CN107641824A - Graphene conductive polymer composites and preparation method thereof - Google Patents
Graphene conductive polymer composites and preparation method thereof Download PDFInfo
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- CN107641824A CN107641824A CN201710881660.9A CN201710881660A CN107641824A CN 107641824 A CN107641824 A CN 107641824A CN 201710881660 A CN201710881660 A CN 201710881660A CN 107641824 A CN107641824 A CN 107641824A
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Abstract
The invention discloses a kind of graphene conductive polymer composites and preparation method thereof.The preparation method includes：Using three-dimensional grapheme macroscopic body as working electrode or the electric conductor to be loaded with three-dimensional grapheme macroscopic body is used as working electrode, and with to electrode, the electrolyte comprising polymer monomer structure electrochemical reaction system, and, conducting polymer is deposited by graphene nanometer sheet surface of the electrochemical method in the three-dimensional grapheme macroscopic body, obtains target product.The preparation method of the present invention is simple efficiently, process conditions are controllable, cost is cheap, it is environmentally friendly, suitable for large-scale industrial production, obtained composite has the advantages that stability is good, electrical conductivity is high, in Thin Film Transistor-LCD, the connection of ultra-fine circuit, energy production conversion and energy storage device, electromagnetic shielding, heat conduction and heat radiation, sensor, biological medicine, inhale the field such as ripple and catalysis and have wide application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of graphene-conducting polymer composite material, more particularly to a kind of electrochemistry
The method for preparing graphene composite material, belongs to field of material technology.
Background technology
Graphene is the New Two Dimensional atomic crystal that the monoatomic layer connected by carbon atom with sp2 hydridization is formed, because having
The excellent properties such as higher mechanical strength, good electrical conductivity and great specific surface area receive significant attention.With CNT
Similar, graphene is difficult to be turned out a produce as single raw material, and mainly utilizes its prominent characteristic and other materials system
Carry out compound, so as to obtain the advanced composite material (ACM) with excellent properties, thus graphene composite material turns into graphene application
An important research direction in field.Graphene is the functional stuffing of Nano grade, and polymer is compound can improve material
Mechanical property, hot property, electrical property etc., be expected in lithium ion battery, ultracapacitor, effective catalyst and biology sensor
Widely application is obtained Deng field.The preparation method of graphene/polymer composites mainly has solution mixing, melt blending
And situ aggregation method.Solution blending is that graphene and polymer are carried out into solution blending to prepare graphene/polymer composites.
Solution blended process needs substantial amounts of solvent, and cost is high, and environmental pollution is serious.Melt-blending process generally exists graphene and polymer
It is blended under molten condition and composite is made.In nano composite material prepared by melt-blending process, graphene dispersion is poor.
Situ aggregation method is to mix graphene with polymer monomer, adds initiator initiation reaction, and composite is finally made.It is in situ
Graphene uniform can be dispersed in polymeric matrix by polymerization, but add the viscosity increase of the polymer of graphene, be made
Obtaining polymerisation becomes complicated, reacts poor controllability.
The content of the invention
It is a primary object of the present invention to provide a kind of graphene-conducting polymer composite material and preparation method thereof, with
Overcome deficiency of the prior art.
For achieving the above object, present invention employs following technical scheme：
The embodiments of the invention provide a kind of preparation method of graphene-conducting polymer composite material, it includes：
Using three-dimensional grapheme macroscopic body as working electrode or using be loaded with the electric conductor of three-dimensional grapheme macroscopic body as
Working electrode, and with to electrode, the electrolyte comprising polymer monomer structure electrochemical reaction system, and
Conducting polymer is deposited by graphene nanometer sheet surface of the electrochemical method in the three-dimensional grapheme macroscopic body
Thing, form graphene-conducting polymer composite material.
Further, the polymer monomer includes aniline, pyrroles, thiophene or acetylene etc., and not limited to this.
Further, the electrochemical method includes cyclic voltammetry, pulse voltammetry, controls potentiometry or control current method
Deng, and not limited to this.
The embodiments of the invention provide the graphene-conducting polymer composite material prepared by preceding method.
Compared with prior art, advantages of the present invention at least that：
(1) the simple efficient, process conditions of the preparation method of graphene-conducting polymer composite material provided by the invention can
Control, cost is cheap, it is environmentally friendly, suitable for large-scale industrial production；
(2) conducting polymer disperses in graphenic surface in graphene-conducting polymer composite material provided by the invention
It is more uniformly distributed, adhesion is strong between the two so that the composite has the advantages that stability is good, electrical conductivity is high, brilliant in film
Body pipe liquid crystal display, ultra-fine circuit connection, energy production conversion with energy storage device, electromagnetic shielding, heat conduction and heat radiation, sensor,
Biological medicine, inhale the field such as ripple and catalysis and have wide application prospects.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 obtains grapheme/polyaniline composite material；
Fig. 2 is the transmission electron microscope picture that the embodiment of the present invention 1 obtains grapheme/polyaniline composite material.
Embodiment
A kind of preparation method bag for graphene-conducting polymer composite material that the one side of the embodiment of the present invention provides
Include：
Using three-dimensional grapheme macroscopic body as working electrode or using be loaded with the electric conductor of three-dimensional grapheme macroscopic body as
Working electrode, and with to electrode, the electrolyte comprising polymer monomer structure electrochemical reaction system, and
Conducting polymer is deposited by graphene nanometer sheet surface of the electrochemical method in the three-dimensional grapheme macroscopic body
Thing, form graphene-conducting polymer composite material.
Further, the three-dimensional grapheme macroscopic body assembles the grapheme foam to be formed including graphene nanometer sheet.
For example, the three-dimensional grapheme macroscopic body can be selected from passes through three-dimensional made from hydro-thermal reaction using graphene oxide
Graphene macroform.
Preferably, the aperture of hole contained by the grapheme foam is 1 nanometer~100 microns.
For example, the three-dimensional grapheme macroscopic body can be selected from using metal foaming material as substrate, pass through chemical vapor deposition
Three-dimensional grapheme macroscopic body made from area method.Preferably, the metal foaming material includes nickel foam or foam copper etc., and unlimited
In this.
Further, the material of the electric conductor metal such as including Au, Ag, Pt, Fe, Co, Ni, Cu or Ru, also may be used certainly
To be other nonmetallic materials with excellent conductive performance etc..
Further, the electrolyte includes polymer monomer, electrolyte, solvent etc..
Further, the solvent in the electrolyte includes water and/or organic solvent.Wherein, the organic solvent can be with
Including methanol, ethanol, ethylene glycol, acetone, dimethylformamide, dimethyl sulfoxide (DMSO), chloroform, ethyl acetate or propene carbonate
Deng, and not limited to this.
Further, the electrolyte in the electrolyte can include sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, sodium chloride, sulphur
Sour sodium, sodium nitrate, potassium chloride, potassium nitrate or potassium sulfate etc., and not limited to this.
More preferable, the electrolyte concentration in the electrolyte can be 0.1~1mol/L.
More preferable, the polymer monomer concentration in the electrolyte can be 0.01~10mol/L.
Further, the polymer monomer includes aniline, pyrroles, thiophene or acetylene etc., and not limited to this.
Further, the electrochemical method includes cyclic voltammetry, pulse voltammetry, controls potentiometry or control current method
Deng, and not limited to this.
Further, the electrochemical reaction system also includes reference electrode, such as Ag/AgCl reference electrodes etc., and not
It is limited to this.Obvious, in the electrochemical operation system, working electrode, electrode etc. is immersed in electrolyte.
Preferably, for the potential range used in the electrochemical method for -3V~+3V, current range is 0~10A, deposition
Time is 0~10h.
The embodiment of the present invention another aspect provides the graphene prepared by preceding method-conducting polymer composite wood
Material, the wherein mass ratio of graphene and conducting polymer are 1：100~100：1.
The present invention mainly utilizes conducting polymer monomer, and carries out original on three-dimensional grapheme surface by electrochemical techniques
Position polymerization obtains graphene-conducting polymer composite material.In the preparation process of the composite, by glucose current equation,
The regulation and control of the experiment parameters such as electrolyte component, the control for conducting polymer size, pattern etc. can be effectively realized, makes conduction
Polymer is more uniformly distributed in graphene nanometer sheet Dispersion on surface, and both combinations are more firm, so that obtained graphene-conduction
Polymer composites have the advantages such as stability is good, electrical conductivity is high.
Make more detailed illustrate to technical scheme below in conjunction with accompanying drawing and some preferred embodiments.
Embodiment 1：Grapheme foam is made through 180 DEG C of hydro-thermal reaction 12h using 1mg/mL graphene dispersing solutions.By graphite
Alkene foam is adhered to foam nickel surface by tablet press machine and is used as working electrode, immerses H containing 0.5M2SO4It is water-soluble with 0.1M aniline
Liquid；Pt pieces are done does reference electrode to electrode, Ag/AgCl；Electropolymerization is carried out using cyclic voltammetry, electric potential scanning scope is -0.2
~0.8V, cycle-index 10 times, sweep speed 50mV/s；Reaction product is peeled off from platinum electrode, through 60 degree of vacuum drying
5h, graphene-polyaniline composite material is made.It is that graphene-polyaniline is compound made from the present embodiment to refer to Fig. 1 and Fig. 2
The scanning electron microscope (SEM) photograph of material, transparent gauze-like is graphene nanometer sheet in figure, surface attachment polyaniline nano band.The stone
The electrical conductivity of black alkene-polyaniline composite material is~250S/m.
Embodiment 2：Grapheme foam is made through 200 DEG C of hydro-thermal reaction 8h using 1.5mg/mL graphene dispersing solutions.By platinum
Silk electrode is bonded on grapheme foam with conductive silver glue, and as working electrode, Pt silks are done to electrode, and Ag/AgCl does reference electricity
Pole；The mixed liquor of 0.3mol/L thiophene and BFEE (BFEE) is cooked electrolyte；Controlling potential is in 1.3V, deposition 10min.
Reaction product is dried in vacuo 5h under 80 degree, graphene-polythiophene composite material is made.The graphene-polythiophene composite wood
The electrical conductivity of material is~210S/m.
Embodiment 3：Grapheme foam is made through 180 DEG C of hydro-thermal reaction 12h using 2mg/mL graphene dispersing solutions.By graphite
Alkene foam is adhered to nickel sheet surface by conductive silver glue and worked electrode, and Pt silks are done does reference electrode to electrode, Ag/AgCl；Contain
The aqueous solution of 0.1mol/L pyrroles and 0.1mol/L dodecyl sodium sulfates does electrolyte；It is heavy that electricity is carried out using cyclic voltammetry
Product, electric potential scanning scope are -0.2~0.9V, cycle-index 10 times, sweep speed 20mV/s；By 60 degree of dryings of reaction product
5h, graphene-polypyrrole composite is made.The electrical conductivity of the graphene-polypyrrole composite is~200S/m.
Embodiment 4：Grapheme foam is made through 180 DEG C of hydro-thermal reaction 12h using 5mg/mL graphene dispersing solutions.By graphite
Alkene foam is adhered to nickel sheet surface by tablet press machine and worked electrode, and Pt silks are done does reference electrode to electrode, Ag/AgCl；Immerse
H containing 0.5M2SO4Electrolyte is done with the aqueous solution of 0.5M aniline；Electro-deposition is carried out using current method is controlled, control electric current density is
5mA/cm2；By 60 degree of dry 5h of reaction product, graphene-polyaniline composite material is made.The graphene-polyaniline composite wood
The electrical conductivity of material is~300S/m.
Comparative example 1：0.2g graphenes are added in the certain density PVP aqueous solution, ultrasound
30min, put it into mechanical agitation 10min in ice-water bath.50mL0.5mol/L hydrochloric acid and 9.3g aniline monomer are added
Into above-mentioned mixed solution, pre- stirring a period of time in ice bath.11.4g ammonium persulfates are taken to be dissolved in 50mL distilled water and ice
To 0 DEG C, then it is disposably added to initiation reaction in above-mentioned mixed liquor, initial temperature is controlled at 0~2 DEG C.Reaction terminates
Product is centrifuged afterwards, dried, graphene-polyaniline composite material is made, its electrical conductivity is about 140S/m.As a result illustrate, use
The electrical conductivity of graphene-polyaniline composite material prepared by situ aggregation method is relatively low, and preparation process is relative complex.
Comparative example 2：
0.1 graphene oxide is added in 100mL water after ultrasonic disperse, adds 4.6g aniline monomers further ultrasound point
Dissipate and form uniform mixed liquor；The mixed liquor is coated on electrode and spontaneously dried, two terminal battery is formed using above-mentioned electrode,
0.5MH is injected between electrode2SO4Acidic electrolysis bath；The battery two electrodes apply scan round voltage, voltage range for-
0.2~+1.0V, circulate 10 times, reaction splits battery after terminating in water, that is, obtains graphene/polyaniline complexes membrane, its electricity
Conductance is about 100S/m.
It is pointed out that described above and preferred embodiment may not be interpreted as limiting the design philosophy of the present invention.At this
Change can be improved by the technical thought of the present invention in the form of various by holding identical skill in the technical field of invention, this
The improvement and change of sample are interpreted as belonging in protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of graphene-conducting polymer composite material, it is characterised in that including：Using three-dimensional grapheme macroscopic body as working electrode or the electric conductor to be loaded with three-dimensional grapheme macroscopic body is used as work Electrode, and with to electrode, the electrolyte comprising polymer monomer structure electrochemical reaction system, andConducting polymer, shape are deposited by graphene nanometer sheet surface of the electrochemical method in the three-dimensional grapheme macroscopic body Into graphene-conducting polymer composite material.
- 2. preparation method according to claim 1, it is characterised in that：The three-dimensional grapheme macroscopic body is received including graphene Rice piece assembles the grapheme foam to be formed, and the aperture of hole contained by the grapheme foam is 1 nanometer~100 microns.
- 3. preparation method according to claim 2, it is characterised in that：The three-dimensional grapheme macroscopic body, which is selected from, utilizes oxidation Graphene passes through three-dimensional grapheme macroscopic body made from hydro-thermal reaction；Or the three-dimensional grapheme macroscopic body is selected from metal Foamed material is substrate, passes through three-dimensional grapheme macroscopic body made from chemical vapour deposition technique；Preferably, the metal foam material Material includes nickel foam or foam copper.
- 4. preparation method according to claim 1, it is characterised in that：The material of the electric conductor include Au, Ag, Pt, Fe, Co, Ni, Cu or Ru.
- 5. preparation method according to claim 1, it is characterised in that：Solvent in the electrolyte includes water and/or had Solvent；Preferably, the organic solvent include methanol, ethanol, ethylene glycol, acetone, dimethylformamide, dimethyl sulfoxide (DMSO), Chloroform, ethyl acetate or propene carbonate.
- 6. preparation method according to claim 1, it is characterised in that：Electrolyte in the electrolyte includes sulfuric acid, salt Acid, nitric acid, perchloric acid, sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium nitrate or potassium sulfate；And/or in the electrolyte Electrolyte concentration be 0.1~1mol/L.
- 7. preparation method according to claim 1, it is characterised in that：Polymer monomer concentration in the electrolyte is 0.01~10M；And/or the polymer monomer includes aniline, pyrroles, thiophene or acetylene.
- 8. preparation method according to claim 1, it is characterised in that：The electrochemical method includes cyclic voltammetry, arteries and veins Voltammetry is rushed, controls potentiometry or control current method；Preferably, the potential range used in the electrochemical method for -3V~+3V, Current range is 0~10A, and sedimentation time is 0~10h.
- 9. according to the preparation method any one of claim 1-8, it is characterised in that：The electrochemical reaction system is also wrapped Include reference electrode；Preferably, the reference electrode includes Ag/AgCl reference electrodes.
- 10. graphene-conducting polymer composite material prepared by the method as any one of claim 1-9, wherein graphite The mass ratio of alkene and conducting polymer is 1：100~100：1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136694A (en) * | 2018-10-15 | 2019-01-04 | 贵州航天风华精密设备有限公司 | A kind of aluminium alloy and its processing method with electro-magnetic screen function |
| CN109244540A (en) * | 2018-11-19 | 2019-01-18 | 中国科学院宁波材料技术与工程研究所 | A kind of solid polymer electrolyte, preparation method and lithium ion battery |
| CN110171814A (en) * | 2019-05-13 | 2019-08-27 | 电子科技大学 | Water-soluble KCl catalyzes and synthesizes the method and energy storage, sustained release application of carbon nanosheet |
| CN111276335A (en) * | 2020-02-17 | 2020-06-12 | 南京理工大学 | Aramid nanofiber/graphene/conductive polymer flexible composite electrode and preparation method thereof |
| CN114307674A (en) * | 2021-12-28 | 2022-04-12 | 北京林业大学 | Preparation method of special hydrophilic and hydrophobic membrane based on electric gradient morphology regulation |
| WO2022126875A1 (en) * | 2020-12-15 | 2022-06-23 | 广东凯金新能源科技股份有限公司 | Carbon-based composite electrode material and preparation method therefor |
-
2017
- 2017-09-26 CN CN201710881660.9A patent/CN107641824A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| LIQIONG WU: "MnO2 nanoflowers and polyaniline nanoribbons grown on hybrid grapheme/Ni 3D scaffolds by in situ electrochemical techniques for high-performance asymmetric supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136694A (en) * | 2018-10-15 | 2019-01-04 | 贵州航天风华精密设备有限公司 | A kind of aluminium alloy and its processing method with electro-magnetic screen function |
| CN109244540A (en) * | 2018-11-19 | 2019-01-18 | 中国科学院宁波材料技术与工程研究所 | A kind of solid polymer electrolyte, preparation method and lithium ion battery |
| CN110171814A (en) * | 2019-05-13 | 2019-08-27 | 电子科技大学 | Water-soluble KCl catalyzes and synthesizes the method and energy storage, sustained release application of carbon nanosheet |
| CN111276335A (en) * | 2020-02-17 | 2020-06-12 | 南京理工大学 | Aramid nanofiber/graphene/conductive polymer flexible composite electrode and preparation method thereof |
| WO2022126875A1 (en) * | 2020-12-15 | 2022-06-23 | 广东凯金新能源科技股份有限公司 | Carbon-based composite electrode material and preparation method therefor |
| CN114307674A (en) * | 2021-12-28 | 2022-04-12 | 北京林业大学 | Preparation method of special hydrophilic and hydrophobic membrane based on electric gradient morphology regulation |
| CN114307674B (en) * | 2021-12-28 | 2022-12-09 | 北京林业大学 | Preparation method of special hydrophilic and hydrophobic membrane based on electric gradient morphology regulation |
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Application publication date: 20180130 |