CN104151751A - Carbon nano tube/amorphous carbon core-shell structure-polymer dielectric composite material - Google Patents
Carbon nano tube/amorphous carbon core-shell structure-polymer dielectric composite material Download PDFInfo
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- CN104151751A CN104151751A CN201410250376.8A CN201410250376A CN104151751A CN 104151751 A CN104151751 A CN 104151751A CN 201410250376 A CN201410250376 A CN 201410250376A CN 104151751 A CN104151751 A CN 104151751A
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Abstract
The invention provides a preparation method for a carbon nano tube/amorphous carbon core-shell structure-polymer dielectric composite material. The preparation method comprises the following steps of: mixing the carbon nano tube with glucose in an aqueous solution and carrying out a hydrothermal reaction to prepare a carbon nano tube/amorphous carbon core-shell-structured material; and then, preparing the dielectric composite material by mixing the carbon nano tube/amorphous carbon core-shell-structured material with a polymer. A dielectric constant of the composite material can reach 5910 and the dielectric loss of the composite material is only 2.5. The method disclosed by the invention is simple in preparation, low in material cost and good in repeatability, and has very good application value and prospect.
Description
Technical field
The invention belongs to technical field of composite materials, particularly a kind of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material and preparation method thereof.
Background technology
In recent years, polymer-based carbon dielectric composite material is subject to extensive concern because having high-k, low-dielectric loss and excellent mechanical property.It is the dielectric properties that filler improves polymkeric substance that traditional method adopts stupalith, but the volume fraction of ceramic packing generally surpasses 30%, has reduced the snappiness of dielectric composite material, has limited its application in electrical condenser.
Current, it is found that and in polymkeric substance, add a small amount of (being less than 10vol%) electrical-conductive nanometer carbon material, as carbon nano fiber, nano-graphite, Graphene, carbon nanotube etc., can significantly improve the specific inductivity of dielectric composite material, keep good snappiness simultaneously.Wherein, carbon nanotube is because having excellent calorifics, electricity and mechanical property, and is widely used in preparing dielectric composite material.But carbon nanotube is very easily reunited, cannot be dispersed in polymkeric substance, seriously restricted the practical application of carbon nanotube.Extensive work shows, chemically modified can stop carbon nanotube to be reunited, and improves its dispersiveness in polymkeric substance, and then obtains the dielectric composite material of excellent performance.For example, the people such as R.R.Kohlmeyer have prepared hydroxyl modified multi-walled carbon nano-tubes, and itself and polymkeric substance is compound, in the situation that carbon nano tube-doped amount is 8vol%, having obtained specific inductivity is 2200, the dielectric composite material that dielectric loss is 5 (J.Phys.Chem.C, 2009,113,17626).Yet the people such as Liu point out, although chemically modified can improve the specific inductivity of matrix material, cannot solve the too high problem of dielectric loss (Adv.Mater., 2011,23,5104).This is that the leakage current of matrix material is larger, and then causes too high dielectric loss because chemically modified cannot be avoided the direct contact of carbon nanotube.Therefore,, in order to obtain the dielectric composite material of high-k, low-dielectric loss, crucial problem is, when preventing that carbon nanotube from reuniting, to avoid the direct contact of carbon nanotube.
In order to address the above problem, we adopt hydrothermal method to prepare a kind of carbon nanotube/amorphous carbon nucleocapsid structure material.The amorphous carbon shell of insulation wraps up carbon nanotube completely, not only can prevent carbon nanotube reunion, can also avoid the direct contact of carbon nanotube.Therefore, carbon nanotube/amorphous carbon nucleocapsid structure material and the polymkeric substance of preparation is compound, under lower doping, just obtained the dielectric composite material of high-k, low-dielectric loss.The method preparation is simple, and raw materials cost is low, and favorable repeatability has good using value and prospect.
Summary of the invention
The object of the invention is: by hydrothermal method, prepare a kind of carbon nanotube/amorphous carbon nucleocapsid structure material, and itself and polymkeric substance is compound, prepare a kind of dielectric composite material with high dielectric property.
With diameter 40-60 nanometer, the carbon nanotube of length 5-15 micron is the concise and to the point elaboration of example implementation procedure of the present invention below.First carbon nanotube is mixed in solution with glucose powder, by hydrothermal treatment consists, eccentric cleaning and low-temperature curing, obtained carbon nanotube/amorphous carbon nucleocapsid structure material, then by itself and the compound dielectric composite material that obtains of polymkeric substance.This nucleocapsid structure not only can prevent that carbon nanotube from reuniting, and can also avoid the direct contact of carbon nanotube, and this makes itself and the polymkeric substance can be evenly compound, thereby obviously improves dielectric properties.
This kind of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material can be realized by following steps:
(1) take a certain amount of carbon nanotube, be dispersed in quantitative deionized water, then add 2 Triton, ultrasonic dispersion 2 hours, obtains uniform carbon nano tube dispersion liquid.
(2) take a certain amount of glucose powder, join in above-mentioned carbon nano tube dispersion liquid, continue ultrasonic dispersion 2 hours, carbon nanotube is mixed with glucose.
(3) mixing solutions (2) step being obtained is poured 100 milliliters take in the stainless steel cauldron that tetrafluoroethylene is substrate into, then reactor is placed in homogeneous reactor, under 180 ℃ of high temperature and 3 revs/min of rotating speeds, reacts 12 hours.After reaction finishes, naturally cool to room temperature.
(4) by reacted product, the high speed centrifugation by 12000 revs/min cleans, and single centrifugation time is 15 minutes, and respectively washes three times with deionized water and ethanol.Take out the throw out after centrifugal, be placed in the loft drier of 50 ℃ and dry.
(5) by the powder of (4) gained, be placed in tube furnace, under nitrogen protection, 300 ℃ of low-temperature curings 2 hours, obtain carbon nanotube/amorphous carbon nucleocapsid structure.
(6) take the carbon nanotube of a certain amount of process (1)-(5) step process, join in a certain amount of ethanol, ultrasonic dispersion 3 hours, then takes a certain amount of polyvinylidene difluoride (PVDF) powder and joins in above-mentioned mixed solution, continue ultrasonic dispersion 2 hours, the suspension liquid that obtains mixing.Suspension liquid is poured in watch-glass, at 70 ℃ dry 4 hours, dried product is ground and obtains trickle powder in agate mortar.
(7) fine-powder (6) step being obtained, in powder compressing machine, with the pressure of 20 MPas, be pressed into the thin slice of approximately 1 millimeter of thickness, then be placed at 200 ℃ and be incubated 3 hours, obtain carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material.By slice surfaces polishing, surface-coated conductive silver glue, can carry out the measurement of electrical properties.
By said process, can obtain carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material, compare with Carbon Nanotube/Polymer Composite, the former dielectric properties significantly improve.Under room temperature and 1 kilohertz, the specific inductivity of carbon nano tube-polymer dielectric composite material is 1040 to the maximum, loss is 2.5 left and right, and carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material can reach 5910 under identical loss, and specific inductivity has improved 6 times.And the dielectric properties of our prepared carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material are better than known most of carbon nano tube-polymer dielectric composite materials at present.
The novel method of preparing carbon nanotube/amorphous carbon nucleocapsid structure provided by the present invention, not only can prevent carbon nanotube reunion, also can prevent the direct contact of the carbon nanotube of conduction simultaneously, itself and polymkeric substance be carried out compound, obtain the matrix material of dielectric properties excellences.The method preparation is simple, and raw materials cost is low, and favorable repeatability has good using value and prospect.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material of preparing of the present invention.
Fig. 2 is that the specific conductivity of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material of different dopings is with frequency change schematic diagram.
Fig. 3 is under 1 kilohertz and room temperature, and the specific inductivity of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material and dielectric loss are with the variation schematic diagram of doping.
Fig. 4 is that the specific conductivity of carbon nano tube-polymer dielectric composite material of different dopings is with frequency change schematic diagram.
Fig. 5 is under 1 kilohertz and room temperature, and the specific inductivity of carbon nano tube-polymer dielectric composite material and dielectric loss are with the variation schematic diagram of doping.
Embodiment
Below in conjunction with drawings and Examples, describe the present invention in detail.
Embodiment 1, takes 60 milligrams of diameter 40-60 nanometers, and the carbon nanotube of length 5-15 micron joins in 60 ml deionized water solution, in order to improve dispersiveness, drips 2 Triton, ultrasonic dispersion 2 hours, the carbon nano tube dispersion liquid being uniformly mixed.Take 1.5 grams of glucose powder and join in above-mentioned dispersion liquid, continue ultrasonic 2 hours, carbon nanotube is mixed with glucose.Subsequently, pour mixing solutions into 100 milliliters take in the stainless steel cauldron that tetrafluoroethylene is substrate, then reactor is placed in homogeneous reactor, under the rotating speed of 180 ℃ of high temperature and 3 revs/min, react 12 hours.After reaction finishes, naturally cool to room temperature.In order to remove residue, by ultracentrifugal method, clean, rotating speed is 12000 revs/min, keeps 15 minutes, and respectively washes three times with deionized water and ethanol.Take out the throw out after centrifugal, be placed in the loft drier of 50 ℃ and dry, obtain powdery product.Finally powdery product is placed in tube furnace, under nitrogen protection, 300 ℃ of low-temperature curings 2 hours, have just obtained carbon nanotube/amorphous carbon nucleocapsid structure material.
Get a certain amount of prepared carbon nanotube/amorphous carbon nucleocapsid structure material, join in 20 milliliters of ethanolic solns, ultrasonic dispersion 3 hours, adds a certain amount of polyvinylidene difluoride (PVDF) powder to continue ultrasonic dispersion 2 hours, the dispersion liquid that obtains mixing subsequently.Dispersion liquid is poured in watch-glass, at 70 ℃ dry 4 hours, dried product is ground to form to trickle powder with agate mortar.Then powder is put into powder compressing machine, apply the pressure of 20 MPas and keep 10 minutes, obtain about 15 millimeters of diameter, the thin slice that thickness is about 1 millimeter, thin slice is positioned at 200 ℃ and is incubated 3 hours, can obtain carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material, its structure as shown in Figure 1.By slice surfaces polishing, surface-coated conductive silver glue, finally carries out the measurement of electrical properties to matrix material with HP4194A.According to different ratio requirement, repeat aforesaid operations, make the matrix material of a series of different dopings.The specific conductivity of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material of different dopings with the variation relation of frequency as shown in Figure 2; Under 1 kilohertz and room temperature, specific inductivity and dielectric loss are with the variation relation of doping as shown in Figure 3.The maximum dielectric constant of carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material is 5910, and loss is 2.5 left and right.
Take a certain amount of diameter 40-60 nanometer, the carbon nanotube of length 5-15 micron, joins in 20 milliliters of ethanolic solns, and ultrasonic dispersion 3 hours adds a certain amount of polyvinylidene difluoride (PVDF) powder to continue ultrasonic dispersion 2 hours, the dispersion liquid that obtains mixing subsequently.Dispersion liquid is imported in watch-glass, at 70 ℃ dry 4 hours, dried product is ground to form to trickle powder with agate mortar.Then powder is put into powder compressing machine, apply the pressure of 20 MPas and keep 10 minutes, obtain about 15 millimeters of diameter, the thin slice that thickness is about 1 millimeter, is positioned over thin slice at 200 ℃ and is incubated 3 hours, can obtain carbon nano tube-polymer dielectric composite material.By slice surfaces polishing, surface-coated conductive silver glue, finally carries out the measurement of electrical properties to matrix material with HP4194A.According to different ratio requirement, repeat aforesaid operations, make the matrix material of a series of different dopings.The specific conductivity of the carbon nano tube-polymer dielectric composite material of different dopings with the variation relation of frequency as shown in Figure 4; Under 1 kilohertz and room temperature, specific inductivity and dielectric loss are with the variation relation of doping as shown in Figure 5.The maximum dielectric constant of carbon nano tube-polymer dielectric composite material is 1040, and loss is 2.5 left and right.
Claims (2)
1. a preparation method for carbon nanotube/amorphous carbon nucleocapsid structure material, its step comprises:
(1) take 60 milligrams of diameter 40-60 nanometers, the carbon nanotube of length 5-15 micron joins in 60 ml deionized water solution, drips 2 Triton, ultrasonic dispersion 2 hours, the carbon nano tube dispersion liquid being uniformly mixed;
(2) take 1.5 grams of glucose powder and join in above-mentioned dispersion liquid, continue ultrasonic 2 hours, carbon nanotube is mixed with glucose;
(3) mixing solutions (2) step being obtained is poured 100 milliliters take in the stainless steel cauldron that tetrafluoroethylene is substrate into, is then placed in homogeneous reactor, under 180 ℃ of high temperature and 3 revs/min of rotating speeds, reacts 12 hours.After reaction finishes, naturally cool to room temperature;
(4) by reacted product, the high speed centrifugation by 12000 revs/min cleans, and single centrifugation time is 15 minutes, and respectively washes three times with deionized water and ethanol.Take out the throw out after centrifugal, be placed in the loft drier of 50 ℃ and dry;
(5) by the powder of (4) gained, be placed in tube furnace, under nitrogen protection, 300 ℃ of low-temperature curings 2 hours, obtain carbon nanotube/amorphous carbon nucleocapsid structure material.
2. a preparation method for carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material, described nucleocapsid structure material is prepared by method according to claim 1, step comprises:
(6) take carbon nanotube/amorphous carbon nucleocapsid structure material prepared by a certain amount of process (1)-(5) step, join in a certain amount of ethanol, ultrasonic dispersion 3 hours, then taking a certain amount of polyvinylidene difluoride (PVDF) powder joins in above-mentioned mixed solution, continue ultrasonic dispersion 2 hours, the suspension liquid that obtains mixing.Suspension liquid is poured in watch-glass, at 70 ℃ dry 4 hours, dried product is ground and obtains trickle powder in agate mortar;
(7) fine-powder (6) step being obtained, in powder compressing machine, with the pressure of 20 MPas, be pressed into the thin slice of approximately 1 millimeter of thickness, then be placed at 200 ℃ and be incubated 3 hours, obtain carbon nanotube/amorphous carbon nucleocapsid structure-polymkeric substance dielectric composite material.By slice surfaces polishing, surface-coated conductive silver glue, can carry out the measurement of electrical properties.
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