CN108794732B - A kind of side's acids high molecular polymer, preparation method and application - Google Patents
A kind of side's acids high molecular polymer, preparation method and application Download PDFInfo
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Abstract
The invention belongs to (OSCs) in organic solar batteries and the field of new materials in perovskite solar battery (PVSCs), more particularly, to a kind of side's acids high molecular polymer, preparation method and application.The high molecular polymer is covalently attached the segment to be formed as copolymerization units using asymmetry side's acid and indacene 1,4-Dithiapentalene, the high molecular polymer synthesis process is simple, photo absorption performance is good, hole mobility is high, the hole mobile material that can be respectively applied in organic solar batteries donor material and trans- perovskite solar battery, gained peak efficiency are respectively 6.35% and 18.29%.
Description
Technical field
The invention belongs to (OSCs) in organic solar batteries and the new material in perovskite solar battery (PVSCs) to lead
Domain, more particularly, to a kind of side's acids high molecular polymer, preparation method and application.
Background technique
Inorganic solar cell is the maturing appts with relatively high solar energy conversion efficiency, can reach about 15-20%,
Therefore, it has become the dominant technologies of photovoltaic industry.However, it is contemplated that growth of the whole world to electricity needs, in addition inorganic solar energy
The high cost and relevant environment problem of battery hamper their extensive use to a certain extent, and researcher is all promoted to make great efforts to visit
The alternative materials of rope alternative inorganic semiconductor.Organic solar batteries (hereinafter referred to as OSCs) have low cost and can be a large amount of
The characteristics of production, and energy level is easy to regulate and control, and can form light-duty, flexible device, has incomparable compared with inorganic semiconductor
Advantage.In consideration of it, having been extensively studied the performance for being dedicated to understanding and improve OSCs, the especially conjunction of new material all over the world
At and application.
In organic solar batteries donor material, high-molecular compound is a kind of important material, has good film-forming property,
Processing performance is excellent, the high feature of energy conversion efficiency (PCE), therefore has numerous researchs and be dedicated to macromolecule donor new material
Synthesis and application.Square acid is the organic dye molecule of a quasi-tradition, have raw material are cheap, synthesis is simple, absorptivity is big,
The features such as molecular conjugation degree is high, thus there is when as donor material unique advantage.It is organic to have some side's acids at present
Small molecule material is synthesized and is applied in the active layer donor material of OSCs, can get the photoelectric conversion efficiency of highest 7%.So
And square acids organic conjugate polymer material is but seldom by the active layer donor material as OSCs, in only several reports,
Gained photoelectric conversion efficiency is only 1% or so.Currently, the square acids conjugated polymer side of the being all based on acid of most reports is small
The homopolymer of molecule causes to cause exciton dissociation ineffective there are the effect of very strong electronics coupled between monomer.In addition, side
Sour homopolymer is there is also dissolubility, processing performance are bad, and the problems such as compatibility is poor between fullerene acceptor molecule.It is comprehensive
On, it is badly in need of photovoltaic performance of the exploitation novel polymeric strategy to the side's of raising acids conjugated polymer.
In addition, perovskite as a kind of hybrid inorganic-organic active material in recent decades in solar cells
It is widely applied, it is the effective material that can be matched in excellence or beauty with traditional inorganic monocrystalline silicon semiconductor that peak efficiency, which has broken through 22%,.In perovskite
It is typically required for the presence of hole mobile material in solar battery (hereinafter referred to as PVSCs) with stable hole and transmits injection just
Pole, the hole mobile material being widely used in trans- device at present are PEDOT-PSS, which has conductivity height, infiltration
Property good feature, but unfortunately its work function mismatches, and molecule has acid with water suction property, is unfavorable for battery device
Stability.Therefore, design synthesizing new organic hole transport material with have both efficiently and stability PVSCs research in seem
It is most important.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of side's acids high molecular polymer,
Preparation method and application, its object is to by synthesizing a kind of side using asymmetry side's acid and indacene 1,4-Dithiapentalene as monomer
Acids high molecular polymer, and be applied in solar cell material, accordingly obtain a kind of good height of photovoltaic performance
Thus Molecularly Imprinted Polymer material solves prior art small molecule side acrylic materials and turns as solar battery active layer material photoelectricity
It changes low efficiency and existing perovskite solar battery hole transmission layer work function mismatches, influences the technology of stability test
Problem.
To achieve the above object, according to one aspect of the present invention, a kind of side's acids high molecular polymer is provided, with
Asymmetry side's acid be connected with indacene 1,4-Dithiapentalene after segment as copolymerization units, and the asymmetry side is sour and indacene
1,4-Dithiapentalene is coupled by Stille to form C -- C single bond after be connected.
Preferably, two end groups of asymmetry side's acid are respectively 1,3,3- trimethylbenzene diindyls and 4- (N, N
Diphenylamines) -2,6 dihydroxy benzenes.
Preferably, the high molecular polymer has the general structure as shown in formula (one):
Wherein, n 20-30.
Other side according to the invention provides the preparation method of square acids high molecular polymer described in one kind,
Include the following steps:
(1) by asymmetry side's acid compound and the tin trimethyl reagent of indacene 1,4-Dithiapentalene according to molar ratio 1:1~1:
1.1 dissolutions in organic solvent, catalyst and ligand are added under inert atmosphere protection, is warming up to reflux, with this condition instead
It answers 48-72 hours, end-capping reagent, the reaction system after being blocked is added；
(2) reaction system after step (1) described sealing end is cooled to room temperature, then mixes, is separated by solid-liquid separation with methanol
To precipitating, which is successively subjected to Soxhlet extraction using methanol, acetone, n-hexane, chloroform as solvent, resulting chloroform is mentioned
It is mixed again with methanol after taking liquid to be concentrated, obtains solidliquid mixture, solid-liquid separation solid, the solid obtains after washing, drying
Side's acids high molecular polymer.
Preferably, step (1) catalyst is Pd2(dba)3, the ligand is three (o-tolyl) phosphines.
Preferably, step (1) end-capping reagent is 2- bromothiophene and 2- tributyltin thiophene, and the end-capping reagent is added
When 2- bromothiophene is first added, add 2- tributyltin thiophene.
Other side according to the invention provides the application of square acids high molecular polymer described in one kind, as
Semiconducting polymer's material is applied to area of solar cell.
Preferably, which is used as the active layer material of organic solar batteries.
Preferably, which is used as the hole mobile material of perovskite solar battery.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) the present invention provides a kind of side's acids high molecular polymers, and it includes asymmetry side's acid and indacene and two thiophenes
Two copolymerization units of pheno.
(2) the present invention provides a kind of preparation method of side's acids high molecular polymer, preparation method is simple, yield
Height, it is reproducible.
(3) side's acids high molecular polymer provided by the invention has suitable extinction model as semiconducting polymer's material
It encloses and molecular entergy level, can be applied in body heterojunction organic solar batteries.It is 100mW cm in intensity of illumination-2Simulation too
Under sunlight AM 1.5G irradiation condition, highest PCE value can reach 6.35%.
(4) side's acids high molecular polymer hole mobility with higher provided by the invention, can be used as undoped sky
Hole transport materials.When it is applied in trans- planar structure perovskite solar battery, very high photoelectric conversion effect is shown
Rate reaches as high as 18.29%.
Detailed description of the invention
Fig. 1 is the structural formula of present invention side's acids high molecular polymer.
Fig. 2 is the synthetic route chart of the P1 of embodiment 1.
Fig. 3 is the hydrogen nuclear magnetic spectrogram of the P1 of embodiment 1.
Fig. 4 is the uv-visible absorption spectra of the P1 of embodiment 1.
Fig. 5 is the cyclic voltammetry curve of the P1 of embodiment 1.
Fig. 6 is that the P1 of embodiment 1 makees donor material applied to the optimal device J-V curve in OSCs.
Fig. 7 is optimal device J-V curve of the P1 of embodiment 1 as PVSCs hole mobile material.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
A kind of side's acids high molecular polymer provided by the invention is connected with asymmetry side's acid with indacene 1,4-Dithiapentalene
Segment after connecing is as copolymerization units, and asymmetry side acid and indacene 1,4-Dithiapentalene are coupled to form C-C by Stille
It is connected after singly-bound.Two end groups of preferably scheme, asymmetry side's acid are respectively 1,3,3- trimethylbenzene diindyls and 4-
(N, N diphenylamines) -2,6 dihydroxy benzenes, the high molecular polymer can be used as a kind of semiconducting polymer's material be applied to it is organic too
Positive energy battery or trans- perovskite field of solar energy, photoelectric conversion efficiency height with higher and hole mobility.
The polymer is represented by the general structure as shown in formula (one):
Wherein, n 20-30, high molecular polymer within this range can serve as solar cell material, and have compared with
High photoelectric conversion efficiency.
A kind of preparation method of square acids high molecular polymer of the invention, includes the following steps:
(1) by asymmetry side acid compound I and the tin trimethyl reagent of indacene 1,4-Dithiapentalene according to molar ratio 1:1~1:
1.1 dissolutions in organic solvent, catalyst and ligand are added under inert atmosphere protection, is warming up to reflux, with this condition instead
It answers 48-72 hours, end-capping reagent, the reaction system after being blocked is added；Preferably, catalyst Pd2(dba)3, ligand three
(o-tolyl) phosphine.End-capping reagent is 2- bromothiophene and 2- tributyltin thiophene, and to ensure to block completely, the sealing end is added
2- bromothiophene is first added when agent, adds 2- tributyltin thiophene.
(2) reaction system after step (1) described sealing end is cooled to room temperature, is then mixed with methanol, remove small molecule
Monomer, separation of solid and liquid are precipitated, which is successively carried out Soxhlet as solvent using methanol, acetone, n-hexane, chloroform and is mentioned
It takes, will mix again with methanol after the concentration of resulting chloroform extracted solution, and obtain solidliquid mixture, solid-liquid separation solid, wash,
The solid obtains side's acids high molecular polymer after drying.Here it different solvents is respectively adopted successively carries out Soxhlet and mention
It takes, its object is to remove the oligomer of different molecular weight ranges respectively, molecular weight ranges is poly- in final acquisition target interval
Close object.
The application of square acids high molecular polymer of the invention can be used as semiconducting polymer's material applied to solar-electricity
Pond field, including being used as the active layer material of organic solar batteries or as the hole transport material of perovskite solar battery
Material.
The present invention provides a kind of side's acids high molecular polymers, and with general structure as shown in Figure 1, it includes not
Symmetrical side's acid and indacene 1,4-Dithiapentalene (IDT) two copolymerization units, the present invention are sour with indacene 1,4-Dithiapentalene by asymmetry side
It is coupled by Stille and realizes that C-C is covalently keyed.Square acids molecule usually haves the defects that self aggregation is too strong, and passes through copolymerization
Reaction, which introduces IDT unit, can inhibit intermolecular strong aggregation, improve high molecular dissolubility and processing performance.In addition, by the two
In conjunction with high molecular polymer is made, can the side's of making up acids molecule light absorption range it is narrow and phase point easily occurs for while mixing with fullerene acceptor
From defect, and then improve material photovoltaic performance.
The present invention provides a kind of synthetic methods of side's acids high molecular polymer, and the sun can be applied to by also providing one kind
The novel high molecular polymer material of energy field of batteries.Side's acids high molecular polymer hole with higher provided by the invention
Mobility can be used as undoped hole mobile material.When it is applied in trans- planar structure perovskite solar battery, table
Reveal very high photoelectric conversion efficiency, reaches as high as 18.29%.
The following are embodiments:
Embodiment 1
A kind of side's acids high molecular polymer P1, synthetic route is as shown in Fig. 2, first no by 90mg (0.1mmol)
The tin trimethyl reagent (IDT-Sn) of the indacene 1,4-Dithiapentalene of symmetrical side's acid compound 1,151mg (0.1mmol) is dissolved in 8mL
Dry toluene in and fill row argon gas 6 times, then under protection of argon gas be added 3.4mg (0.004mmol) Pd2(dba)3With
Three (o-tolyl) phosphines of 4.5mg (0.015mmol).The system is warming up to reflux and with this condition reaction two days, then
2- bromothiophene and 2- tributyltin thiophene are sequentially added as end-capping reagent.Then reaction system is cooled to room temperature and pours into first
In alcohol, the solid particulate filters being settled out are collected and successively with methanol, acetone, n-hexane, chloroform Soxhlet extraction, resulting chlorine
It pours into methanol and precipitates again after imitative extracting solution concentration, obtained solid can obtain depth after filtering, methanol are washed and is dried in vacuo
Green product (150mg).
1H NMR(400MHz,CDCl3)δ12.21(ArH),8.19(ArH),7.96(ArH),7.64(ArH),7.57-
7.47(ArH),7.46-7.37(ArH),7.24-7.20(ArH),7.20-7.12(ArH),7.12-7.03(ArH),6.04-
5.90 (ArH ,-C=CH), 3.82 (- NCH3),2.61-2.48(-CH2-),2.00(-(CH3)2),1.39-1.19(-CH2-),
0.95-0.78(-CH3).Mw:38600；PDI:2.68.
The hydrogen nuclear magnetic spectrogram of P1 is shown in that Fig. 3, uv-visible absorption spectra are shown in that Fig. 4, cyclic voltammetry curve are shown in Fig. 5, wherein solution
In ultraviolet-ray visible absorbing be after 0.01 milligram every milliliter of P1 dissolves in chloroform through SHIMADZU UV-3600 it is ultraviolet-can
See that spectrophotometer measures.Wherein, the film of P1 and solution absorb the range that can cover 300-800nm, through cyclic voltammetric song
Line and optical band gap calculate polymer HOMO energy level be -5.16eV, lumo energy be -3.61eV.
In the present embodiment side's acids high molecular polymer preparation method, when polymerization reaction occurs for square acids molecule and IDT,
This is as uncontrollable polymerization, but under the above conditions, and when repeating to test, in 20000-40000g/mol, i.e., molecular weight can be stablized
N in counter structure general formula (one) is 20-30, and repeatability is preferably.
Embodiment 2
Embodiment 1 is synthesized to the device that obtained high molecular polymer P1 is used as donor material in OSCs.
When P1 is made donor material applied in OSCs, using specific device architecture is ITO/MoO3/P1:PC71BM/
BCP/Al is 100mW cm in intensity of illumination-2Simulated solar irradiation AM 1.5G irradiation condition under, highest PCE value can reach
6.35%, device J-V curve is as shown in Figure 6.
Embodiment 3
Embodiment 1 is synthesized to the device that obtained high molecular polymer P1 is used as hole mobile material in the trans- device of PVSCs
Part.It is 4.11 × 10 using the hole mobility that the method for space charge limit value electric current measures P1-5cm2V-1s-1, show that it has
Higher hole mobility can satisfy the requirement of hole mobile material in perovskite solar battery.It is passed P1 as hole
Defeated material is applied in the trans- device of perovskite solar battery, specific structure ITO/P1/Perovskite/C60/BCP/
Ag, the J-V curve of optimal device is as shown in fig. 7, PCE reaches as high as 18.29%.
Above-mentioned side's acids high molecular polymer is used as the active layer material or perovskite solar-electricity of organic solar batteries
When the hole mobile material of pond, wherein combination of devices mode is not limited in above-described embodiment, and other materials layer is conventional in device
Solar cell material type.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of side's acids high molecular polymer, which is characterized in that it is connected with asymmetry side's acid with indacene 1,4-Dithiapentalene
Segment afterwards is as copolymerization units, and asymmetry side acid and indacene 1,4-Dithiapentalene are coupled that form C-C mono- by Stille
It is connected after key；
The high molecular polymer has the general structure as shown in formula (one):
Wherein, n 20-30.
2. a kind of preparation method of side's acids high molecular polymer, which comprises the steps of:
(1) by asymmetry side acid compound I and the tin trimethyl reagent II of indacene 1,4-Dithiapentalene according to molar ratio 1:1~1:
1.1 dissolutions in organic solvent, catalyst and ligand are added under inert atmosphere protection, is warming up to reflux, with this condition instead
It answers 48-72 hours, end-capping reagent, the reaction system after being blocked is added；Wherein, asymmetry side's acid compound I has such as
Under structural formula:
The tin trimethyl reagent II of the indacene 1,4-Dithiapentalene has following structural formula:
(2) reaction system after step (1) described sealing end is cooled to room temperature, is then mixed with methanol, separation of solid and liquid is sunk
It forms sediment, which is successively subjected to Soxhlet extraction using methanol, acetone, n-hexane, chloroform as solvent, by resulting chloroform extracted solution
It is mixed again with methanol after concentration, obtains solidliquid mixture, solid-liquid separation solid obtains after washing, the dry solid described
Square acids high molecular polymer.
3. preparation method as claimed in claim 2, which is characterized in that step (1) catalyst is Pd2(dba)3, described to match
Body is three (o-tolyl) phosphines.
4. preparation method as claimed in claim 2, which is characterized in that step (1) end-capping reagent is 2- bromothiophene and 2- (three
Butyl tinbase) thiophene, and 2- bromothiophene is first added when the addition end-capping reagent, add 2- (tributyltin) thiophene.
5. the application of side's acids high molecular polymer as described in claim 1, which is characterized in that as semiconducting polymer's material
Material is applied to area of solar cell.
6. application as claimed in claim 5, which is characterized in that the high molecular polymer is used as the activity of organic solar batteries
Layer material.
7. application as claimed in claim 5, which is characterized in that the high molecular polymer is used as the sky of perovskite solar battery
Hole transport materials.
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| CN201810639555.9A CN108794732B (en) | 2018-06-20 | 2018-06-20 | A kind of side's acids high molecular polymer, preparation method and application |
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| CN103848964A (en) * | 2012-11-28 | 2014-06-11 | 海洋王照明科技股份有限公司 | Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device |
| CN105885019A (en) * | 2016-04-15 | 2016-08-24 | 东南大学 | Electrochromic material based on triphenylamine conjugated polymer as well as preparation method and application of electrochromic material |
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| CN103848964A (en) * | 2012-11-28 | 2014-06-11 | 海洋王照明科技股份有限公司 | Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device |
| CN105885019A (en) * | 2016-04-15 | 2016-08-24 | 东南大学 | Electrochromic material based on triphenylamine conjugated polymer as well as preparation method and application of electrochromic material |
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| Synthesis, structure and material properties of thiopyranylidene-based asymmetrical squaraines;Qi Xiao，et al.;《Dyes and Pigments》;20180303;137-144 * |
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