullerene electron acceptor material be widely used in prepare high-performance it is organic too
Positive energy battery device.
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of organic solar batteries electron acceptor material, it is characterised in that：Using three thiophene of benzo as core, with several thiophene
Organic solar batteries electron acceptor material is constructed using strong electron-withdrawing group group as end group for unit bridges；General structure structure is as follows
Shown in formula 1：
Wherein, it is integer that n, which is the quantity of thiophene unit, 0≤n≤10, and n,；
R1、R2Independent is hydrogen atom, C1~C30Alkyl chain, C1~C30Oxyalkyl chain, C5~C30Naphthenic base or C2
~C30One of miscellaneous alkyl chain；
End group A is selected from one of following group A1-A16：
Wherein, * is link position；C is carbon atom；H is hydrogen atom；O is oxygen atom；N is nitrogen-atoms；F is fluorine atom.
2. organic solar batteries electron acceptor material according to claim 1, it is characterised in that：The n is thiophene
The quantity of unit, preferably n=1,2 or 3；The R1、R2Independent is hydrogen atom, C1~C10Alkyl chain, C1~
C10Oxyalkyl chain, C5~C10One of naphthenic base chain.
3. the preparation method of organic solar batteries electron acceptor material according to claim 2, it is characterised in that：It is described
R1、R2Independent is hydrogen atom, C1~C10Straight chained alkyl or C1~C10One of branched alkyl.
4. the preparation method of organic solar batteries electron acceptor material according to claim 2, it is characterised in that：It is described
N be thiophene unit quantity, preferably n=1,2；The R1、R2Independent is hydrogen atom, C1~C10Straight chain alkane
Base, C1~C10One of branched alkyl, C5~C10One of naphthenic base chain, including following structural formula：
5. the preparation method of organic solar batteries electron acceptor material according to any one of claims 1 to 4, feature exist
In：Borneo camphor Wen Gaier Knoevenagel condensation reaction is carried out with the thiophene aldehyde radical with bromine using end group and generates intermediate, then will
The tin reagent of intermediate and three thiophene of benzo carries out Stille coupling reaction and generates final product.
6. the preparation method of organic solar batteries electron acceptor material according to claim 5, it is characterised in that：Specifically
Include the following steps：
Step 1：End group and bromo alkyl thiophene aldehyde are dissolved in chloroform, bromo alkyl thiophene aldehyde molar equivalent number is instilled
0.1% triethylamine stirring one hour of room temperature reaction, after extracting and washing, drying, filtering and concentrating, during column Chromatographic purification obtains
Mesosome BrRTCN；
Step 2：Intermediate and three thiophene tin reagent of benzo are added to inside microwave tube, chlorobenzene dissolution substrate is simultaneously bubbled with nitrogen
Then deoxygenation is added the tetra-triphenylphosphine palladium of three thiophene molar equivalent number 3% of benzo, microwave tube is finally placed on microwave reactor
It reacts 15 minutes 150 DEG C of the inside；After extracting and washing, drying, filtering and concentrating, column Chromatographic purification obtains final product BTTCN.
7. the preparation method of organic solar batteries electron acceptor material according to claim 6, it is characterised in that：Step
In 1, the molar ratio range of the end group and bromo alkyl thiophene aldehyde is 0.01:1-100:1；Bromo alkyl thiophene aldehyde is in chlorine herein
Solute concentration is 0.01-100mg/mL in imitative.
8. the preparation method of organic solar batteries electron acceptor material according to claim 6, it is characterised in that：Step
In 2, the molar ratio range of the intermediate and three thiophene tin reagent of benzo is 0.01:1~100:1；Three thiophene tin of benzo herein
Solute concentration is 0.01~500mg/mL to reagent in a solvent.
9. the preparation method of organic solar batteries electron acceptor material according to claim 6, it is characterised in that：Step
In 2, the dosage of triethylamine is the 0.001%-50% of substrate equivalents, and the dosage of tetra-triphenylphosphine palladium is substrate equivalents
0.01%-10%.
10. the application of organic solar batteries electron acceptor material according to any one of claims 1 to 6, it is characterised in that：
The material is used for binary or polynary organic solar batteries device as electron acceptor material.
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| CN110194778A (en) * | 2019-06-11 | 2019-09-03 | 南京邮电大学 | A kind of multi-arm structure organic photovoltaic material and the preparation method and application thereof |
| WO2020119503A1 (en) * | 2018-12-10 | 2020-06-18 | 广州华睿光电材料有限公司 | Organic electroluminescent device comprising light extraction layer, heteroatom polyaromatic ring compound, and composition |
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| CN113480560A (en) * | 2021-06-17 | 2021-10-08 | 南京邮电大学 | Preparation method of non-fullerene electron acceptor, product and application |
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