CN108075041B - Flexible composite electrode, preparation method and application thereof - Google Patents
Flexible composite electrode, preparation method and application thereof Download PDFInfo
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- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
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- H—ELECTRICITY
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Abstract
The invention provides a flexible composite electrode, a preparation method and application thereof, wherein the preparation method of the flexible composite electrode comprises the following steps: pyridine, a ferric salt catalyst and an alcohol solvent are uniformly mixed to obtain a prepolymer mixed solution, the prepolymer mixed solution is uniformly coated on a substrate, the prepolymer mixed solution is heated and dried in an anhydrous oxygen environment, the prepolymer mixed solution is placed into a reaction kettle dropwise added with a 3, 4-ethylene dioxythiophene monomer, and the reaction kettle is heated and gas is introduced to carry out gas phase polymerization reaction to obtain the flexible composite electrode. By adopting the method, graphene sheets with smaller sizes can be connected in series, so that the large-area flexible composite electrode prepared by a solution method is realized, and the method has wide application in organic electroluminescent devices and solar cells.
Description
Technical Field
The invention relates to the technical field of preparation of flexible composite electrodes, in particular to a graphene flexible composite electrode, an organic electroluminescent device with the same and a flexible composite electrode.
Background
Organic Light Emitting devices (abbreviated as OLEDs) are used as next generation lighting and display technologies, and have the advantages of wide color gamut, fast response, wide viewing angle, no pollution, high contrast, planarization, and the like.
A typical organic electroluminescent device generally includes a transparent substrate, a first transparent electrode, a second electrode, and an organic light emitting unit disposed between the two electrodes. The currently used transparent electrode is generally ITO, and because the mechanical property of ITO is poor, the ITO is generally considered to be not suitable for being used as a flexible transparent electrode. At present, metal nanowires, graphene and the like are considered as ideal materials for manufacturing flexible electrodes in the industry. However, how to prepare and transfer graphene in a large area, how to utilize the existing graphene with smaller dimension, how to utilize and expand the two-dimensional conductivity of the graphene material, and the like, still need to be solved.
CN105118681A discloses a method for manufacturing a graphene-based ternary composite flexible electrode, comprising: dissolving a first conductive polymer in an organic solvent to obtain a first conductive polymer solution; spin-coating a first conductive polymer solution on a flexible substrate and drying to form a first conductive polymer layer; forming a graphene layer by using a cyclic voltammetry method by using the first conductive polymer layer as a working electrode and using the graphene oxide dispersion liquid as an electrolyte; and (3) carrying out air-spraying of an oxidant on the first conductive polymer/graphene composite film and carrying out vapor deposition in the atmosphere of a second conductive polymer monomer to form the first conductive polymer/graphene/second conductive polymer composite film. The conductive polymer obtained by the method is unstable and generally contains acidic substances, such as p-toluenesulfonic acid PSS; in addition, the cyclic voltammetry has poor film-forming uniformity and complex process flow, and is not beneficial to large-scale industrial production.
CN105552333A A preparation method of a graphene/silicon/conducting polymer composite negative electrode material belongs to the field of electrochemistry and new energy materials. The preparation method comprises the steps of firstly preparing a graphene oxide material, mixing the graphene oxide with silicon powder and a polymer monomer, polymerizing the polymer monomer under a certain condition, then directly drying to obtain a graphene oxide/silicon/conductive polymer film composite material, and then preparing the graphene/silicon/conductive polymer foam composite material by adopting a hydrazine hydrate steam reduction method. The film-forming roughness of the method is very large, and the method cannot be applied to the display field; and a large amount of chemical reactions, byproducts and particles are difficult to control in the preparation process.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the existing graphene composite electrode material cannot be prepared in a large area in the preparation process, and further, the invention provides a preparation method of a flexible composite electrode, which can be used for preparing the large-area flexible composite electrode by a solution method by connecting graphene sheets with smaller sizes in series.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a flexible composite electrode comprises the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain a prepolymer mixed solution;
s2, adding graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing graphene, pyridine and a ferric salt catalyst;
s3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomer, and heating the reaction kettle and introducing gas to carry out gas-phase polymerization reaction to obtain a flexible composite electrode; the gas is N2And/or an inert gas.
Pyridine in the prepolymer mixed liquid: trivalent iron salt catalyst: the molar ratio of the alcohol solvent is (0.95-1.05): (9.5-10.5): 95-105.
The ferric salt catalyst is ferric p-toluenesulfonate or ferric trichloride, and the alcohol solvent is n-butanol.
The gas flow rate in the step S3 is 0-1m3H, preferably from 0.1 to 1m3The heating temperature is 40-90 ℃ and preferably 50-60 ℃.
The reaction process comprises the following steps:
by heating the reaction kettle and simultaneously introducing gas, the 3, 4-ethylene dioxythiophene monomer EDOT is gasified and contacts with the catalyst on the substrate in a gas form, and a polymerization reaction is carried out under the catalytic action of the catalyst, so that the EDOT monomer is changed into a PEDOT (polyethylene dioxythiophene) polymer. In the process of polymerization reaction, graphene does not participate in the reaction, but in the process, the polymer can connect fragmented graphene into a piece like a piece of split cloth in the growth process.
The preparation method of the flexible composite electrode further comprises the following steps:
and S4, cleaning the flexible composite electrode obtained in the step S3 by adopting water or an alcohol solvent, and removing the ferric salt catalyst on the surface of the flexible composite electrode.
A flexible composite electrode is prepared by the method.
An organic light-emitting device comprises a substrate, and a first electrode layer, a light-emitting unit and a second electrode layer which are sequentially formed on the substrate, wherein the first electrode and/or the second electrode are/is a flexible composite electrode, and the thickness of the flexible composite electrode is 50nm-1000 nm.
The organic electroluminescent device is a top-emitting organic electroluminescent device, and the first electrode of the organic electroluminescent device is the flexible composite electrode.
A solar cell piece, comprising an anode, a photoelectric conversion unit and a light-transmitting cathode which are sequentially stacked, wherein the light-transmitting cathode is the flexible composite electrode as claimed in claim 7.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of a flexible composite electrode, which comprises the following steps: uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain a prepolymer mixed solution; adding graphene into the prepolymer mixed liquid, performing gas-phase polymerization reaction to obtain a flexible composite electrode, and washing off the catalyst on the surface of the electrode. By adopting the method, graphene sheets with smaller sizes can be connected in series, and the preparation of the large-area flexible composite electrode by a solution method is realized.
In the reaction process, the reaction kettle is heated and gas is introduced at the same time, the 3, 4-ethylene dioxythiophene monomer EDOT is gasified and contacts with the catalyst on the substrate in a gas form, and a polymerization reaction is carried out under the catalytic action of the catalyst, so that the EDOT monomer is changed into a PEDOT (polyethylene dioxythiophene) polymer. In the process of polymerization reaction, graphene does not participate in the reaction, but in the process, the polymer can connect fragmented graphene into a piece like a piece of split cloth in the growth process.
2. The reactant of the invention has no special requirement on graphene, as long as the graphene is not blocky or aggregated in a large area, and the addition amount of the graphene can be added at will according to the requirements of electric conductivity and light transmittance, so that the graphene has wide industrial prospect.
3. The invention adopts a gas-phase polymerization reaction mode, and the inventor carries out intensive research on the flow rate of gas to find that the higher the flow rate of gas is, the higher the film forming speed of polymerization reaction is, but the conductivity is not good; the smaller the flow rate of the gas, the longer the reaction time, and the thicker the film thickness of the polymerization reaction, the better the conductivity, but the lower the light transmittance. The inventors of the present invention have made repeated experiments and finally determined the gas flow rate to be 0 to 1m3H, preferably from 0.1 to 1m3/h。
4. The inventors have conducted intensive studies on the temperature of the phase polymerization reaction, and as a result, have found that the film forming speed is faster as the temperature is higher, but there is a difference in the electrical conductivity, and as a result of repeated studies and experiments, the reaction temperature is finally determined to be 40 to 90 c, preferably 50 to 60 c.
5. The OLED device and the solar cell adopting the flexible composite electrode have excellent mechanical bending, and can be bent and curled according to requirements.
Drawings
FIG. 1 is a schematic diagram of a flexible composite electrode preparation process;
FIG. 2 is a schematic structural diagram of a top-emitting organic electroluminescent device;
fig. 3 is a schematic structural diagram of a solar cell.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. It will be understood that when an element such as a layer, region or substrate is referred to as being "formed on" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly formed on" or "directly disposed on" another element, there are no intervening elements present.
A preparation method of a flexible composite electrode comprises the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain a prepolymer mixed solution.
Pyridine in the prepolymer mixed liquid: trivalent iron salt catalyst: the molar ratio of the alcohol solvent is (0.95-1.05): (9.5-10.5): 95-105. The ferric salt catalyst can be ferric p-toluenesulfonate or ferric trichloride, and the alcohol solvent can be n-butanol. S2, adding graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing graphene, pyridine and a ferric salt catalyst; the temperature for heating and drying is not critical, as long as the alcohol solvent can be promoted to evaporate.
S3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomer, and heating the reaction kettle and introducing gas to carry out gas-phase polymerization reaction to obtain a flexible composite electrode; the gas is N2And/or an inert gas at a flow rate of 0-1m3H, preferably from 0.1 to 1m3The heating temperature in step S3 is 40-90 ℃, preferably 50-60 ℃.
And S4, cleaning the flexible composite electrode obtained in the step S3 by adopting water or an alcohol solvent, and removing the ferric salt catalyst on the surface of the flexible composite electrode.
The reaction process comprises the following steps: by heating the reaction kettle and simultaneously introducing gas, the 3, 4-ethylene dioxythiophene monomer EDOT is gasified and contacts with the catalyst on the substrate in a gas form, and a polymerization reaction is carried out under the catalytic action of the catalyst, so that the EDOT monomer is changed into a PEDOT (polyethylene dioxythiophene) polymer. In the process of polymerization reaction, graphene does not participate in the reaction, but in the process, the polymer can connect fragmented graphene into a piece like a piece of split cloth in the growth process.
A flexible composite electrode is prepared by the method.
An organic electroluminescent device comprises a substrate, and a first electrode layer, a light-emitting unit and a second electrode layer which are sequentially formed on the substrate, and is characterized in that the first electrode and/or the second electrode are/is a flexible composite electrode, and the thickness of the flexible composite electrode is 50nm-1000 nm.
The organic electroluminescent device is a top-emitting organic electroluminescent device, and the first electrode of the organic electroluminescent device is the flexible composite electrode.
A solar cell slice comprises an anode, a photoelectric conversion unit and a light-transmitting cathode which are sequentially overlapped, and is characterized in that the light-transmitting cathode is a flexible composite electrode.
Example 1
As shown in fig. 1, the method for manufacturing a flexible composite electrode of the present embodiment includes the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain 100g of prepolymer mixed liquid; wherein the ratio of pyridine: ferric salt catalyst (iron p-toluenesulfonate): the molar ratio of the alcohol solvent (n-butanol) is 1:10: 100.
S2, adding 50g of graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing the graphene, pyridine and a ferric salt catalyst;
s3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomer, heating the reaction kettle to 50-60 ℃, and introducing the gas at a flow rate of 0.5-1m3N of/h2Carrying out gas-phase polymerization reaction on the gas to obtain a flexible composite electrode;
and S4, cleaning the flexible composite electrode obtained in the step S3 by using distilled water, and removing the ferric salt catalyst on the surface of the flexible composite electrode to obtain the flexible composite electrode.
Example 2
The preparation method of the flexible composite electrode of the embodiment comprises the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain 100g of prepolymer mixed liquid; wherein the ratio of pyridine: ferric salt catalyst (ferric chloride): the molar ratio of the alcohol solvent (n-butanol) is 0.95:10.5: 95.
S2, adding 60g of graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing graphene, pyridine and a ferric salt catalyst;
s3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomer, and carrying out reactionHeating the reaction kettle to 40-50 ℃, and introducing the gas at a flow rate of 0-0.5m3Carrying out gas-phase polymerization reaction on the inert gas to obtain a flexible composite electrode;
and S4, cleaning the flexible composite electrode obtained in the step S3 by adopting an ethanol solution, and removing the ferric salt catalyst on the surface of the flexible composite electrode to obtain the flexible composite electrode.
Example 3
The preparation method of the flexible composite electrode of the embodiment comprises the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain 100g of prepolymer mixed liquid; wherein the ratio of pyridine: ferric salt catalyst (iron p-toluenesulfonate): the molar ratio of the alcohol solvent (n-butanol) is 1.05:9.5: 105.
S2, adding 20g of graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing the graphene, pyridine and a ferric salt catalyst;
s3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomer, heating the reaction kettle to 60-90 ℃, and introducing the gas at a flow rate of 0.1-0.5m3N of/h2Carrying out gas-phase polymerization reaction on the gas to obtain a flexible composite electrode;
and S4, cleaning the flexible composite electrode obtained in the step S3 by using distilled water, and removing the ferric salt catalyst on the surface of the flexible composite electrode to obtain the flexible composite electrode.
The flexible composite electrode of the present invention has no special requirement for graphene, and may be added in any amount as long as it is free from bulk or large-area aggregation, and the amount of the flexible composite electrode is not limited to the amount used in examples 1 to 3, as long as it is free from bulk or large-area aggregation.
Example 4
As shown in fig. 2, a top-emission organic electroluminescent device includes a substrate 1, and a first electrode layer 2, a light-emitting unit 3, and a second electrode layer 4 sequentially formed on the substrate, where the first electrode layer 2 is a Hybrid-electrode prepared in embodiments 1 to 3, and the thickness of the flexible composite electrode is 50nm to 1000 nm. The light emitting unit 3 is a conventional light emitting layer, and generally includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. The flexible composite electrode provided by the invention has universality and has no special requirements on a light-emitting unit.
Example 5
As shown in fig. 3, a solar cell comprises a substrate 5, an anode 6, a photoelectric conversion unit 7 and a light-transmitting cathode 8, which are sequentially stacked, wherein the light-transmitting cathode 8 is a flexible composite electrode prepared in embodiments 1 to 3. The photoelectric conversion unit 7 is of a conventional structure, and the flexible composite electrode provided by the invention has universality and has no special requirements on the photoelectric conversion unit. Since the photoelectric conversion unit is not the invention of the present application, it is not described in detail.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. An organic electroluminescent device comprises a substrate, and a first electrode, a light-emitting unit and a second electrode which are sequentially formed on the substrate, and is characterized in that the first electrode and/or the second electrode are/is a flexible composite electrode prepared by the following method, and the thickness of the flexible composite electrode is 50nm-1000 nm;
the preparation method of the flexible composite electrode comprises the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain a prepolymer mixed solution;
s2, adding graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing graphene, pyridine and a ferric salt catalyst;
s3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomers, heating the reaction kettle, introducing gas to carry out gas-phase polymerization reaction, wherein graphene does not participate in the reaction in the polymerization reaction generation process, and the fragmented graphene is connected into a piece like a piece-sewing cloth in the growth process of a polymer to obtain a flexible composite electrode; the gas is N2 and/or inert gas;
the gas flow rate in the step S3 is 0.1-1m3/h, and the heating temperature in the step S3 is 40-90 ℃;
pyridine in the prepolymer mixed liquid: trivalent iron salt catalyst: the molar ratio of the alcohol solvent is (0.95-1.05): (9.5-10.5): 95-105;
the ferric salt catalyst is ferric p-toluenesulfonate or ferric trichloride, and the alcohol solvent is n-butanol.
2. The organic electroluminescent device as claimed in claim 1, wherein the heating temperature in step S3 is 50-60 ℃.
3. The organic electroluminescent device according to claim 1 or 2, further comprising the steps of:
and S4, cleaning the flexible composite electrode obtained in the step S3 by adopting water or an alcohol solvent, and removing the ferric salt catalyst on the surface of the flexible composite electrode.
4. The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device is a top-emitting organic electroluminescent device, and the first electrode is the flexible composite electrode.
5. A solar cell slice comprises an anode, a photoelectric conversion unit and a light-transmitting cathode which are sequentially superposed, and is characterized in that the light-transmitting cathode is a flexible composite electrode prepared by the following method;
the preparation method of the flexible composite electrode comprises the following steps:
s1, uniformly mixing pyridine, a ferric salt catalyst and an alcohol solvent to obtain a prepolymer mixed solution;
s2, adding graphene into the prepolymer mixed liquid prepared in the step S1, uniformly coating the mixture on a substrate, and heating and drying the substrate in an anhydrous oxygen environment to obtain a dry substrate containing graphene, pyridine and a ferric salt catalyst;
s3, putting the dried substrate prepared in the step S2 into a reaction kettle dropwise added with 3, 4-ethylenedioxythiophene monomers, heating the reaction kettle, introducing gas to carry out gas-phase polymerization reaction, wherein graphene does not participate in the reaction in the polymerization reaction generation process, and the fragmented graphene is connected into a piece like a piece-sewing cloth in the growth process of a polymer to obtain a flexible composite electrode; the gas is N2 and/or inert gas;
the gas flow rate in the step S3 is 0.1-1m3/h, and the heating temperature in the step S3 is 40-90 ℃;
pyridine in the prepolymer mixed liquid: trivalent iron salt catalyst: the molar ratio of the alcohol solvent is (0.95-1.05): (9.5-10.5): 95-105;
the ferric salt catalyst is ferric p-toluenesulfonate or ferric trichloride, and the alcohol solvent is n-butanol.
6. The solar cell sheet according to claim 5, wherein the heating temperature in the step S3 is 50-60 ℃.
7. The solar cell sheet according to claim 5 or 6, further comprising the steps of:
and S4, cleaning the flexible composite electrode obtained in the step S3 by adopting water or an alcohol solvent, and removing the ferric salt catalyst on the surface of the flexible composite electrode.
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