CN103980703A - Flocculent-polyaniline-coated graphene composite material and preparation method and application thereof - Google Patents
Flocculent-polyaniline-coated graphene composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a flocculent-polyaniline-coated graphene composite material and a preparation method and an application thereof. By using a single graphene layer as a framework, and flocculent polyaniline grows on both sides of the graphene layer and is connected with the graphene layer through covalent bonds. The composite material has good conductivity and high specific surface. As an electrode material, the composite material has very high specific capacitance, and good circular charge-discharge stability of the electrode is ensured due to stability of the covalent bonds. The synergistic effect of graphene and polyaniline lays a foundation for application of the electrode material to a supercapacitor.
Description
Technical field
The invention belongs to material and synthesize and electrochemical field, be specifically related to a kind of cotton-shaped polyaniline-coated graphene composite material and its preparation method and application.
Background technology
Graphene is a kind of by the independently New Two Dimensional material of the tightly packed one-tenth hexagon cellular of carbon atom shape crystalline structure of individual layer.Due to its unique electronic transmission performance, superior mechanical property and high-ratio surface, potential Application Areas is very extensive, and therefore its discoverer has obtained the Nobel prize in 2010, subsequently its research has been reached to climax.The two-dimentional conjugated structure of Graphene uniqueness has been given its good electroconductibility, can lower greatly the internal resistance of ultracapacitor, has improved the output rating of device, meanwhile, other carbon materials relatively, the specific surface area of Graphene can reach 2630m
2/ g, has improved the ratio electric capacity of ultracapacitor.Therefore Graphene is fabulous potential substituting of electrode material for super capacitor.But because the energy storage mechanism of Graphene belongs to the electrostatic double layer mechanism of adsorbing zwitterion storage power, its electric capacity can only reach 100-250F/g, has seriously limited the energy density of ultracapacitor.Therefore be current focus by the Material cladding of itself and fake capacitance mechanism.
Polyaniline is as a kind of synthetic conductive polymers simple, that easily process, and people have prepared the material of various structures, as nanotube, nanofiber etc.There is very high ratio electric capacity, by the two-dimensional material of polyaniline and the compound preparation of Graphene, bring into play greatly the feature performance benefit of each component, can bring into play matrix material good application in ultracapacitor.
Summary of the invention
The object of the present invention is to provide a kind of cotton-shaped polyaniline-coated graphene composite material and its preparation method and application, this matrix material has good electroconductibility and high specific surface, have very high ratio electric capacity as electrode materials, the stability of covalent linkage has ensured the cycle charge discharge elctrical stability that electrode is good.
For achieving the above object, the present invention adopts following technical scheme:
A kind of cotton-shaped polyaniline-coated graphene composite material, is taking single-layer graphene as skeleton, and cotton-shaped polyaniline is in the growth of graphene sheet layer two sides, and polyaniline is connected with covalent linkage with graphene film interlayer.
The preparation method of described cotton-shaped polyaniline-coated graphene composite material, that 4-amino-benzene diazonium tetrafluoroborate is reacted to the Graphene of preparing amino-benzene modification with redox graphene, then with aniline monomer under acidic conditions, low-temp reaction 24h, product, through washing, filtration, dry, makes cotton-shaped polyaniline-coated graphene composite material.Comprise the following steps:
(1) preparation of 4-amino-benzene diazonium tetrafluoroborate
Adopt diazotization reaction, under room temperature, Ursol D is dissolved in excessive dilute hydrochloric acid, being placed in 0-5 DEG C of low-temp reaction bathes, then slowly drip sodium nitrite solution, until excessive a little, after reaction 30min, the solution obtaining is joined in cold fluoroboric acid or Sodium tetrafluoroborate solution, the crystal filtration of separating out, washing, room temperature is fully dry, obtain 4-amino-benzene diazonium tetrafluoroborate;
(2) preparation of redox graphene
Adopt Improved-hummer method, natural flake graphite is scattered in the mixing acid of the vitriol oil and phosphoric acid, then in 0-5 DEG C of low temperature is bathed, under rapid stirring, slowly add potassium permanganate simultaneously, after adding, system is heated to 50 DEG C of reaction 10-12h, reactant is cooling, and washing obtains graphene oxide, finally by graphene oxide under pH=9 condition, 95 DEG C of hydrazine hydrate reduction 2h obtain redox graphene;
(3) be scattered in acetonitrile ultrasonic redox graphene, then drip 4-amino-benzene diazonium tetrafluoroborate solution, under illumination condition, react 5h, acetone, deionized water wash for product are dried, obtain the Graphene of amino-benzene modification;
(4) Graphene of amino-benzene modification and aniline monomer are dissolved in the mixing solutions of acid ethanol and water, under-10 DEG C of conditions, slowly drip oxygenant ammonium persulphate, reaction 24h, by ethanol product for, deionized water wash, be dried and obtain cotton-shaped polyaniline-coated graphene composite material.
In the mixing acid of step (2), the volume ratio of the vitriol oil and phosphoric acid is 9:1.
In step (3), the concentration of redox graphene acetonitrile solution is 1-10mg/mL.
In step (4), the Graphene of amino-benzene modification and the mol ratio of aniline monomer are 0.5:1-1:0.5.
In step (4), the mass ratio of aniline and ammonium persulphate is 3:2.
The perchloric acid solution that in step (4), the ethanol of acidity and the mixing solutions of water are 1mol/L.
In the mixing solutions of step (4) ethanol and water, the volume ratio of ethanol and water is 3:1.
Described cotton-shaped polyaniline-coated graphene composite material is for the preparation of electrode material for super capacitor.
Remarkable advantage of the present invention is:
(1) constructional feature of the cotton-shaped polyaniline-coated graphene composite material of preparing is that polyaniline is cotton-shaped, and is evenly distributed.
(2) constructional feature of the cotton-shaped polyaniline-coated graphene composite material of preparing is that cotton-shaped polyaniline has evenly prevented the defect that Graphene is easily reunited by complete graphene coated, has brought into play each component performance separately greatly.
(3) when being as electrode materials, the performance characteristics of the cotton-shaped polyaniline-coated graphene composite material of preparing can reach 300.2F/g than electric capacity.Graphene or polyaniline with respect to single component are all greatly improved.
(4) performance characteristics of the cotton-shaped polyaniline-coated graphene composite material of preparing is superior cycle charge discharge electrical property, after circulation 1000 circles, still has 282F/g than electric capacity, and stability reaches 94%.
Brief description of the drawings
Fig. 1 is the SEM figure of the cotton-shaped polyaniline-coated graphene composite material that makes of embodiment 2.
Fig. 2 is the FT-IR figure of the cotton-shaped polyaniline-coated graphene composite material that makes of embodiment 2.
Fig. 3 is the continuous current charge-discharge curve of the cotton-shaped polyaniline-coated graphene composite material that makes of embodiment 2.
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to the following example.
A preparation method for cotton-shaped polyaniline-coated graphene composite material, detailed process is:
The preparation of step 1:4-amino-benzene diazonium salt, adopt diazotization reaction, first Ursol D is dissolved in excessive dilute hydrochloric acid in room temperature, system is placed in to 0-5 DEG C of low-temp reaction bathes, then slowly drip sodium nitrite in aqueous solution, until excessive a little, after reaction 30min, the solution obtaining is joined to cold fluoroboric acid (HBF
4) or Sodium tetrafluoroborate (NaBF
4) in solution, the crystal of separating out is filtered to washing, the fully dry 4-amino-benzene diazonium tetrafluoroborate that obtains of room temperature.
Step 2: the preparation of redox graphene (rGO), adopt Improved-hummer method, natural flake graphite is scattered in the vitriol oil and phosphoric acid (v/v=9:1) mixing acid, then in 0-5 DEG C of low temperature is bathed, under rapid stirring, slowly add potassium permanganate simultaneously, after adding, system is heated to 50 DEG C of reaction 10-12h, reactant is cooling, washing obtains graphene oxide, finally by graphene oxide under pH=9 condition, 95 DEG C of hydrazine hydrate reduction 2h obtain redox graphene (rGO).
Step 3: be scattered in acetonitrile ultrasonic the redox graphene obtaining in step 2, then the 4-amino-benzene diazonium tetrafluoroborate in step 1 is added drop-wise in above-mentioned solution, under illumination condition, react 5h, by acetone, the dry Graphene (f-rGO) that obtains amino-benzene modification of deionized water wash for product.
Step 4: the amino-benzene modified graphene (f-rGO) in step 3 and aniline monomer are dissolved in acid ethanol/water (v/v=3:1) mixing solutions, under-10 DEG C of conditions, slowly drip oxygenant ammonium persulphate (aniline: APS=3:2), dropwise rear continuation reaction 24h, by ethanol, deionized water wash product for, be dried and obtain cotton-shaped polyaniline/graphene composite material.
embodiment 1
The preparation of step 1:4-amino-benzene diazonium salt, adopt diazotization reaction, first (25ml in 0.01mol (1.08g) Ursol D is dissolved in excessive dilute hydrochloric acid by room temperature, 1mol/L), system is placed in to 0 DEG C of low-temp reaction and bathes, then slowly drip sodium nitrite in aqueous solution (30%), until excessive a little, after reaction 30min, the solution obtaining is joined to cold fluoroboric acid (HBF
4) in solution, the crystal of separating out is filtered to washing, the fully dry 4-amino-benzene diazonium tetrafluoroborate that obtains of room temperature.
Step 2: the preparation of redox graphene (rGO), adopt Improved-hummer method, natural flake graphite (1g) is scattered in the 50ml vitriol oil and phosphoric acid (v/v=9:1) mixing acid, then in 0 DEG C of low temperature is bathed, under rapid stirring, slowly add 6g potassium permanganate simultaneously, after adding, system is heated to 50 DEG C of reaction 10h, reactant is cooling, washing obtains graphene oxide, finally by graphene oxide under pH=9 condition, 95 DEG C of hydrazine hydrate reduction 2h obtain redox graphene (rGO).
Step 3: be scattered in acetonitrile ultrasonic the redox graphene 30mg obtaining in step 2, then the 4-amino-benzene diazonium tetrafluoroborate (10mmol) in step 1 is added drop-wise in above-mentioned solution, under illumination condition, react 5h, by acetone, the dry Graphene (f-rGO) that obtains amino-benzene modification of deionized water wash for product.
Step 4: amino-benzene modified graphene (f-rGO) 3.4mg in step 3 and aniline monomer 0.01mol are dissolved in acid ethanol/water (v/v=3:1) mixing solutions, under-10 DEG C of conditions, slowly drip oxygenant ammonium persulphate (aniline: APS=3:2), dropwise rear continuation reaction 24h, by ethanol, deionized water wash product for, be dried and obtain cotton-shaped polyaniline/graphene composite material.
embodiment 2
The preparation of step 1:4-amino-benzene diazonium salt, adopt diazotization reaction, first (25ml in 0.01mol (1.08g) Ursol D is dissolved in excessive dilute hydrochloric acid by room temperature, 1mol/L), system is placed in to 5 DEG C of low-temp reactions and bathes, then slowly drip sodium nitrite in aqueous solution (30%), until excessive a little, after reaction 30min, the solution obtaining is joined to cold Sodium tetrafluoroborate (NaBF
4) in solution, the crystal of separating out is filtered to washing, the fully dry 4-amino-benzene diazonium tetrafluoroborate that obtains of room temperature.
Step 2: the preparation of redox graphene (rGO), adopt Improved-hummer method, natural flake graphite (1g) is scattered in the 50ml vitriol oil and phosphoric acid (v/v=9:1) mixing acid, then in 5 DEG C of low temperature are bathed, under rapid stirring, slowly add 6g potassium permanganate simultaneously, after adding, system is heated to 50 DEG C of reaction 12h, reactant is cooling, washing obtains graphene oxide, finally by graphene oxide under pH=9 condition, 95 DEG C of hydrazine hydrate reduction 2h obtain redox graphene (rGO).
Step 3: be scattered in acetonitrile ultrasonic the redox graphene 30mg obtaining in step 2, then the 4-amino-benzene diazonium tetrafluoroborate (20mmol) in step 1 is added drop-wise in above-mentioned solution, under illumination condition, react 5h, by acetone, the dry Graphene (f-rGO) that obtains amino-benzene modification of deionized water wash for product.
Step 4: amino-benzene modified graphene (f-rGO) 3.4mg in step 3 and aniline monomer 0.05mol are dissolved in acid ethanol/water (v/v=3:1) mixing solutions, under-10 DEG C of conditions, slowly drip oxygenant ammonium persulphate (aniline: APS=3:2), dropwise rear continuation reaction 24h, by ethanol, deionized water wash product for, be dried and obtain cotton-shaped polyaniline/graphene composite material.
embodiment 3
The preparation of step 1:4-amino-benzene diazonium salt, adopt diazotization reaction, first (25ml in 0.01mol (1.08g) Ursol D is dissolved in excessive dilute hydrochloric acid by room temperature, 1mol/L), system is placed in to 2 DEG C of low-temp reactions and bathes, then slowly drip sodium nitrite in aqueous solution (30%), until excessive a little, after reaction 30min, the solution obtaining is joined to cold fluoroboric acid (HBF
4) or Sodium tetrafluoroborate (NaBF
4) in solution, the crystal of separating out is filtered to washing, the fully dry 4-amino-benzene diazonium tetrafluoroborate that obtains of room temperature.
Step 2: the preparation of redox graphene (rGO), adopt Improved-hummer method, natural flake graphite (1g) is scattered in the 50ml vitriol oil and phosphoric acid (v/v=9:1) mixing acid, then in 2 DEG C of low temperature are bathed, under rapid stirring, slowly add 6g potassium permanganate simultaneously, after adding, system is heated to 50 DEG C of reaction 11h, reactant is cooling, washing obtains graphene oxide, finally by graphene oxide under pH=9 condition, 95 DEG C of hydrazine hydrate reduction 2h obtain redox graphene (rGO).
Step 3: be scattered in acetonitrile ultrasonic the redox graphene 30mg obtaining in step 2, then the 4-amino-benzene diazonium tetrafluoroborate (10mmol) in step 1 is added drop-wise in above-mentioned solution, under illumination condition, react 5h, by acetone, the dry Graphene (f-rGO) that obtains amino-benzene modification of deionized water wash for product.
Step 4: amino-benzene modified graphene (f-rGO) 3.4mg in step 3 and aniline monomer 0.02mol are dissolved in acid ethanol/water (v/v=3:1) mixing solutions, under-10 DEG C of conditions, slowly drip oxygenant ammonium persulphate (aniline: APS=3:2), dropwise rear continuation reaction 24h, by ethanol, deionized water wash product for, be dried and obtain cotton-shaped polyaniline/graphene composite material.
Cotton-shaped polyaniline-coated graphene composite material prepared by case study on implementation 2 carries out field emission scanning electron microscope sign, Fourier-infrared spectrum characterization, charge-discharge performance and characterizes: Fig. 1 has shown that the Graphene of individual layer is two-sided and has been coated a thick layer of cotton-shaped polyaniline, thickness is in 20-50nm left and right, and covered effect is more even.1640cm in Fig. 2
-1, 1496cm
-1, 1302 cm
-1with 1124 cm
-1be respectively the C=N in polyaniline molecule structure, C=C, the absorption peak of C-N and C-H.From Fig. 3, we can find out, cotton-shaped polyaniline-coated graphene composite material is carried out to constant current charge-discharge test, and the curve obtaining is comparatively symmetrical, shows that this matrix material has good charge-discharge performance, in the time that current density is 1A/g, reach 300.2F/g than electric capacity simultaneously.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. a cotton-shaped polyaniline-coated graphene composite material, is characterized in that: taking single-layer graphene as skeleton, cotton-shaped polyaniline is in the growth of graphene sheet layer two sides, and polyaniline is connected with covalent linkage with graphene film interlayer.
2. prepare the method for cotton-shaped polyaniline-coated graphene composite material as claimed in claim 1 for one kind, it is characterized in that: 4-amino-benzene diazonium tetrafluoroborate is reacted to the Graphene of preparing amino-benzene modification with redox graphene, then with aniline monomer under acidic conditions, low-temp reaction 24h, product, through washing, filtration, dry, makes cotton-shaped polyaniline-coated graphene composite material.
3. method according to claim 2, is characterized in that: comprise the following steps:
(1) preparation of 4-amino-benzene diazonium tetrafluoroborate
Adopt diazotization reaction, under room temperature, Ursol D is dissolved in excessive dilute hydrochloric acid, being placed in 0-5 DEG C of low-temp reaction bathes, then slowly drip sodium nitrite solution, until excessive a little, after reaction 30min, the solution obtaining is joined in cold fluoroboric acid or Sodium tetrafluoroborate solution, the crystal filtration of separating out, washing, room temperature is fully dry, obtain 4-amino-benzene diazonium tetrafluoroborate;
(2) preparation of redox graphene
Adopt Improved-hummer method, natural flake graphite is scattered in the mixing acid of the vitriol oil and phosphoric acid, then in 0-5 DEG C of low temperature is bathed, under rapid stirring, slowly add potassium permanganate simultaneously, after adding, system is heated to 50 DEG C of reaction 10-12h, reactant is cooling, and washing obtains graphene oxide, finally by graphene oxide under pH=9 condition, 95 DEG C of hydrazine hydrate reduction 2h obtain redox graphene;
(3) be scattered in acetonitrile ultrasonic redox graphene, then drip 4-amino-benzene diazonium tetrafluoroborate solution, under illumination condition, react 5h, acetone, deionized water wash for product are dried, obtain the Graphene of amino-benzene modification;
(4) Graphene of amino-benzene modification and aniline monomer are dissolved in the mixing solutions of acid ethanol and water, under-10 DEG C of conditions, slowly drip oxygenant ammonium persulphate, reaction 24h, by ethanol product for, deionized water wash, be dried and obtain cotton-shaped polyaniline-coated graphene composite material.
4. method according to claim 3, is characterized in that: in the mixing acid of step (2), the volume ratio of the vitriol oil and phosphoric acid is 9:1.
5. method according to claim 3, is characterized in that: in step (3), the concentration of redox graphene acetonitrile solution is 1-10mg/mL.
6. method according to claim 3, is characterized in that: in step (4), the Graphene of amino-benzene modification and the mol ratio of aniline monomer are 0.5:1-1:0.5.
7. method according to claim 3, is characterized in that: in step (4), the mass ratio of aniline and ammonium persulphate is 3:2.
8. method according to claim 3, is characterized in that: the perchloric acid solution that in step (4), the ethanol of acidity and the mixing solutions of water are 1mol/L.
9. method according to claim 3, is characterized in that: in the mixing solutions of step (4) ethanol and water, the volume ratio of ethanol and water is 3:1.
10. an application for cotton-shaped polyaniline-coated graphene composite material as claimed in claim 1, is characterized in that: described cotton-shaped polyaniline-coated graphene composite material is for the preparation of electrode material for super capacitor.
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| PCT/CN2015/071113 WO2015184815A1 (en) | 2014-06-04 | 2015-01-20 | Flocculent-polyaniline-coated graphene composite material, method for preparation thereof, and use thereof |
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