CN113078001B - Graphene oxide/polyaniline/nano-copper composite electrode coating - Google Patents
Graphene oxide/polyaniline/nano-copper composite electrode coating Download PDFInfo
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- CN113078001B CN113078001B CN202110366336.XA CN202110366336A CN113078001B CN 113078001 B CN113078001 B CN 113078001B CN 202110366336 A CN202110366336 A CN 202110366336A CN 113078001 B CN113078001 B CN 113078001B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a preparation method of a graphene oxide/polyaniline/nano-copper composite electrode coating, wherein the electrode coating is formed by compounding graphene oxide, polyaniline and nano-copper; the method is characterized in that: the coating is prepared by in-situ polymerization of aminated modified graphene oxide and polyaniline-nano copper, wherein the graphene oxide is modified by using a silane coupling agent, and an amino group is introduced to the surface of the graphene oxide to form graftable graphene oxide; the graftable graphene oxide and aniline monomer are mixed, ultrasonically dispersed, and ammonium persulfate and copper nitrate are added for common oxidation to obtain the graphene oxide/polyaniline/nano-copper composite electrode coating. The raw materials used in the preparation method are easy to obtain, the method is simple, and the prepared electrode coating has higher conductivity, chemical structure stability, multiple-cycle discharge loss rate and specific capacitance than a single material.
Description
Technical Field
The invention relates to the technical field of conductive coatings, in particular to a preparation method of a graphene oxide/polyaniline/nano-copper composite electrode coating.
Background
In modern society today, energy storage technology has become more and more a critical technology. China is a world large country for automobile production and sale, and nowadays, the energy problem and the environmental pollution problem are continuously aggravated, the development of new energy automobiles is an important strategy for meeting the national requirements of energy conservation, emission reduction and low-carbon economy, and the development key of the new energy automobiles lies in the progress and innovation of battery technology.
The super capacitor is used as a novel electric energy storage device with excellent performance between a battery and a traditional capacitor, and can completely meet the requirements of the battery of a new energy automobile due to the characteristics of large stored energy, large power density, high charging and discharging speed, economy and environmental protection, so that the super capacitor is concerned by broad students and researchers. The technical key of the super capacitor lies in the selection and preparation of electrode materials.
Polyaniline is a good conductive polymer, has the characteristics of low cost, unique doping mechanism, reversible oxidation reduction, easily available raw materials, simple synthesis method and good environmental stability, is widely concerned, but has poor chemical stability, structural stability and mechanical property; graphene is a substance with high specific surface area, high conductivity, and good chemical stability and structural stability, and a composite material made of the graphene and polyaniline can have the advantages of the graphene and the polyaniline.
According to the preparation method, a silane coupling agent is used for modifying graphene oxide, and amino groups are introduced to the surface of the graphene oxide to form graftable graphene oxide; the graftable graphene oxide and aniline monomer are mixed, ultrasonically dispersed, and ammonium persulfate and copper nitrate are added to be jointly oxidized to obtain the graphene oxide/polyaniline/nano-copper composite electrode coating.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide/polyaniline/nano-copper composite electrode coating; the raw materials used by the preparation method are easy to obtain, the method is simple, and the prepared electrode coating has higher conductivity, chemical structure stability, multiple-cycle discharge loss rate and specific capacitance than a single material.
The invention adopts the following technical scheme for realizing the purpose of the invention:
a preparation method of graphene oxide/polyaniline/nano-copper composite electrode coating comprises the following steps: 10% -45% of graphene oxide; 30% -70% of polyaniline; 1% -10% of nano copper; 1% -1.5% of reducing agent; 1% -2% of a coupling agent.
Further, the graphene oxide is modified graphene oxide through amination.
Further, the polyaniline is prepared by an in-situ polymerization method.
Further, the nano copper is obtained by adding copper nitrate in the in-situ polymerization process and co-oxidizing, and the particle size is 50-100nm.
Further, the coupling agent is a silane coupling agent.
Further, the defoaming agent is polydimethylsiloxane.
Further, the protective agent is ammonium dodecylbenzene sulfonate.
A preparation method of graphene oxide/polyaniline/nano-copper composite electrode paint comprises the following steps
Preparing graphene oxide powder in step (1): preparing the flake graphite into graphene oxide powder by a modified hummers method.
Preparing ammonia amination graphene oxide: preparing 1g of graphene oxide powder and 50ml of toluene into a solution, adding 0.1g of silane coupling agent KH550 into the solution, performing ultrasonic dispersion at normal temperature for 15min, and reacting the solution at 100 ℃ for 6h to obtain the aminated graphene oxide.
Preparing an aniline nitric acid solution: 0.05g of aniline was weighed and dissolved in 15ml of a 1mol/L nitric acid solution.
Preparing an in-situ polymerization oxidation liquid: weigh 0.05g ammonium persulfate and 0.084g CuNO 3 The resulting mixture was dissolved in 15ml of a 1mol/L nitric acid solution to prepare an oxidizing solution.
And (5) mixing the 2,3,4 solution, adding a defoaming agent and a protective agent, reacting for 6 hours in an ice-water bath, stirring for 6 hours at room temperature, and performing suction filtration. And (5) washing the product obtained in the step (5) by using distilled water and ethanol in sequence, and drying in vacuum to obtain the graphene oxide/polyaniline/nano-copper composite electrode coating.
Further, the step 1 specifically includes: taking a proper amount of concentrated sulfuric acid, sodium nitrate and 2g of flake graphite, uniformly mixing at 0 ℃, slowly dropwise adding 6g of potassium permanganate, reacting at 30 ℃ for 30min, adding a proper amount of deionized water and a hydrogen peroxide solution, continuously reacting for 10min, repeatedly washing the obtained product with the deionized water and a dilute hydrochloric acid solution, and finally freeze-drying to obtain the graphene oxide.
Further, the step 2 specifically includes: adding 1g of graphene oxide, 50ml of toluene solution and 0.1g of silane coupling agent KH550 into a 250ml beaker, performing ultrasonic dispersion for 15min, and stirring and reacting for 6h at 100 ℃ by using a magnetic stirrer to obtain the aminated modified graphene oxide.
Further, the step 3 specifically includes: adding 15ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, adding 0.05g of aniline, and performing ultrasonic dispersion for 15min.
Further, the step 4 specifically includes: adding 15ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, and then adding 0.05g of ammonium persulfate and 0.084g of CuNO 3 And carrying out ultrasonic dispersion for 15min.
Further, the step 5 specifically includes: and (3) slowly introducing the solution of 3,4 into the beaker in the step (2), adding an antifoaming agent polydimethylsiloxane and a protective agent ammonium dodecylbenzene sulfonate, reacting for 6 hours in an ice-water bath, stirring for 6 hours on a magnetic stirrer, washing for 3 times by using distilled water and alcohol, and performing vacuum drying to obtain the electrode coating.
Has the advantages that:
compared with the prior art, the invention and the utility model have the advantages that: as a novel conductive coating, the amine-group-graftable polyaniline is introduced on the surface of graphene oxide by adding the silane coupling agent KH550, and the electrode coating can be obtained by adding the nano-copper and the amine-group-modified graphene oxide in the process of polyaniline in-situ polymerization reaction to generate polyaniline.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
The electrode coating comprises the following components in parts by mass: 30% graphene oxide; 60% of polyaniline; 5% of nano copper; 5% of additive.
The graphene oxide in the components is amino-modified graphene oxide, and the additive comprises 1% of coupling agent, 2% of defoaming agent and 2% of protective agent.
The graphene oxide/polyaniline/nano-copper composite electrode coating is prepared by the following steps:
step 1, taking a proper amount of concentrated sulfuric acid, uniformly mixing sodium nitrate and 2g of flake graphite at 0 ℃, then slowly dropwise adding 6g of potassium permanganate, reacting at 30 ℃ for 30min, adding a proper amount of deionized water and a hydrogen peroxide solution, continuing to react for 10min, repeatedly washing the obtained product with the deionized water and a dilute hydrochloric acid solution, and finally freeze-drying to obtain the graphene oxide.
And 2, adding 1g of graphene oxide, 50ml of toluene solution and 0.1g of silane coupling agent KH550 into a 250ml beaker, performing ultrasonic dispersion for 15min, and stirring and reacting for 6h at 100 ℃ by using a magnetic stirrer to obtain the aminated modified graphene oxide.
And 3, adding 10ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, adding 0.03g of aniline, and performing ultrasonic dispersion for 15min.
Step 4, adding 10ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, and then adding 0.03g of ammonium persulfate and 0.08g of CuNO 3 And carrying out ultrasonic dispersion for 15min.
And 5, slowly introducing the solution of 3,4 into the beaker in the step 2, adding 2ml of polydimethylsiloxane and 2ml of ammonium dodecylbenzenesulfonate, reacting for 6 hours in an ice-water bath, stirring for 6 hours on a magnetic stirrer, washing for 3 times by using distilled water and alcohol, and performing vacuum drying to obtain the electrode coating.
Example 2
The electrode coating comprises the following components in parts by mass: 45% graphene oxide; 45% of polyaniline; 5% of nano copper; 5% of additive.
In the components, the graphene oxide is amino-modified graphene oxide, and the additive comprises 2% of a coupling agent, 1% of a defoaming agent and 2% of a protective agent.
The graphene oxide/polyaniline/nano-copper composite electrode coating is prepared by the following steps:
step 1, taking a proper amount of concentrated sulfuric acid, uniformly mixing sodium nitrate and 2g of flake graphite at 0 ℃, then slowly dropwise adding 6g of potassium permanganate, reacting at 30 ℃ for 30min, adding a proper amount of deionized water and a hydrogen peroxide solution, continuing to react for 10min, repeatedly washing the obtained product with the deionized water and a dilute hydrochloric acid solution, and finally freeze-drying to obtain the graphene oxide.
And 2, adding 1.2g of graphene oxide, 50ml of toluene solution and 0.15g of silane coupling agent KH550 into a 250ml beaker, performing ultrasonic dispersion for 15min, and stirring and reacting for 6h at 90 ℃ by using a magnetic stirrer to obtain the aminated modified graphene oxide.
And 3, adding 15ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, adding 0.05g of aniline, and performing ultrasonic dispersion for 15min.
Step 4, adding 15ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, and then adding 0.05g of ammonium persulfate and 0.09g of CuNO 3 And carrying out ultrasonic dispersion for 15min.
And 5, slowly introducing the solution of 3,4 into the beaker in the step 2, adding 1ml of polydimethylsiloxane and 2ml of ammonium dodecylbenzenesulfonate, reacting for 6 hours in an ice-water bath, stirring for 6 hours on a magnetic stirrer, washing for 3 times by using distilled water and alcohol, and performing vacuum drying to obtain the electrode coating.
Example 3
The electrode coating comprises the following components in parts by mass: 55% graphene oxide; 35% of polyaniline; 5% of nano copper; 5% of additive.
The graphene oxide in the components is amino-modified graphene oxide, and the additive comprises 3% of a coupling agent, 1% of a defoaming agent and 1% of a protective agent.
The graphene oxide/polyaniline/nano-copper composite electrode coating is prepared by the following steps:
step 1, taking a proper amount of concentrated sulfuric acid, uniformly mixing sodium nitrate and 3g of flake graphite at 0 ℃, slowly dropwise adding 9g of potassium permanganate, reacting at 30 ℃ for 30min, adding a proper amount of deionized water and a hydrogen peroxide solution, continuously reacting for 10min, repeatedly washing the obtained product with the deionized water and a dilute hydrochloric acid solution, and finally freeze-drying to obtain the graphene oxide.
And 2, adding 1.5g of graphene oxide, 50ml of toluene solution and 0.2g of silane coupling agent KH550 into a 250ml beaker, performing ultrasonic dispersion for 15min, and stirring and reacting for 6h at 100 ℃ by using a magnetic stirrer to obtain the aminated modified graphene oxide.
And 3, adding 20ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, adding 0.065g of aniline, and performing ultrasonic dispersion for 15min.
Step 4, adding 20ml of nitric acid solution with the concentration of 1mol/L into a 50ml beaker, and then adding 0.065g of persulfuric acidAmmonium and 0.1g CuNO 3 And carrying out ultrasonic dispersion for 20min.
And 5, slowly introducing the solution of 3,4 into the beaker in the step 2, adding 1ml of polydimethylsiloxane and 1ml of ammonium dodecylbenzenesulfonate, reacting for 6 hours in an ice-water bath, stirring for 6 hours on a magnetic stirrer, washing for 3 times by using distilled water and alcohol, and performing vacuum drying to obtain the electrode coating.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (4)
1. A preparation method of graphene oxide/polyaniline/nano-copper composite electrode coating is characterized by comprising the following steps: the preparation method comprises (1) preparing crystalline flake graphite into graphene oxide powder; (2) Preparing 1g of graphene oxide powder and 50ml of toluene into a solution; (3) Adding 0.1g of silane coupling agent into the solution in the step 2, and performing ultrasonic dispersion for 15min at normal temperature; (4) Step 3, reacting the solution at 100 ℃ for 6 hours to obtain amination modified graphene oxide; (5) Weighing 0.05g of aniline monomer, and dissolving in 15ml of nitric acid solution with the concentration of 1 mol/L; (6) Weigh 0.05g ammonium persulfate and 0.084g CuNO 3 Dissolving in 15ml nitric acid solution with the concentration of 1mol/L to prepare oxidation solution; (7) Mixing the 4,5,6 solution, adding an organic silicon defoaming agent and an ammonium dodecylbenzene sulfonate protective agent, reacting for 6 hours in an ice water bath, stirring for 6 hours at room temperature, and performing suction filtration; (8) Washing the product obtained in the step (7) with distilled water and ethanol in sequence, and drying in vacuum to obtain the graphene oxide/polyaniline/nano-copper composite electrode coating; the electrode coating comprises the following components in percentage by mass: 10% -45% of graphene oxide; 30% -70% of polyaniline; 1% -10% of nano copper; 1% -3% of a coupling agent;
1% -3% of a protective agent; 1% -3% of defoaming agent.
2. The graphene oxide/polyaniline/nano-copper composite electrode coating according to claim 1, wherein: the particle size of the nano copper is 50-100nm.
3. The graphene oxide/polyaniline/nano-copper composite electrode coating as claimed in claim 1, wherein: the silane coupling agent is KH550.
4. The graphene oxide/polyaniline/nano-copper composite electrode coating as claimed in claim 1, wherein: the defoaming agent is polydimethylsiloxane.
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Citations (3)
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| CN104693796A (en) * | 2015-03-06 | 2015-06-10 | 苏州欢颜电气有限公司 | Preparation and application of conducting composite material polyaniline/graphene/copper |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN108987127A (en) * | 2018-08-08 | 2018-12-11 | 合肥滴答科技有限公司 | A kind of polyaniline capacitance material and preparation method thereof |
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| CN103193978B (en) * | 2013-04-24 | 2015-07-08 | 黑龙江大学 | Preparation method for polyaniline/graphene/nano-copper composite material |
| CN109559899A (en) * | 2018-12-04 | 2019-04-02 | 黑龙江大学 | The preparation method of the graphene-supported cupro-nickel solid solution composite material of polyaniline-coated |
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Patent Citations (3)
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| CN104693796A (en) * | 2015-03-06 | 2015-06-10 | 苏州欢颜电气有限公司 | Preparation and application of conducting composite material polyaniline/graphene/copper |
| CN104910378A (en) * | 2015-05-26 | 2015-09-16 | 浙江理工大学 | Preparation method for polyaniline/graphene oxide nanocomposite |
| CN108987127A (en) * | 2018-08-08 | 2018-12-11 | 合肥滴答科技有限公司 | A kind of polyaniline capacitance material and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| "Graphene Oxide Decorated Nanometal-Poly(Anilino-Dodecylbenzene Sulfonic Acid) for Application in High Performance Supercapacitors";Nomxolisi R. Dywili, et al.;《Micromachines》;20190211;第10卷;第115页 * |
| "Preparation of conductive polyaniline grafted graphene hybrid composites via graft polymerization at room temperature";Baoli Ou,et al.;《RSC Adv.》;20140804;第4卷;第43212-43219页 * |
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