CN105244443A - Transparent electrode and preparation method thereof, and organic solar cell - Google Patents
Transparent electrode and preparation method thereof, and organic solar cell Download PDFInfo
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- 229920001940 conductive polymer Polymers 0.000 claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 71
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- 239000002322 conducting polymer Substances 0.000 claims description 68
- 229920000642 polymer Polymers 0.000 claims description 46
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- 239000011259 mixed solution Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
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- 238000004528 spin coating Methods 0.000 claims description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
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- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 5
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- 238000010438 heat treatment Methods 0.000 claims description 4
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- 239000002131 composite material Substances 0.000 abstract description 10
- 229920002521 macromolecule Polymers 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 7
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- 239000008367 deionised water Substances 0.000 description 4
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
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- 238000012986 modification Methods 0.000 description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- -1 ITO Chemical compound 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
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Classifications
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
A first aspect of the embodiments of the invention provides a transparent electrode. The transparent electrode comprises a substrate and a transparent conductive film arranged on the surface of the substrate. The materials of the transparent conductive film include a graphene material and a conductive polymer of which the chemical structural formula is shown in formula (I), the graphene material includes graphene or doped graphene, and the graphene material is evenly dispersed in the transparent conductive film. As the side chain of the conductive polymer contains no long alkyl chain, the oil solubility is low, and the conductive polymer is less susceptible to corrosion of oil-soluble solvents in the subsequent application. Therefore, the stability of the transparent electrode is improved, and the problem in the prior art that the conductive macromolecule layer of the graphene conductive macromolecule composite transparent electrode fails as the conductive macromolecule layer is susceptible to corrosion of oil-soluble solvents is solved. The embodiments of the invention further provide a preparation method of the transparent electrode and an organic solar cell containing the transparent electrode.
Description
Technical field
The present invention relates to electrode technology field, particularly a kind of transparency electrode and preparation method thereof and organic solar batteries.
Background technology
Current, the most frequently used transparent electrode material is metal oxide based on conventional inorganic material or fluoride, such as ITO, IZO or FTO etc., but along with rare metal increasingly deficient, price is growing and the problem such as the complexity of transparent conductive film poor heat stability, flexible difference and preparation process, limits their application in photoelectric functional devices field.Therefore, exploitation has abundant raw materials, cheap, flexible, the electrode material that transparent and electrically conductive is high, significant to field development such as photoelectric functional devices.
Graphene is owing to having high mobility, and excellent mechanical performance and the excellent specific property such as good light transmission and thermal stability, become the new material of the transparency electrodes such as the current existing ITO of the most potential replacement.But the large-area graphene can prepared at present is polycrystalline structure, has more defect and crystal boundary, greatly have impact on its photoelectric properties.In order to address this problem, industry has prepared a kind of graphene composite transparent electrode, and this transparency electrode is provided with graphene layer and electroconductive polymer layer in flexible transparent substrate; This graphene composite transparent electrode combines the advantage of both conducting polymer and Graphene, has excellent photoelectric properties and flexibility.But this transparency electrode is when the later stage is applied, such as when active layer is prepared on this transparency electrode surface, usually active layer material is dissolved in oil-dissolving solvent as after chlorobenzene again transparency electrode surface spin coating, spin coating process oil-soluble solvent meeting corrosion electroconductive polymer layer, will cause the inefficacy of electroconductive polymer layer.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of transparency electrode, in order to solve in graphene conductive macromolecule composite transparent electrode of the prior art, because conducting polymer is easily by oil-dissolving solvent corrosion, cause the problem that electroconductive polymer layer lost efficacy.
First aspect, embodiments provide a kind of transparency electrode, comprise substrate and be arranged on the transparent conductive film of described substrate surface, the material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), described grapheme material comprises Graphene or doped graphene, described grapheme material is dispersed in described transparent conductive film
formula (I),
Wherein, n is 10 ~ 30.
In embodiment of the present invention, in described transparent conductive film, the mass ratio of described conducting polymer and described grapheme material is 1:1 ~ 10:1.
In embodiment of the present invention, the number of plies of described grapheme material is single or multiple lift.
In embodiment of the present invention, described doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, the material of described substrate is glass, polyimides, PETG, PEN, polymethyl methacrylate, Merlon or polyurethane.
In embodiment of the present invention, the thickness of described transparent conductive film is 1 ~ 10nm.
The transparency electrode that embodiment of the present invention first aspect provides, its transparent conductive film comprises the conducting polymer shown in formula (I), the side chain of this conducting polymer is not containing long alkyl chain, the oil-soluble of conducting polymer is lower, therefore in subsequent applications, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, solve in prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by problem that oil-dissolving solvent corrosion causes electroconductive polymer layer to lose efficacy.
Second aspect, embodiments provides a kind of preparation method of transparency electrode, comprises the following steps:
Substrate is provided, grapheme material and chemical structural formula is dissolved in polar solvent such as formula the polymer shown in (II), obtains mixed solution; Described mixed solution is coated in described substrate surface and forms film; Described grapheme material comprises Graphene or doped graphene
formula (II); Wherein, R to be carbon number be 4 ~ 15 alkyl, n is 10 ~ 30;
Heat described film, make described chemical structural formula such as formula the polymer generation pyrolytic reaction shown in (II), generate chemical structural formula such as formula the conducting polymer shown in (I), obtain transparent conductive film, thus obtain transparency electrode; The material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), and described grapheme material is dispersed in described transparent conductive film,
formula (I),
Wherein, n is 10 ~ 30.
In embodiment of the present invention, described R is 1, Isosorbide-5-Nitrae, 8-tetramethyl nonyl.
In embodiment of the present invention, in described mixed solution, described chemical structural formula is 1 ~ 10g/L such as formula the concentration of the polymer shown in (II), and the concentration of described grapheme material is 0.1 ~ 3g/L.
In embodiment of the present invention, described polar solvent is at least one in water, ethanol, acetonitrile, acetone, oxolane and dimethyl formamide.
In embodiment of the present invention, the method for described coating comprises spin coating, spraying or blade coating.
In embodiment of the present invention, described heating-up temperature is 150 DEG C ~ 250 DEG C, and heating time is 0.5 ~ 1h.
In embodiment of the present invention, in described transparent conductive film, the mass ratio of described conducting polymer and described grapheme material is 1:1 ~ 10:1.
In embodiment of the present invention, the number of plies of described grapheme material is single or multiple lift.
In embodiment of the present invention, described doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, the material of described substrate is glass, polyimides, PETG, PEN, polymethyl methacrylate, Merlon or polyurethane.
In embodiment of the present invention, the thickness of described transparent conductive film is 1 ~ 10nm.
In embodiment of the present invention, described chemical structural formula adopts following methods to prepare such as formula the polymer shown in (II):
Under oxygen-free environment, by equimolar ratio such as formula shown in (3) compound and dissolve in being added into containing catalyst solvent such as formula the compound shown in (4), obtain reactant liquor, described reactant liquor is carried out suzuki coupling reaction at 85 DEG C ~ 110 DEG C, reaction time is 12 ~ 48 hours, and obtained chemical structural formula is such as formula the polymer shown in (II);
wherein, R to be carbon number be 4 ~ 15 alkyl.
In embodiment of the present invention, described solvent is the mixed liquor of toluene or oxolane and sodium carbonate formation.
In embodiment of the present invention, described catalyst is that four (triphenyl phosphorus) close palladium or dichloro two (triphenyl phosphorus) closes palladium.
The preparation method of the transparency electrode that embodiment of the present invention second aspect provides, technique is simple, and preparation cost is low, is easy to suitability for industrialized production.
The third aspect, embodiments provide a kind of organic solar batteries, comprise negative electrode, active layer and anode, described negative electrode is transparency electrode, described transparency electrode comprises substrate and is arranged on the transparent conductive film of described substrate surface, the material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), described grapheme material comprises Graphene or doped graphene, described grapheme material is dispersed in described transparent conductive film
formula (I),
Wherein, n is 10 ~ 30.
The organic solar batteries that the embodiment of the present invention third aspect provides, because the oil-soluble of the conducting polymer in the transparency electrode of employing is lower, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, adopt this transparency electrode to have good stability as the organic solar batteries of negative electrode.
To sum up, the transparency electrode that embodiment of the present invention first aspect provides, its transparent conductive film comprises the conducting polymer shown in formula (I), the side chain of this conducting polymer is not containing long alkyl chain, the oil-soluble of conducting polymer is lower, therefore in subsequent applications, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, solve in prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by problem that oil-dissolving solvent corrosion causes electroconductive polymer layer to lose efficacy.The preparation method of the transparency electrode that embodiment of the present invention second aspect provides, technique is simple, and preparation cost is low, is easy to suitability for industrialized production.The organic solar batteries that the embodiment of the present invention third aspect provides, has good stability.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can be known by the enforcement of the embodiment of the present invention.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
The transparency electrode that embodiment of the present invention first aspect provides, its transparent conductive film comprises the conducting polymer shown in formula (I), the side chain of this conducting polymer is not containing long alkyl chain, the oil-soluble of conducting polymer is lower, therefore in subsequent applications, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, solve in prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by problem that oil-dissolving solvent corrosion causes electroconductive polymer layer to lose efficacy.
First aspect, embodiments provide a kind of transparency electrode, comprise substrate and be arranged on the transparent conductive film of described substrate surface, the material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), described grapheme material comprises Graphene or doped graphene, described grapheme material is dispersed in described transparent conductive film
formula (I),
Wherein, n is 10 ~ 30.
In embodiment of the present invention, in described transparent conductive film, the mass ratio of described conducting polymer and described grapheme material is 1:1 ~ 10:1.
In embodiment of the present invention, the number of plies of described grapheme material is single or multiple lift.
In embodiment of the present invention, the number of plies of described grapheme material is 2 ~ 5 layers.
In embodiment of the present invention, described doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, described doped graphene is nitrogen-doped graphene.
In embodiment of the present invention, the material of described substrate is glass, polyimides (PI), PETG (PET), PEN (PEN), polymethyl methacrylate (PMMA), Merlon (PC) or polyurethane (PU).
In embodiment of the present invention, the thickness of described transparent conductive film is 1 ~ 10nm.
In embodiment of the present invention, described oil-dissolving solvent is the organic solvent insoluble mutually with water.
Described conducting polymer is conjugated polymer, has higher electron affinity energy, can play the effect of electrode modification layer, makes grapheme material more easily obtain electric charge.Grapheme material bonding can be got up by described conducting polymer simultaneously, serve the effect of similar binding agent, described conducting polymer and grapheme material is made to form the transparent conductive film of continous-stable, the light transmittance of the transparency electrode finally obtained is high, conductivity and having good stability, and can be advantageously applied to the fields such as organic solar batteries.
The transparency electrode that embodiment of the present invention first aspect provides, its transparent conductive film comprises the conducting polymer shown in formula (I), the side chain of this conducting polymer is not containing long alkyl chain, the oil-soluble of conducting polymer is lower, therefore in subsequent applications, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, solve in prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by problem that oil-dissolving solvent corrosion causes electroconductive polymer layer to lose efficacy.
Second aspect, embodiments provides a kind of preparation method of transparency electrode, comprises the following steps:
Substrate is provided, grapheme material and chemical structural formula is dissolved in polar solvent such as formula the polymer shown in (II), obtains mixed solution; Described mixed solution is coated in described substrate surface and forms film; Described grapheme material comprises Graphene or doped graphene,
formula (II); Wherein, R to be carbon number be 4 ~ 15 alkyl, n is 10 ~ 30;
Heat described film, make described chemical structural formula such as formula the polymer generation pyrolytic reaction shown in (II), generate chemical structural formula such as formula the conducting polymer shown in (I), obtain transparent conductive film, thus obtain transparency electrode; The material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), and described grapheme material is dispersed in described transparent conductive film,
formula (I),
Wherein, n is 10 ~ 30.
In embodiment of the present invention, described R is 1, Isosorbide-5-Nitrae, 8-tetramethyl nonyl.
In embodiment of the present invention, in described mixed solution, described chemical structural formula is 1 ~ 10g/L such as formula the concentration of the polymer shown in (II), and the concentration of described grapheme material is 0.1 ~ 3g/L.
In embodiment of the present invention, described polar solvent is at least one in water, ethanol, acetonitrile, acetone, oxolane and dimethyl formamide.
In embodiment of the present invention, the method for described coating comprises spin coating, spraying or blade coating.
In embodiment of the present invention, rotating speed during described spin coating is 500 ~ 2000r/min.
In embodiment of the present invention, described heating-up temperature is 150 DEG C ~ 250 DEG C, and heating time is 0.5 ~ 1h.
In embodiment of the present invention, in described transparent conductive film, the mass ratio of described conducting polymer and described grapheme material is 1:1 ~ 10:1.
In embodiment of the present invention, the number of plies of described grapheme material is single or multiple lift.
In embodiment of the present invention, the number of plies of described grapheme material is 2 ~ 5 layers.
In embodiment of the present invention, described doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, described doped graphene is nitrogen-doped graphene.
In embodiment of the present invention, the methods such as micromechanics stripping method, SiC thermal decomposition epitaxy growth method, chemical vapour deposition technique or chemistry redox method that described grapheme material can be reported according to document are prepared, but are not limited to these methods.
In embodiment of the present invention, described grapheme material adopts chemistry redox method to prepare.
In embodiment of the present invention, the material of described substrate is glass, polyimides, PETG, PEN, polymethyl methacrylate, Merlon or polyurethane.
In embodiment of the present invention, clean described substrate, cleaning method is: substrate surface is used water-detergent solution successively, deionized water and acetone cleaning, and is dried up by substrate surface with nitrogen.
In embodiment of the present invention, the thickness of described transparent conductive film is 1 ~ 10nm.
In embodiment of the present invention, described chemical structural formula such as formula the reaction equation of the polymer generation pyrolytic reaction shown in (II) is:
In embodiment of the present invention, described chemical structural formula adopts following methods to prepare such as formula the polymer shown in (II):
Under oxygen-free environment, by equimolar ratio such as formula shown in (3) compound and dissolve in being added into containing catalyst solvent such as formula the compound shown in (4), obtain reactant liquor, described reactant liquor is carried out suzuki coupling reaction at 85 DEG C ~ 110 DEG C, reaction time is 12 ~ 48 hours, and obtained chemical structural formula is such as formula the polymer shown in (II);
wherein, R to be carbon number be 4 ~ 15 alkyl.
The reaction equation of suzuki coupling reaction is:
In embodiment of the present invention, described solvent is the mixed liquor of toluene or oxolane and sodium carbonate formation.
In embodiment of the present invention, the mixed liquor that the aqueous sodium carbonate of described solvent to be toluene or oxolane and concentration be 2mol/L is formed, the volume ratio of described toluene or oxolane and aqueous sodium carbonate is 2:1.
In embodiment of the present invention, described catalyst is that four (triphenyl phosphorus) close palladium or dichloro two (triphenyl phosphorus) closes palladium.
Described chemical structural formula such as formula in the polymer shown in (II) containing can pyrolysis group as ester group, by described polymer with grapheme material is water-soluble or in alcohol polar solvent, after forming film by the method for coating again, to described film heating, make chemical structural formula such as formula the polymer generation pyrolysis shown in (II), thus removal affects polymer conductivity and oil-soluble long alkyl chain, the oil-soluble of conducting polymer can be reduced, improve the electric conductivity of grapheme material simultaneously.The transparency electrode finally obtained has good conductivity and stability.
Described conducting polymer is conjugated polymer, has higher electron affinity energy, can play the effect of electrode modification layer, so that the charge transport between active layer and transparency electrode.Simultaneously after pyrolytic reaction, grapheme material bonding can be got up by described conducting polymer, serves the effect of similar binding agent, makes described conducting polymer and grapheme material form the transparent conductive film of continous-stable.
Embodiment of the present invention second aspect provides a kind of preparation method of transparency electrode, and described preparation method's technique is simple, and preparation cost is low simultaneously, is easy to suitability for industrialized production.
The third aspect, embodiments provide a kind of organic solar batteries, comprise negative electrode, active layer and anode, described negative electrode is transparency electrode, described transparency electrode comprises substrate and is arranged on the transparent conductive film of described substrate surface, the material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), described grapheme material comprises Graphene or doped graphene, described grapheme material is dispersed in described transparent conductive film
formula (I),
Wherein, n is 10 ~ 30.
In embodiment of the present invention, described active layer comprises donor material and acceptor material, and described donor material and acceptor material can be the bulk heterojunction Rotating fields of mixing manufacture, also can be the duplex hetero junction layer structure that is made of film forming respectively.
In embodiment of the present invention, the selection of described donor material and acceptor material is not particularly limited, existing available all can.
In embodiment of the present invention, the material of described anode can be metal or conductive oxide, such as, the alloy of one or more in aluminium (Al), magnesium (Mg), silver (Ag), gold (Au), platinum (Pt), copper (Cu), as almag (Mg/Al), silver-colored magnesium alloy (Ag/Ag), described metal can also be layer structure, as being lithium fluoride: aluminium (LiF/Al).The manufacture method of anode adopts vapour deposition method to deposit usually, certainly also can adopt other deposition process.
The organic solar batteries that the embodiment of the present invention third aspect provides, because the oil-soluble of the conducting polymer in the transparency electrode of employing is lower, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, adopt this transparency electrode to have good stability as the organic solar batteries of negative electrode.
To sum up, the transparency electrode that embodiment of the present invention first aspect provides, its transparent conductive film comprises the conducting polymer shown in formula (I), the side chain of this conducting polymer is not containing long alkyl chain, the oil-soluble of conducting polymer is lower, therefore in subsequent applications, described conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, solve in prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by problem that oil-dissolving solvent corrosion causes electroconductive polymer layer to lose efficacy.The preparation method of the transparency electrode that embodiment of the present invention second aspect provides, technique is simple, and preparation cost is low, is easy to suitability for industrialized production.The organic solar batteries that the embodiment of the present invention third aspect provides, has good stability.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.Wherein, the embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable is changed and implements.
Embodiment one
A preparation method for transparency electrode, comprises the following steps:
(1) preparative chemistry structural formula such as formula (II a) shown in polymer, comprise the following steps:
Under oxygen-free environment, by equimolar ratio such as formula shown in (3a) compound and be added into close in the solvent of palladium containing four (triphenyl phosphorus) such as formula the compound shown in (4) and dissolve, the aqueous sodium carbonate of solvent to be toluene and concentration be 2mol/L is mixed liquor that the ratio of 2:1 is formed by volume; Obtain reactant liquor, reactant liquor is carried out suzuki coupling reaction at 85 DEG C, the reaction time is 48 hours, obtained chemical structural formula such as formula (II a) shown in polymer;
(2) adopt clear glass as substrate, glass surface is used water-detergent solution successively, deionized water, acetone cleans, and is dried up by glass surface with nitrogen;
By chemical structural formula such as formula (II a) shown in polymer and graphene dispersion in ethanol and carry out ultrasonic dissolution, obtain mixed solution, in mixed solution, the concentration of polymer is 5g/L, and the concentration of Graphene is 1.5g/L;
Mixed solution is spin-coated on transparent glass surface with the rotating speed of 1000r/min, forms the film of flat transparent;
(3) substrate of glass of film there is is to be placed in thermal station the spin coating that step (2) obtains, be heated to 200 DEG C, chemical structural formula such as formula (II a) shown in polymer generation pyrolytic reaction, generate such as formula (I a) shown in conducting polymer, after question response half an hour, substrate is cooled to room temperature, obtain transparent conductive film, thus obtain transparency electrode, the material of transparent conductive film comprise chemical structural formula such as formula (I a) shown in conducting polymer and Graphene, graphene uniform is dispersed in transparent conductive film, this transparent conductive film thickness is about 1nm,
Embodiment two
A preparation method for transparency electrode, comprises the following steps:
(1) preparative chemistry structural formula such as formula (II b) shown in polymer, comprise the following steps:
Under oxygen-free environment, by equimolar ratio such as formula shown in (3b) compound and be added into close in the solvent of palladium containing dichloro two (triphenyl phosphorus) such as formula the compound shown in (4) and dissolve, the aqueous sodium carbonate of solvent to be toluene and concentration be 2mol/L is mixed liquor that the ratio of 2:1 is formed by volume; Obtain reactant liquor, reactant liquor is carried out suzuki coupling reaction at 110 DEG C, the reaction time is 12 hours, obtained chemical structural formula such as formula (II b) shown in polymer;
(2) adopt PET as substrate, water-detergent solution is used successively in pet sheet face, deionized water, acetone cleans, and is dried up by substrate surface with nitrogen;
By chemical structural formula such as formula (II b) shown in polymer and graphene dispersion in ethanol and carry out ultrasonic dissolution, obtain mixed solution, in mixed solution, the concentration of polymer is 3g/L, and the concentration of Graphene is 2g/L;
At the above-mentioned mixed solution of PET base surface spraying of 40 DEG C, form the film of flat transparent;
(3) PET base of film there is is to be placed in thermal station the spin coating that step (2) obtains, be heated to 200 DEG C, chemical structural formula such as formula (II b) shown in polymer generation pyrolytic reaction, generate such as formula (I b) shown in conducting polymer, after question response half an hour, substrate is cooled to room temperature, obtain transparent conductive film, thus obtain transparency electrode, the material of transparent conductive film comprise chemical structural formula such as formula (I b) shown in conducting polymer and Graphene, graphene uniform is dispersed in transparent conductive film, this transparent conductive film thickness is about 1nm,
Embodiment three
A preparation method for transparency electrode, comprises the following steps:
(1) preparative chemistry structural formula such as formula (II c) shown in polymer, comprise the following steps:
Under oxygen-free environment, by equimolar ratio such as formula shown in (3c) compound and be added into close in the solvent of palladium containing dichloro two (triphenyl phosphorus) such as formula the compound shown in (4) and dissolve, the aqueous sodium carbonate of solvent to be oxolane and concentration be 2mol/L is mixed liquor that the ratio of 2:1 is formed by volume; Obtain reactant liquor, reactant liquor is carried out suzuki coupling reaction at 100 DEG C, the reaction time is 36 hours, obtained chemical structural formula such as formula (II c) shown in polymer;
(2) adopt PET as substrate, water-detergent solution is used successively in PET base surface, deionized water, acetone cleans, and is dried up by substrate surface with nitrogen;
By chemical structural formula such as formula (II c) shown in polymer and nitrogen-doped graphene dispersion in ethanol and carry out ultrasonic dissolution, obtain mixed solution, in mixed solution, the concentration of polymer is 3g/L, and the concentration of nitrogen-doped graphene is 1g/L;
At the above-mentioned mixed solution of PET base surface spraying of 70 DEG C, form the film of flat transparent;
(3) substrate of glass of film there is is to be placed in thermal station the spin coating that step (2) obtains, be heated to 200 DEG C, chemical structural formula such as formula (II c) shown in polymer generation pyrolytic reaction, generate such as formula (I c) shown in conducting polymer, after question response half an hour, substrate is cooled to room temperature, obtain transparent conductive film, thus obtain transparency electrode, the material of transparent conductive film comprise chemical structural formula such as formula (I c) shown in conducting polymer and nitrogen-doped graphene, nitrogen-doped graphene is dispersed in transparent conductive film, this transparent conductive film thickness is about 1nm.
Effect example
For providing powerful support for the beneficial effect of the embodiment of the present invention, provide effect example as follows, in order to evaluate and test the performance of the product that the embodiment of the present invention provides.
Transparency electrode obtained for the embodiment of the present invention 1 ~ 3 is carried out the test of light transmittance, test result is as follows:
Embodiment one: the light transmittance of transparency electrode reaches 90%;
Embodiment two: the light transmittance of transparency electrode reaches 89%;
Embodiment three: the light transmittance of transparency electrode reaches 89%.
The obtained transparency electrode light transmittance of the embodiment of the present invention all reach 89% and more than, light transmission is good.
The transparency electrode that the embodiment of the present invention is obtained, in its transparent conductive film, grapheme material and conducting polymer are flexible material, and the transparency electrode of formation is better flexible.
The transparency electrode that the embodiment of the present invention is obtained, its conducting polymer shown in transparent conductive film Chinese style (I) is obtained by reacting by the Polymer-pyrolysis shown in formula (II), pyrolytic reaction eliminates affects polymer conductivity and oil-soluble long alkyl chain, improve the electric conductivity of conducting polymer, reduce the oil-soluble of conducting polymer simultaneously, therefore in subsequent applications, this conducting polymer is not vulnerable to the corrosion of oil-dissolving solvent, thus improve the stability of transparency electrode, to solve in prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by problem that oil-dissolving solvent corrosion causes electroconductive polymer layer to lose efficacy.
To sum up, the transparency electrode light transmittance that the embodiment of the present invention is obtained is high, flexible, conductivity and having good stability.
Claims (21)
1. a transparency electrode, it is characterized in that, comprise substrate and be arranged on the transparent conductive film of described substrate surface, the material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), described grapheme material comprises Graphene or doped graphene, described grapheme material is dispersed in described transparent conductive film
formula (I),
Wherein, n is 10 ~ 30.
2. transparency electrode as claimed in claim 1, it is characterized in that, in described transparent conductive film, the mass ratio of described conducting polymer and described grapheme material is 1:1 ~ 10:1.
3. transparency electrode as claimed in claim 1 or 2, it is characterized in that, the number of plies of described grapheme material is single or multiple lift.
4. the transparency electrode as described in any one of claims 1 to 3, is characterized in that, described doped graphene is nitrogen-doped graphene or boron doped graphene.
5. the transparency electrode as described in any one of Claims 1 to 4, is characterized in that, the thickness of described transparent conductive film is 1 ~ 10nm.
6. the transparency electrode as described in any one of Claims 1 to 5, is characterized in that, the material of described substrate is glass, polyimides, PETG, PEN, polymethyl methacrylate, Merlon or polyurethane.
7. a preparation method for transparency electrode, is characterized in that, comprises the following steps:
Substrate is provided, grapheme material and chemical structural formula is dissolved in polar solvent such as formula the polymer shown in (II), obtains mixed solution; Described mixed solution is coated in described substrate surface and forms film; Described grapheme material comprises Graphene or doped graphene,
formula (II); Wherein R to be carbon number be 4 ~ 15 alkyl, n is 10 ~ 30;
Heat described film, make described chemical structural formula such as formula the polymer generation pyrolytic reaction shown in (II), generate chemical structural formula such as formula the conducting polymer shown in (I), obtain transparent conductive film, thus obtain transparency electrode; The material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), and described grapheme material is dispersed in described transparent conductive film,
formula (I),
Wherein, n is 10 ~ 30.
8. the preparation method of transparency electrode as claimed in claim 7, it is characterized in that, described R is 1, Isosorbide-5-Nitrae, 8-tetramethyl nonyl.
9. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterized in that, in described mixed solution, described chemical structural formula is 1 ~ 10g/L such as formula the concentration of the polymer shown in (II), and the concentration of described grapheme material is 0.1 ~ 3g/L.
10. the preparation method of the transparency electrode as described in any one of claim 7 ~ 9, is characterized in that, described polar solvent is at least one in water, ethanol, acetonitrile, acetone, oxolane and dimethyl formamide.
The preparation method of 11. transparency electrodes as described in any one of claim 7 ~ 10, it is characterized in that, the method for described coating comprises spin coating, spraying or blade coating.
The preparation method of 12. transparency electrodes as described in any one of claim 7 ~ 11, it is characterized in that, described heating-up temperature is 150 DEG C ~ 250 DEG C, and heating time is 0.5 ~ 1h.
The preparation method of 13. transparency electrodes as described in any one of claim 7 ~ 12, it is characterized in that, in described transparent conductive film, the mass ratio of described conducting polymer and described grapheme material is 1:1 ~ 10:1.
The preparation method of 14. transparency electrodes as described in any one of claim 7 ~ 13, it is characterized in that, the number of plies of described grapheme material is single or multiple lift.
The preparation method of 15. transparency electrodes as described in any one of claim 7 ~ 14, it is characterized in that, described doped graphene is nitrogen-doped graphene or boron doped graphene.
The preparation method of 16. transparency electrodes as described in any one of claim 7 ~ 15, it is characterized in that, the material of described substrate is glass, polyimides, PETG, PEN, polymethyl methacrylate, Merlon or polyurethane.
The preparation method of 17. transparency electrodes as described in any one of claim 7 ~ 16, it is characterized in that, the thickness of described transparent conductive film is 1 ~ 10nm.
The preparation method of 18. transparency electrodes as described in any one of claim 7 ~ 17, is characterized in that, described chemical structural formula adopts following methods to prepare such as formula the polymer shown in (II):
Under oxygen-free environment, by equimolar ratio such as formula shown in (3) compound and dissolve in being added into containing catalyst solvent such as formula the compound shown in (4), obtain reactant liquor, described reactant liquor is carried out suzuki coupling reaction at 85 DEG C ~ 110 DEG C, reaction time is 12 ~ 48 hours, and obtained chemical structural formula is such as formula the polymer shown in (II);
wherein, R to be carbon number be 4 ~ 15 alkyl.
The preparation method of 19. transparency electrodes as claimed in claim 18, is characterized in that, described solvent is the mixed liquor of toluene or oxolane and sodium carbonate formation.
The preparation method of 20. transparency electrodes as described in claim 18 or 19, is characterized in that, described catalyst is that four (triphenyl phosphorus) close palladium or dichloro two (triphenyl phosphorus) closes palladium.
21. 1 kinds of organic solar batteries, comprise negative electrode, active layer and anode, it is characterized in that, described negative electrode is transparency electrode, described transparency electrode comprises substrate and is arranged on the transparent conductive film of described substrate surface, and the material of described transparent conductive film comprises grapheme material and chemical structural formula such as formula the conducting polymer shown in (I), and described grapheme material comprises Graphene or doped graphene, described grapheme material is dispersed in described transparent conductive film
formula (I),
Wherein, n is 10 ~ 30.
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