CN105244443B - A kind of transparency electrode and preparation method thereof and organic solar batteries - Google Patents
A kind of transparency electrode and preparation method thereof and organic solar batteries Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 69
- 239000002322 conducting polymer Substances 0.000 claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 graphite Alkene Chemical class 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 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 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004425 Makrolon Substances 0.000 claims description 6
- 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
- 229920000515 polycarbonate Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 10
- 229920002521 macromolecule Polymers 0.000 abstract description 8
- 238000004528 spin coating Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
First aspect of the embodiment of the present invention provides a kind of transparency electrode, including substrate and the transparent conductive film for being arranged on the substrate surface, the material of the transparent conductive film includes conducting polymer grapheme material and chemical structural formula as shown in formula (I), the grapheme material includes graphene or doped graphene, the grapheme material is dispersed in the transparent conductive film
Description
Technical field
The present invention relates to electrode technology field, more particularly to a kind of transparency electrode and preparation method thereof and organic solar electricity
Pond.
Background technology
Currently, the most frequently used transparent electrode material is metal oxide or fluoride based on traditional inorganic material, such as
ITO, IZO or FTO etc., however as rare metal it is increasingly deficient, price is growing and transparent conductive film is thermally-stabilised
The poor, flexibility of property is poor and the problems such as preparation process complexity, limits their applications in photoelectric functional devices field.Therefore, open
Hair has abundant raw materials, and cheap, flexible, the high electrode material of transparent and electrically conductive is led to photoelectric functional device etc.
Domain development is significant.
Graphene is because with high mobility, excellent mechanical performance and good translucency and heat endurance etc. are excellent
Characteristic, as the most new material of the transparency electrode such as existing ITO of potential replacement at present.But the large area stone of preparation hitherto
Black alkene is polycrystalline structure, with more defect and crystal boundary, greatly affected its photoelectric properties.In order to solve this problem,
Industry has prepared a kind of graphene composite transparent electrode, and the transparency electrode is provided with graphene layer in flexible transparent substrate
And electroconductive polymer layer；The graphene composite transparent electrode combines conducting polymer and the advantage both graphene, tool
There are excellent photoelectric properties and flexibility.But the transparency electrode is when applying in the later stage, for example, prepare activity on the transparency electrode surface
During layer, generally active layer material is dissolved in oil-dissolving solvent after such as chlorobenzene again in transparency electrode surface spin coating, spin coating process
Oil-dissolving solvent meeting corrosion electroconductive polymer layer, will cause the failure of electroconductive polymer layer.
The content of the invention
In view of this, first aspect of the embodiment of the present invention provides a kind of transparency electrode, of the prior art to solve
In graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily by oil-dissolving solvent corrosion, cause conductive polymer
The problem of sublayer fails.
In a first aspect, the embodiments of the invention provide a kind of transparency electrode, including substrate and it is arranged on the substrate surface
Transparent conductive film, the material of the transparent conductive film includes grapheme material and chemical structural formula as shown in formula (I)
Conducting polymer, the grapheme material includes graphene or doped graphene, and the grapheme material is dispersed in described
In transparent conductive film,
Formula (I),
Wherein, n is 10~30.
In embodiment of the present invention, in the transparent conductive film, the conducting polymer and the grapheme material
Mass ratio is 1:1~10:1.
In embodiment of the present invention, the number of plies of the grapheme material is single or multiple lift.
In embodiment of the present invention, the doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, the material of the substrate is glass, polyimides, polyethylene terephthalate,
PEN, polymethyl methacrylate, makrolon or polyurethane.
In embodiment of the present invention, the thickness of the transparent conductive film is 1~10nm.
The transparency electrode that first aspect of the embodiment of the present invention is provided, its transparent conductive film includes leading shown in formula (I)
Electric polymer, the side chain of the conducting polymer does not contain long alkyl chain, and the oil-soluble of conducting polymer is relatively low, therefore subsequently should
In, the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve the stability of transparency electrode, solves
In the prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily caused by oil-dissolving solvent corrosion
The problem of electroconductive polymer layer fails.
Second aspect, the embodiments of the invention provide a kind of preparation method of transparency electrode, comprises the following steps：
Substrate is provided, the polymer of grapheme material and chemical structural formula as shown in formula (II) is dissolved in polar solvent,
Obtain mixed solution；The mixed solution is coated in the substrate surface formation film；The grapheme material includes graphite
Alkene or doped graphene
Formula (II)；
Wherein, R is the alkyl that carbon number is 4~15, and n is 10~30；
The film is heated, polymer of the chemical structural formula as shown in formula (II) is occurred pyrolytic reaction, generationization
Conducting polymer of the structural formula as shown in formula (I) is learned, transparent conductive film is obtained, so as to obtain transparency electrode；It is described transparent to lead
The material of conductive film includes conducting polymer grapheme material and chemical structural formula as shown in formula (I), the grapheme material
It is dispersed in the transparent conductive film,
Formula (I),
Wherein, n is 10~30.
In embodiment of the present invention, the R is 1, Isosorbide-5-Nitrae, 8- tetramethyl nonyls.
In embodiment of the present invention, in the mixed solution, polymer of the chemical structural formula as shown in formula (II)
Concentration is 1~10g/L, and the concentration of the grapheme material is 0.1~3g/L.
In embodiment of the present invention, the polar solvent is water, ethanol, acetonitrile, acetone, tetrahydrofuran and dimethyl formyl
At least one of amine.
In embodiment of the present invention, the method for the coating includes spin coating, spraying or scratched.
In embodiment of the present invention, the heating-up temperature is 150 DEG C~250 DEG C, and the heat time is 0.5~1h.
In embodiment of the present invention, in the transparent conductive film, the conducting polymer and the grapheme material
Mass ratio is 1:1~10:1.
In embodiment of the present invention, the number of plies of the grapheme material is single or multiple lift.
In embodiment of the present invention, the doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, the material of the substrate is glass, polyimides, polyethylene terephthalate,
PEN, polymethyl methacrylate, makrolon or polyurethane.
In embodiment of the present invention, the thickness of the transparent conductive film is 1~10nm.
In embodiment of the present invention, polymer of the chemical structural formula as shown in formula (II) is prepared into using following methods
Arrive：
Under oxygen-free environment, by equimolar than the compound as shown in formula (3) and the compound as shown in formula (4) add
Add in the solvent containing catalyst and dissolve, obtain reaction solution, the reaction solution is carried out to suzuki idols at 85 DEG C~110 DEG C
Connection reaction, the reaction time is 12~48 hours, and polymer of the chemical structural formula as shown in formula (II) is made；
Wherein, R is the alkyl that carbon number is 4~15.
In embodiment of the present invention, the solvent is the mixed liquor of toluene or tetrahydrofuran and sodium carbonate formation.
In embodiment of the present invention, the catalyst is that four (triphenyl phosphorus) close palladium or dichloro double (triphenyl phosphorus) closes palladium.
The preparation method for the transparency electrode that second aspect of the embodiment of the present invention is provided, technique is simple, prepares cost low, it is easy to
Industrialized production.
The third aspect, the embodiments of the invention provide a kind of organic solar batteries, including negative electrode, active layer and anode,
The negative electrode is transparency electrode, and the transparency electrode includes substrate and is arranged on the transparent conductive film of the substrate surface, institute
State the conducting polymer that the material of transparent conductive film includes grapheme material and chemical structural formula as shown in formula (I), the stone
Black alkene material includes graphene or doped graphene, and the grapheme material is dispersed in the transparent conductive film,
Formula (I),
Wherein, n is 10~30.
The organic solar batteries that the third aspect of the embodiment of the present invention is provided, because the conduction in the transparency electrode of use is gathered
The oil-soluble of compound is relatively low, and the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve transparency electrode
Stability, has good stability using the transparency electrode as the organic solar batteries of negative electrode.
To sum up, the transparency electrode that first aspect of the embodiment of the present invention is provided, its transparent conductive film is included shown in formula (I)
Conducting polymer, the side chain of the conducting polymer do not contain long alkyl chain, and the oil-soluble of conducting polymer is relatively low, therefore rear
In continuous application, the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve the stability of transparency electrode, solves
Determine in graphene conductive macromolecule composite transparent electrode in the prior art, because conducting polymer is easily by oil-dissolving solvent corrosion
Cause the problem of electroconductive polymer layer fails.The preparation method for the transparency electrode that second aspect of the embodiment of the present invention is provided, technique
Simply, cost is prepared low, it is easy to industrialized production.The organic solar batteries that the third aspect of the embodiment of the present invention is provided, have
Good stability.
The advantage of the embodiment of the present invention will be illustrated partly in the following description, a part according to specification be it is aobvious and
It is clear to, or can be known by the implementation of the embodiment of the present invention.
Embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, some improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
The transparency electrode that first aspect of the embodiment of the present invention is provided, its transparent conductive film includes leading shown in formula (I)
Electric polymer, the side chain of the conducting polymer does not contain long alkyl chain, and the oil-soluble of conducting polymer is relatively low, therefore subsequently should
In, the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve the stability of transparency electrode, solves
In the prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily caused by oil-dissolving solvent corrosion
The problem of electroconductive polymer layer fails.
In a first aspect, the embodiments of the invention provide a kind of transparency electrode, including substrate and it is arranged on the substrate surface
Transparent conductive film, the material of the transparent conductive film includes grapheme material and chemical structural formula as shown in formula (I)
Conducting polymer, the grapheme material includes graphene or doped graphene, and the grapheme material is dispersed in described
In transparent conductive film,
Formula (I),
Wherein, n is 10~30.
In embodiment of the present invention, in the transparent conductive film, the conducting polymer and the grapheme material
Mass ratio is 1:1~10:1.
In embodiment of the present invention, the number of plies of the grapheme material is single or multiple lift.
In embodiment of the present invention, the number of plies of the grapheme material is 2~5 layers.
In embodiment of the present invention, the doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, the doped graphene is nitrogen-doped graphene.
In embodiment of the present invention, the material of the substrate is glass, polyimides (PI), polyethylene terephthalate
Ester (PET), PEN (PEN), polymethyl methacrylate (PMMA), makrolon (PC) or polyurethane
(PU)。
In embodiment of the present invention, the thickness of the transparent conductive film is 1~10nm.
In embodiment of the present invention, the oil-dissolving solvent is and the mutual insoluble organic solvent of water.
The conducting polymer is conjugated polymer, with higher electron affinity energy, can play electrode modification layer
Effect, makes grapheme material be easier to obtain electric charge.Grapheme material can be bonded by the conducting polymer simultaneously, be risen
The effect of similar binding agent has been arrived, has made the transparent conductive film of the conducting polymer and grapheme material formation continuous-stable,
The light transmittance of the transparency electrode finally given is high, electric conductivity and have good stability, and can be advantageously applied to organic solar electricity
The fields such as pond.
The transparency electrode that first aspect of the embodiment of the present invention is provided, its transparent conductive film includes leading shown in formula (I)
Electric polymer, the side chain of the conducting polymer does not contain long alkyl chain, and the oil-soluble of conducting polymer is relatively low, therefore subsequently should
In, the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve the stability of transparency electrode, solves
In the prior art in graphene conductive macromolecule composite transparent electrode, because conducting polymer is easily caused by oil-dissolving solvent corrosion
The problem of electroconductive polymer layer fails.
Second aspect, the embodiments of the invention provide a kind of preparation method of transparency electrode, comprises the following steps：
Substrate is provided, grapheme material and polymer of the chemical structural formula as shown in formula (II) are dissolved in polar solvent,
Obtain mixed solution；The mixed solution is coated in the substrate surface formation film；The grapheme material includes graphite
Alkene or doped graphene,
Formula (II)；
Wherein, R is the alkyl that carbon number is 4~15, and n is 10~30；
The film is heated, polymer of the chemical structural formula as shown in formula (II) is occurred pyrolytic reaction, generationization
Conducting polymer of the structural formula as shown in formula (I) is learned, transparent conductive film is obtained, so as to obtain transparency electrode；It is described transparent to lead
The material of conductive film includes conducting polymer grapheme material and chemical structural formula as shown in formula (I), the grapheme material
It is dispersed in the transparent conductive film,
Formula (I),
Wherein, n is 10~30.
In embodiment of the present invention, the R is 1, Isosorbide-5-Nitrae, 8- tetramethyl nonyls.
In embodiment of the present invention, in the mixed solution, polymer of the chemical structural formula as shown in formula (II)
Concentration is 1~10g/L, and the concentration of the grapheme material is 0.1~3g/L.
In embodiment of the present invention, the polar solvent is water, ethanol, acetonitrile, acetone, tetrahydrofuran and dimethyl formyl
At least one of amine.
In embodiment of the present invention, the method for the coating includes spin coating, spraying or scratched.
In embodiment of the present invention, the rotating speed during spin coating is 500~2000r/min.
In embodiment of the present invention, the heating-up temperature is 150 DEG C~250 DEG C, and the heat time is 0.5~1h.
In embodiment of the present invention, in the transparent conductive film, the conducting polymer and the grapheme material
Mass ratio is 1:1~10:1.
In embodiment of the present invention, the number of plies of the grapheme material is single or multiple lift.
In embodiment of the present invention, the number of plies of the grapheme material is 2~5 layers.
In embodiment of the present invention, the doped graphene is nitrogen-doped graphene or boron doped graphene.
In embodiment of the present invention, the doped graphene is nitrogen-doped graphene.
In embodiment of the present invention, micromechanics stripping method that the grapheme material can be reported according to document, SiC pyrolysis
Prepared by the methods such as epitaxial growth method, chemical vapour deposition technique or chemistry redox method, but be not limited to these methods.
In embodiment of the present invention, the grapheme material is prepared using chemistry redox method.
In embodiment of the present invention, the material of the substrate is glass, polyimides, polyethylene terephthalate,
PEN, polymethyl methacrylate, makrolon or polyurethane.
In embodiment of the present invention, the substrate is cleaned, cleaning method is：Substrate surface is used into detergent successively
The aqueous solution, deionized water and acetone cleaning, and dried up substrate surface with nitrogen.
In embodiment of the present invention, the thickness of the transparent conductive film is 1~10nm.
In embodiment of the present invention, the reaction of pyrolytic reaction occurs for polymer of the chemical structural formula as shown in formula (II)
Formula is：
In embodiment of the present invention, polymer of the chemical structural formula as shown in formula (II) is prepared into using following methods
Arrive：
Under oxygen-free environment, by equimolar than the compound as shown in formula (3) and the compound as shown in formula (4) add
Add in the solvent containing catalyst and dissolve, obtain reaction solution, the reaction solution is carried out to suzuki idols at 85 DEG C~110 DEG C
Connection reaction, the reaction time is 12~48 hours, and polymer of the chemical structural formula as shown in formula (II) is made；
Wherein, R is the alkyl that carbon number is 4~15.
The reaction equation of suzuki coupling reactions is：
In embodiment of the present invention, the solvent is the mixed liquor of toluene or tetrahydrofuran and sodium carbonate formation.
In embodiment of the present invention, the aqueous sodium carbonate that the solvent is toluene or tetrahydrofuran and concentration is 2mol/L
The mixed liquor of formation, the volume ratio of the toluene or tetrahydrofuran and aqueous sodium carbonate is 2:1.
In embodiment of the present invention, the catalyst is that four (triphenyl phosphorus) close palladium or dichloro double (triphenyl phosphorus) closes palladium.
Containing group such as ester group can be pyrolyzed in polymer of the chemical structural formula as shown in formula (II), by the polymer
It is dissolved in grapheme material in water or alcohol polar solvent, then after the method formation film for passing through coating, to the film heating,
So that polymer of the chemical structural formula as shown in formula (II) is pyrolyzed, so as to remove influence polymer conductivity and oil-soluble
Long alkyl chain, it is possible to decrease the oil-soluble of conducting polymer, while improving the electric conductivity of grapheme material.What is finally given is transparent
Electrode has good electric conductivity and stability.
The conducting polymer is conjugated polymer, with higher electron affinity energy, can play electrode modification layer
Effect, in order to the charge transport between active layer and transparency electrode.Simultaneously after pyrolytic reaction, the conducting polymer can be by
Grapheme material bonds, and serves the effect of similar binding agent, connects the conducting polymer and grapheme material formation
Continue stable transparent conductive film.
Second aspect of the embodiment of the present invention provides a kind of preparation method of transparency electrode, the preparation method technique letter
It is single, while it is low to prepare cost, it is easy to industrialized production.
The third aspect, the embodiments of the invention provide a kind of organic solar batteries, including negative electrode, active layer and anode,
The negative electrode is transparency electrode, and the transparency electrode includes substrate and is arranged on the transparent conductive film of the substrate surface, institute
State the conducting polymer that the material of transparent conductive film includes grapheme material and chemical structural formula as shown in formula (I), the stone
Black alkene material includes graphene or doped graphene, and the grapheme material is dispersed in the transparent conductive film,
Formula (I),
Wherein, n is 10~30.
In embodiment of the present invention, the active layer includes donor material and acceptor material, the donor material and acceptor
Material can be the bulk heterojunction Rotating fields being made by mixing or the double-deck bulk heterojunction that film forming is made respectively
Rotating fields.
In embodiment of the present invention, the selection of the donor material and acceptor material is not particularly limited, existing available
All may be used.
In embodiment of the present invention, the material of the anode can be metal or conductive oxide, such as aluminium (Al), magnesium
(Mg), one or more of alloys in silver-colored (Ag), golden (Au), platinum (Pt), copper (Cu), such as almag (Mg/Al), silver-colored magnesium are closed
Golden (Ag/Ag), described metal can also be layer structure, such as be lithium fluoride:Aluminium (LiF/Al).The preparation method of anode is usual
Deposited using vapour deposition method, other deposition process can be also used certainly.
The organic solar batteries that the third aspect of the embodiment of the present invention is provided, because the conduction in the transparency electrode of use is gathered
The oil-soluble of compound is relatively low, and the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve transparency electrode
Stability, has good stability using the transparency electrode as the organic solar batteries of negative electrode.
To sum up, the transparency electrode that first aspect of the embodiment of the present invention is provided, its transparent conductive film is included shown in formula (I)
Conducting polymer, the side chain of the conducting polymer do not contain long alkyl chain, and the oil-soluble of conducting polymer is relatively low, therefore rear
In continuous application, the conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve the stability of transparency electrode, solves
Determine in graphene conductive macromolecule composite transparent electrode in the prior art, because conducting polymer is easily by oil-dissolving solvent corrosion
Cause the problem of electroconductive polymer layer fails.The preparation method for the transparency electrode that second aspect of the embodiment of the present invention is provided, technique
Simply, cost is prepared low, it is easy to industrialized production.The organic solar batteries that the third aspect of the embodiment of the present invention is provided, have
Good stability.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is not limited
Due to following specific embodiment.In the range of constant principal right, carry out change implementation that can be appropriate.
Embodiment one
A kind of preparation method of transparency electrode, comprises the following steps：
(1) polymer of the chemical structural formula as shown in formula (II a) is prepared, is comprised the following steps：
Under oxygen-free environment, by equimolar than the compound as shown in formula (3a) and the compound as shown in formula (4)
It is added into the solvent that palladium is closed containing four (triphenyl phosphorus) and dissolves, the aqueous sodium carbonate that solvent is toluene and concentration is 2mol/L
It is 2 by volume:The mixed liquor of 1 ratio formation；Reaction solution is obtained, reaction solution is subjected to suzuki couplings instead at 85 DEG C
Should, the reaction time is 48 hours, and polymer of the chemical structural formula as shown in formula (II a) is made；
(2) glass surface is used by water-detergent solution using clear glass successively as substrate, deionized water, acetone is clear
Wash, and dried up glass surface with nitrogen；
Polymer of the chemical structural formula as shown in formula (II a) and graphene dispersion in ethanol and are subjected to ultrasonic dissolution,
Obtain in mixed solution, 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 1000r/min rotating speed, the film of flat transparent is formed；
(3) substrate of glass that the spin coating for obtaining step (2) has film is placed in thermal station, is heated to 200 DEG C, chemical constitution
Pyrolytic reaction occurs for polymer of the formula as shown in formula (II a), generates the conducting polymer as shown in formula (I a), question response half an hour
Afterwards, substrate is cooled into room temperature, obtains transparent conductive film, so as to obtain transparency electrode, the material of transparent conductive film includes
Conducting polymer and graphene of the chemical structural formula as shown in formula (I a), graphene uniform are dispersed in transparent conductive film, should
Transparent conductive film thickness is about 1nm；
Embodiment two
A kind of preparation method of transparency electrode, comprises the following steps：
(1) polymer of the chemical structural formula as shown in formula (II b) is prepared, is comprised the following steps：
Under oxygen-free environment, by equimolar than the compound as shown in formula (3b) and the compound as shown in formula (4)
It is added into close containing dichloro double (triphenyl phosphorus) and is dissolved in the solvent of palladium, the sodium carbonate that solvent is toluene and concentration is 2mol/L
Solution is 2 by volume:The mixed liquor of 1 ratio formation；Reaction solution is obtained, reaction solution is carried out to suzuki idols at 110 DEG C
Connection reaction, the reaction time is 12 hours, and polymer of the chemical structural formula as shown in formula (II b) is made；
(2) pet sheet face is used by water-detergent solution using PET successively as substrate, deionized water, acetone cleaning is used in combination
Nitrogen dries up substrate surface；
Polymer of the chemical structural formula as shown in formula (II b) and graphene dispersion in ethanol and are subjected to ultrasonic dissolution,
Obtain in mixed solution, mixed solution, the concentration of polymer is 3g/L, and the concentration of graphene is 2g/L；
In 40 DEG C of the above-mentioned mixed solution of PET base surface spraying, the film of flat transparent is formed；
(3) PET base that the spin coating for obtaining step (2) has film is placed in thermal station, is heated to 200 DEG C, chemical constitution
Pyrolytic reaction occurs for polymer of the formula as shown in formula (II b), generates the conducting polymer as shown in formula (I b), question response half an hour
Afterwards, substrate is cooled into room temperature, obtains transparent conductive film, so as to obtain transparency electrode, the material of transparent conductive film includes
Conducting polymer and graphene of the chemical structural formula as shown in formula (I b), graphene uniform are dispersed in transparent conductive film, should
Transparent conductive film thickness is about 1nm；
Embodiment three
A kind of preparation method of transparency electrode, comprises the following steps：
(1) polymer of the chemical structural formula as shown in formula (II c) is prepared, is comprised the following steps：
Under oxygen-free environment, by equimolar than the compound as shown in formula (3c) and the compound as shown in formula (4)
It is added into close containing dichloro double (triphenyl phosphorus) and is dissolved in the solvent of palladium, the carbonic acid that solvent is tetrahydrofuran and concentration is 2mol/L
Sodium water solution is 2 by volume:The mixed liquor of 1 ratio formation；Reaction solution is obtained, reaction solution is carried out at 100 DEG C
Suzuki coupling reactions, the reaction time is 36 hours, and polymer of the chemical structural formula as shown in formula (II c) is made；
(2) PET base surface is used by water-detergent solution using PET successively as substrate, deionized water, acetone is cleaned,
And dried up substrate surface with nitrogen；
In ethanol and ultrasound is carried out by polymer of the chemical structural formula as shown in formula (II c) and nitrogen-doped graphene are scattered
Dissolving, is obtained in mixed solution, mixed solution, and the concentration of polymer is 3g/L, and the concentration of nitrogen-doped graphene is 1g/L；
In 70 DEG C of the above-mentioned mixed solution of PET base surface spraying, the film of flat transparent is formed；
(3) substrate of glass that the spin coating for obtaining step (2) has film is placed in thermal station, is heated to 200 DEG C, chemical constitution
Pyrolytic reaction occurs for polymer of the formula as shown in formula (II c), generates the conducting polymer as shown in formula (I c), question response half an hour
Afterwards, substrate is cooled into room temperature, obtains transparent conductive film, so as to obtain transparency electrode, the material of transparent conductive film includes
Conducting polymer and nitrogen-doped graphene of the chemical structural formula as shown in formula (I c), nitrogen-doped graphene are dispersed in transparent lead
In conductive film, the transparent conductive film thickness is about 1nm.
Effect example
It is as follows there is provided effect example for the beneficial effect that provides powerful support for the embodiment of the present invention, it is of the invention real to evaluate and test
The performance of the product of example offer is provided.
Transparency electrode made from the embodiment of the present invention 1~3 is carried out to 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%.
Transparency electrode light transmittance made from the embodiment of the present invention reach 89% and more than, translucency is good.
Grapheme material and conducting polymer are in transparency electrode made from the embodiment of the present invention, its transparent conductive film
Flexible material, the transparency electrode of formation is flexible preferably.
Transparency electrode made from the embodiment of the present invention, the conducting polymer shown in its transparent conductive film Chinese style (I) is by formula
(II) the Polymer-pyrolysis reaction shown in is obtained, and pyrolytic reaction eliminates influence polymer conductivity and oil-soluble long alkyl
Chain, improves the electric conductivity of conducting polymer, while the oil-soluble of conducting polymer is reduced, therefore in subsequent applications, should
Conducting polymer is not easily susceptible to the corrosion of oil-dissolving solvent, so as to improve the stability of transparency electrode, solves prior art
In middle graphene conductive macromolecule composite transparent electrode, because conducting polymer easily causes conductive polymer by oil-dissolving solvent corrosion
The problem of sublayer fails.
To sum up, transparency electrode light transmittance made from the embodiment of the present invention is high, flexible, electric conductivity and has good stability.
Claims (21)
1. a kind of transparency electrode, it is characterised in that described including substrate and the transparent conductive film for being arranged on the substrate surface
The material of transparent conductive film includes conducting polymer grapheme material and chemical structural formula as shown in formula (I), the graphite
Alkene material includes graphene or doped graphene, and the grapheme material is dispersed in the transparent conductive film,
Wherein, n is 10~30.
2. transparency electrode as claimed in claim 1, it is characterised in that in the transparent conductive film, the conducting polymer
Mass ratio with the grapheme material is 1:1~10:1.
3. transparency electrode as claimed in claim 1 or 2, it is characterised in that the number of plies of the grapheme material is individual layer or many
Layer.
4. transparency electrode as claimed in claim 1 or 2, it is characterised in that the doped graphene be nitrogen-doped graphene or
Boron doped graphene.
5. transparency electrode as claimed in claim 1 or 2, it is characterised in that the thickness of the transparent conductive film is 1~
10nm。
6. transparency electrode as claimed in claim 1 or 2, it is characterised in that the material of the substrate be glass, polyimides,
Polyethylene terephthalate, PEN, polymethyl methacrylate, makrolon or polyurethane.
7. a kind of preparation method of transparency electrode, it is characterised in that comprise the following steps：
Substrate is provided, the polymer of grapheme material and chemical structural formula as shown in formula (II) is dissolved in polar solvent, obtained
Mixed solution；The mixed solution is coated in the substrate surface formation film；The grapheme material include graphene or
Doped graphene,
Wherein R is the alkyl that carbon number is 4~15, and n is 10~30；
The film is heated, polymer of the chemical structural formula as shown in formula (II) is occurred pyrolytic reaction, generation chemistry knot
Conducting polymer of the structure formula as shown in formula (I), obtains transparent conductive film, so as to obtain transparency electrode；The electrically conducting transparent is thin
The material of film includes conducting polymer grapheme material and chemical structural formula as shown in formula (I), and the grapheme material is uniform
It is dispersed in the transparent conductive film,
Wherein, n is 10~30.
8. the preparation method of transparency electrode as claimed in claim 7, it is characterised in that the R is 1, Isosorbide-5-Nitrae, 8- tetramethyl nonyls
Alkyl.
9. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that in the mixed solution, describedization
The concentration for learning polymer of the structural formula as shown in formula (II) is 1~10g/L, and the concentration of the grapheme material is 0.1~3g/L.
10. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the polar solvent is water, second
At least one of alcohol, acetonitrile, acetone, tetrahydrofuran and dimethylformamide.
11. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the method for the coating includes rotation
Apply, spray or scratch.
12. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the heating-up temperature is 150 DEG C
~250 DEG C, the heat time is 0.5~1h.
13. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that in the transparent conductive film,
The mass ratio of the conducting polymer and the grapheme material is 1:1~10:1.
14. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the number of plies of the grapheme material
For single or multiple lift.
15. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the doped graphene is mixed for nitrogen
Miscellaneous graphene or boron doped graphene.
16. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the material of the substrate is glass
Glass, polyimides, polyethylene terephthalate, PEN, polymethyl methacrylate, makrolon
Or polyurethane.
17. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the thickness of the transparent conductive film
Spend for 1~10nm.
18. the preparation method of transparency electrode as claimed in claim 7 or 8, it is characterised in that the chemical structural formula such as formula
(II) polymer shown in is prepared using following methods：
Under oxygen-free environment, by equimolar than the compound as shown in formula (3) and the compound as shown in formula (4) be added into
Dissolved in solvent containing catalyst, obtain reaction solution, the reaction solution is subjected to suzuki couplings instead at 85 DEG C~110 DEG C
Should, the reaction time is 12~48 hours, and polymer of the chemical structural formula as shown in formula (II) is made；
Wherein, R is the alkyl that carbon number is 4~15.
19. the preparation method of transparency electrode as claimed in claim 18, it is characterised in that the solvent is toluene or tetrahydrochysene furan
The mixed liquor muttered with sodium carbonate formation.
20. the preparation method of transparency electrode as claimed in claim 18, it is characterised in that the catalyst is four (triphenyls
Phosphorus) close palladium or dichloro double (triphenyl phosphorus) conjunction palladium.
21. a kind of organic solar batteries, including negative electrode, active layer and anode, it is characterised in that the negative electrode is transparent electricity
Pole, the transparency electrode includes substrate and is arranged on the transparent conductive film of the substrate surface, the transparent conductive film
Material includes conducting polymer grapheme material and chemical structural formula as shown in formula (I), and the grapheme material includes graphite
Alkene or doped graphene, the grapheme material are dispersed in the transparent conductive film,
Wherein, n is 10~30.
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