CN102964754A - High-dielectric-constant polyvinylidene fluoride composite material and preparation method thereof - Google Patents
High-dielectric-constant polyvinylidene fluoride composite material and preparation method thereof Download PDFInfo
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- CN102964754A CN102964754A CN2012104995062A CN201210499506A CN102964754A CN 102964754 A CN102964754 A CN 102964754A CN 2012104995062 A CN2012104995062 A CN 2012104995062A CN 201210499506 A CN201210499506 A CN 201210499506A CN 102964754 A CN102964754 A CN 102964754A
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Abstract
The invention relates to a polyvinylidene fluoride (PVDF) composite material and a preparation method thereof, and particularly relates to a high-dielectric-constant polyvinylidene fluoride composite material and a preparation method thereof. The invention aims to solve the problem that the dielectric constant of the graphene/PVDF composite material prepared by the conventional method is low. The high-dielectric-constant PVDF composite material is prepared from Ag-graphene, N-methyl pyrrolidone and PVDF resin. The preparation method comprises the following steps: I, preparing Ag-graphene/N-methyl pyrrolidone suspension liquid; II, preparing PVDF resin/N-methyl pyrrolidone solution; III, mixing to obtain Ag-graphene /PVDF resin/N-methyl pyrrolidone mixture; IV, filming to obtain Ag-graphene/PVDF three-phase composite material film; and V, molding to obtain the high-dielectric-constant polyvinylidene fluoride composite material. The preparation method is mainly applied to preparing high-dielectric-constant polyvinylidene fluoride composite materials.
Description
Technical field
The present invention relates to a kind of polyvinylidene fluoride-based composite and preparation method thereof.
Background technology
Since the simple micromechanics stripping method of the usefulness such as Geim of Manchester, England in 2004 is at first prepared the Graphene of individual layer, this new carbon becomes rapidly the focus of physics, chemistry and material science research just with its distinctive mechanics, electricity and chemical property and unique accurate two-dimensional sheet molecular structure and the many potential using value that is possessed in following high-tech area.Again because its relative low price, performance that specific surface area is large and excellent become the ideal filler of polymer matrix composite, be expected to synthesize the polymer matrix composite that has high conductivity, high strength, high thermal stability and have certain flame retardant resistance, further enlarge the range of application of polymer materials.Such as people such as Song Hongsong Graphene/PVDF(PVDF resin mainly being referred to the multipolymer of vinylidene fluoride homopolymer or vinylidene and other a small amount of fluorine-containing vinyl monomers) dielectric properties of matrix material are studied discovery when the Graphene consumption reaches 0.25%, its specific inductivity is near 16, improved 70% than pure PVDF, dielectric properties have obtained obvious improvement.But specific inductivity is still on the low side, and Graphene is difficult for disperseing very much.
Summary of the invention
The objective of the invention is to solve the Graphene of existing method preparation/PVDF matrix material and have specific inductivity problem on the low side, and a kind of polyvinylidene fluoride-based composite with high dielectric constant and preparation method thereof is provided.
A kind of polyvinylidene fluoride-based composite with high dielectric constant is prepared from by Ag-Graphene, N-Methyl pyrrolidone and PVDF resin; The mass ratio of described Ag-Graphene and PVDF resin is 1:(5 ~ 50); Described Ag-Graphene and PVDF resin total mass are 1:(6 ~ 125 with the ratio of N-Methyl pyrrolidone quality).
A kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 30min ~ 60min under 40Hz ~ 250Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 50 ℃ ~ 60 ℃ lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: under agitation condition, Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution are mixed, be ultra-sonic dispersion 30min ~ 90min under 40Hz ~ 250Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, then placing temperature is thermostat container freeze-day with constant temperature 6h ~ 12h of 60 ℃ ~ 120 ℃, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 200 ℃ ~ 240 ℃, pressure are hot pressing 10min ~ 30min under 10MPa ~ 40MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant; The mass ratio of the Ag-Graphene described in the step 1 and N-Methyl pyrrolidone is 1:(50 ~ 500); The mass ratio of the PVDF resin described in the step 2 and N-Methyl pyrrolidone is 1:(5 ~ 50); In Ag-Graphene described in the step 3/N-Methyl pyrrolidone suspension in Ag-Graphene and the PVDF resin/N-Methyl pyrrolidone solution mass ratio of PVDF resin be 1:(5 ~ 50).
Advantage of the present invention: the present invention adopts the Ag-Graphene to regulate the specific inductivity of PVDF resin, can significantly improve the specific inductivity of PVDF resin by the addition of adjusting the Ag-Graphene, so the polyvinylidene fluoride-based composite with high dielectric constant of the present invention's preparation has higher specific inductivity, the specific inductivity of matrix material is 50 ~ 710 under the 1KHz condition.
Description of drawings
Fig. 1 is the XRD figure of Ag-Graphene described in test one step 1; Fig. 2 is the SEM figure of Ag-Graphene described in test one step 1; Fig. 3 is that test one is to the polyvinylidene fluoride-based composite with high dielectric constant of test seven preparations and the specific inductivity graphic representation of pure PVDF resin.
Embodiment
Embodiment one: present embodiment is a kind of polyvinylidene fluoride-based composite with high dielectric constant, is prepared from by Ag-Graphene, N-Methyl pyrrolidone and PVDF resin.
The mass ratio of the described Ag-Graphene of present embodiment and PVDF resin is 1:(5 ~ 50); The described Ag-Graphene of present embodiment and PVDF resin total mass are 1:(6 ~ 125 with the ratio of N-Methyl pyrrolidone quality).
The present invention adopts the Ag-Graphene to regulate the specific inductivity of PVDF resin, can significantly improve the specific inductivity of PVDF resin by the addition of adjusting the Ag-Graphene, so described polyvinylidene fluoride-based composite with high dielectric constant has higher specific inductivity, the specific inductivity of matrix material is 10 ~ 710 under the 1000Hz frequency.
Embodiment two: the difference of present embodiment and embodiment one is: described Ag-Graphene is to adopt following step preparation: at first take Graphite Powder 99 as raw material adopts improved Hummers method make graphite oxide, then be under 40Hz ~ 250Hz graphite oxide to be scattered in the deionized water in ultrasonic frequency, the ultra-sonic dispersion time is 1h ~ 3h, namely obtaining concentration is the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL, then adds the AgNO that concentration is 0.01mol/L ~ 1mol/L
3The aqueous solution, and to continue in ultrasonic frequency be to adopt heating in water bath that mixed solution is warming up to 60 ℃ ~ 100 ℃ water-baths from room temperature under 40Hz ~ 250Hz behind ultrasonic 30min ~ 60min, then dropwise adds the NaBH that concentration is 0.05mol/L ~ 0.5mol/L
4The aqueous solution, obtain mixed solution, and be 60 ℃ ~ 100 ℃ lower back flow reaction 2h ~ 8h at bath temperature, after finishing, reaction adopts the Büchner funnel suction filtration, the solid that obtains adopts first distilled water wash 3 ~ 5 times, adopt washing with alcohol 3 ~ 5 times, the solid after the washing is 60 ℃ ~ 80 ℃ lower vacuum-drying 12h ~ 24h in temperature, obtains the Ag-Graphene again; The concentration of described adding is the AgNO of 0.01mol/L ~ 1mol/L
3The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(5 ~ 50); The concentration of described adding is the NaBH of 0.05mol/L ~ 0.5mol/L
4The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(1 ~ 10).Other are identical with embodiment one.
Present embodiment adopts loaded Ag that Graphene has been carried out modification, has solved the problem of Graphene bad dispersibility.
The described improved Hummers method specific operation process of present embodiment is as follows: 5g graphite, 2.5g SODIUMNITRATE, the 115mL98% vitriol oil are mixed placing ice bath, stir 30min, it is fully mixed.Take by weighing 15g KMnO
4, add above-mentioned mixed solution and continue to stir one after the meeting, move into and continue to stir 30min in 35 ℃ of warm water baths.Slowly drip 225mL warm water, make temperature rise to 98 ℃, keep 1h, add 20mL30%H after with distilled water reaction solution (the control temperature is below 100 ℃) being diluted to 700mL
2O
2, filtered while hot is fully washed until use BaCl with 5%HCl and distilled water
2Check in the filtrate without SO
4 2-Ion is used AgNO
3Check is without Cl
-Till the ion, then at 60 ℃ of lower oven dry 24 ~ 48h, obtain graphite oxide.
Embodiment three: present embodiment and one of embodiment one or twos' difference is: the mass ratio of described Ag-Graphene and PVDF resin is 1:(9 ~ 12); The described Ag-Graphene of present embodiment and PVDF resin total mass are 1:(12 ~ 100 with the ratio of N-Methyl pyrrolidone quality).Other are identical with embodiment one or two.
Embodiment four: present embodiment is a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 30min ~ 60min under 40Hz ~ 250Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 50 ℃ ~ 60 ℃ lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under 200r/min ~ 900r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 30min ~ 90min under 40Hz ~ 250Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, then placing temperature is thermostat container freeze-day with constant temperature 6h～12h of 60 ℃ ~ 120 ℃, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 200 ℃ ~ 240 ℃, pressure are hot pressing 10min ~ 30min under 10MPa ~ 40MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of the Ag-Graphene described in the present embodiment step 1 and N-Methyl pyrrolidone is 1:(50 ~ 500).
The mass ratio of the PVDF resin described in the present embodiment step 2 and N-Methyl pyrrolidone is 1:(5 ~ 50).
In Ag-Graphene described in the present embodiment step 3/N-Methyl pyrrolidone suspension in Ag-Graphene and the PVDF resin/N-Methyl pyrrolidone solution mass ratio of PVDF resin be 1:(5 ~ 50).
Present embodiment adopts the Ag-Graphene to regulate the specific inductivity of PVDF resin, can significantly improve the specific inductivity of PVDF resin by the addition of adjusting the Ag-Graphene, so the polyvinylidene fluoride-based composite with high dielectric constant of present embodiment preparation has higher specific inductivity, specific inductivity is 50 ~ 710.
Embodiment five: the difference of present embodiment and embodiment four is: the Ag-Graphene described in the step 1 is to adopt following step preparation: at first take Graphite Powder 99 as raw material adopts improved Hummers method make graphite oxide, then be under 40Hz ~ 250Hz graphite oxide to be scattered in the deionized water in ultrasonic frequency, the ultra-sonic dispersion time is 1h ~ 3h, namely obtaining concentration is the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL, then adds the AgNO that concentration is 0.01mol/L～1mol/L
3The aqueous solution, and to continue in ultrasonic frequency be to adopt heating in water bath that mixed solution is warming up to 60 ℃ ~ 100 ℃ water-baths from room temperature under 40Hz ~ 250Hz behind ultrasonic 30min ~ 60min, then dropwise adds the NaBH that concentration is 0.05mol/L ~ 0.5mol/L
4The aqueous solution, obtain mixed solution, and be 60 ℃ ~ 100 ℃ lower back flow reaction 2h ~ 8h at bath temperature, after finishing, reaction adopts the Büchner funnel suction filtration, the solid that obtains adopts first distilled water wash 3 ~ 5 times, adopt washing with alcohol 3 ~ 5 times, the solid after the washing is 60 ℃ ~ 80 ℃ lower vacuum-drying 12h ~ 24h in temperature, obtains the Ag-Graphene again; The concentration of described adding is the AgNO of 0.01mol/L ~ 1mol/L
3The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(5 ~ 50); The concentration of described adding is the NaBH of 0.05mol/L ~ 0.5mol/L
4The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(1 ~ 10).
Present embodiment adopts loaded Ag that Graphene has been carried out modification, has solved the problem of Graphene bad dispersibility.
The described improved Hummers method specific operation process of present embodiment is as follows: 5g graphite, 2.5g SODIUMNITRATE, the 115mL98% vitriol oil are mixed placing ice bath, stir 30min, it is fully mixed.Take by weighing 15g KMnO
4, add above-mentioned mixed solution and continue to stir one after the meeting, move into and continue to stir 30min in 35 ℃ of warm water baths.Slowly drip 225mL warm water, make temperature rise to 98 ℃, keep 1h, add 20mL30%H after with distilled water reaction solution (the control temperature is below 100 ℃) being diluted to 700mL
2O
2, filtered while hot is fully washed until use BaCl with 5%HCl and distilled water
2Check in the filtrate without SO
4 2-Ion is used AgNO
3Check is without Cl
-Till the ion, then at 60 ℃ of lower oven dry 24 ~ 48h, obtain graphite oxide.
Embodiment six: present embodiment and one of embodiment four or five difference are: be ultra-sonic dispersion 40min ~ 50min under 80Hz ~ 200Hz in ultrasonic frequency in the step 1.Other are identical with embodiment four or five.
Embodiment seven: one of present embodiment and embodiment four to six difference is: the Ag-Graphene described in the step 1 is 1:(100 ~ 400 with the ratio of N-Methyl pyrrolidone quality).Other are identical with embodiment four to six.
Embodiment eight: one of present embodiment and embodiment four to seven difference is: the mass ratio of the PVDF resin described in the step 2 and N-Methyl pyrrolidone is 1:(10 ~ 40).Other are identical with embodiment four to seven.
Embodiment nine: present embodiment with one of embodiment four to eight difference is: the step 3 low whipping speed is under 300r/min ~ 700r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 40min ~ 80min under 80Hz ~ 200Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture.Other are identical with embodiment four to eight.
Embodiment ten: the difference of one of present embodiment and embodiment four to nine is: in the Ag-Graphene described in the step 3/N-Methyl pyrrolidone suspension in Ag-Graphene and the PVDF resin/N-Methyl pyrrolidone solution mass ratio of PVDF resin be 1:(9 ~ 12).Other are identical with embodiment four to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in the step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in the step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in the step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 1:99 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in the step 1 and be and adopt following step preparation: at first take Graphite Powder 99 as raw material adopts improved Hummers method make graphite oxide, then be under the 150Hz graphite oxide to be scattered in the deionized water in ultrasonic frequency, the ultra-sonic dispersion time is 2h, namely obtaining concentration is the graphene oxide dispersion liquid of 1g/L, then adds the AgNO that concentration is 0.05mol/L
3The aqueous solution, and to continue in ultrasonic frequency be to adopt heating in water bath that mixed solution is warming up to 80 ℃ of water-baths from room temperature under the 150Hz behind the ultrasonic 45min, then dropwise adds the NaBH that concentration is 0.1mol/L
4The aqueous solution obtains mixed solution, and is 80 ℃ of lower back flow reaction 5h at bath temperature, adopt the Büchner funnel suction filtration after reaction finishes, the solid that obtains adopts first distilled water wash 4 times, adopts washing with alcohol 4 times again, solid after the washing is 70 ℃ of lower vacuum-drying 18h in temperature, obtains the Ag-Graphene; The concentration of described adding is the AgNO of 0.05mol/L
3The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 1g/L is 1:25; The concentration of described adding is the NaBH of 0.1mol/L
4The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 1g/L is 1:5; Described improved Hummers method specific operation process is as follows: 5g graphite, 2.5g SODIUMNITRATE, 115mL 98% vitriol oil are mixed placing ice bath, stir 30min, it is fully mixed.Take by weighing 15g KMnO
4, add above-mentioned mixed solution and continue to stir one after the meeting, move into and continue to stir 30min in 35 ℃ of warm water baths.Slowly drip 225mL warm water, make temperature rise to 98 ℃, keep 1h, add 20mL30%H after with distilled water reaction solution (the control temperature is below 100 ℃) being diluted to 700mL
2O
2, filtered while hot is fully washed until use BaCl with 5%HCl and distilled water
2Check in the filtrate without SO
4 2-Ion is used AgNO
3Check is without Cl
-Till the ion, then at 60 ℃ of lower oven dry 24 ~ 48h, obtain graphite oxide.
Adopt X-ray diffractometer to detect the Ag-Graphene described in test one step 1, detected result as shown in Figure 1, Fig. 1 is the XRD figure of Ag-Graphene described in test one step 1; Can observe by Fig. 1, test Ag-Graphene 2 θ described in the step 1 and about 38 °, 44 °, 65 ° and 78 °, diffraction peak occurs, these diffraction peaks correspond respectively to (111), (200) of Ag in the face-centred cubic structure, the diffraction of (220) and (311) crystal face, and the characteristic peak of graphite oxide disappears, therefore chemical reduction successfully is reduced to Graphene with graphene oxide as shown in Figure 1, and with the Ag particle load on Graphene.
Adopt sem observation to test the Ag-Graphene described in the step 1, as shown in Figure 2, Fig. 2 is the SEM figure of Ag-Graphene described in test one step 1; Testing as shown in Figure 2 Ag-Graphene described in the step 1 is that flap is graphene platelet, and the Ag nanoparticle is evenly dispersed in the surface of Graphene; The Ag Nanoparticle Size is even, is of a size of 30 ~ 50nm.
Test two: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in two step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in two step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in two step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 3:97 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in two step 1 and be the Ag-Graphene of test one preparation.
Test three: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in three step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in three step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in three step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 5:95 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in three step 1 and be the Ag-Graphene of test one preparation.
Test four: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in four step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in four step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in four step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 7:93 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in four step 1 and be the Ag-Graphene of test one preparation.
Test five: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in five step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in five step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in five step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 8:92 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in five step 1 and be the Ag-Graphene of test one preparation.
Test six: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in six step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in six step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in six step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 9:91 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in six step 1 and be the Ag-Graphene of test one preparation.
Test seven: a kind of preparation method of polyvinylidene fluoride-based composite with high dielectric constant, specifically finish according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 45min under the 150Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 55 ℃ of lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: low whipping speed is under the 550r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 60min under the 150Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, and then placing temperature is 90 ℃ thermostat container freeze-day with constant temperature 9h, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 220 ℃, pressure are hot pressing 20min under the 20MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant.
The mass ratio of testing the Ag-Graphene described in seven step 1 and N-Methyl pyrrolidone is 1:200.
The mass ratio of testing the PVDF resin described in seven step 2 and N-Methyl pyrrolidone is 1:20.
Test in the Ag-Graphene described in seven step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 10:90 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution.
Test the Ag-Graphene described in seven step 1 and be the Ag-Graphene of test one preparation.
Adopt the accurate electric impedance analyzer test of Agilent 4294A under the 1KHz condition, to test one to the polyvinylidene fluoride-based composite with high dielectric constant of test seven preparations and the specific inductivity of pure PVDF resin, detected result as shown in Figure 3, Fig. 3 is that test one is to the specific inductivity graphic representation of the polyvinylidene fluoride-based composite with high dielectric constant of test seven preparations, the X-coordinate ratio of Fig. 3 is test one mass ratio of PVDF resin in Ag-Graphene and the PVDF resin/N-Methyl pyrrolidone solution to the Ag-Graphene of test described in seven step 3/N-Methyl pyrrolidone suspension, and the ordinate zou of Fig. 3 is specific inductivity; As shown in Figure 3 when the polyvinylidene fluoride-based composite with high dielectric constant of test six preparations reaches percolation threshold, it is 710 that the specific inductivity of the polyvinylidene fluoride-based composite with high dielectric constant of test six preparations connects, specific inductivity than pure PVDF resin has improved 84 times, is 44.375 times of existing Graphene/PVDF matrix material specific inductivity.
Claims (10)
1. a polyvinylidene fluoride-based composite with high dielectric constant is characterized in that polyvinylidene fluoride-based composite with high dielectric constant is prepared from by Ag-Graphene, N-Methyl pyrrolidone and PVDF resin; The mass ratio of described Ag-Graphene and PVDF resin is 1:(5 ~ 50); Described Ag-Graphene and PVDF resin total mass are 1:(6 ~ 125 with the ratio of N-Methyl pyrrolidone quality).
2. a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 1, it is characterized in that described Ag-Graphene is to adopt following step preparation: at first take Graphite Powder 99 as raw material adopts improved Hummers method make graphite oxide, then be under 40Hz ~ 250Hz graphite oxide to be scattered in the deionized water in ultrasonic frequency, the ultra-sonic dispersion time is 1h ~ 3h, namely obtaining concentration is the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL, then adds the AgNO that concentration is 0.01mol/L ~ 1mol/L
3The aqueous solution, and to continue in ultrasonic frequency be to adopt heating in water bath that mixed solution is warming up to 60 ℃ ~ 100 ℃ water-baths from room temperature under 40Hz ~ 250Hz behind ultrasonic 30min ~ 60min, then dropwise adding concentration is 0.05mol/L ~ 0.5mol/L NaBH
4The aqueous solution, obtain mixed solution, and be 60 ℃ ~ 100 ℃ lower back flow reaction 2h ~ 8h at bath temperature, after finishing, reaction adopts the Büchner funnel suction filtration, the solid that obtains adopts first distilled water wash 3 ~ 5 times, adopt washing with alcohol 3 ~ 5 times, the solid after the washing is 60 ℃ ~ 80 ℃ lower vacuum-drying 12h ~ 24h in temperature, obtains the Ag-Graphene again; The concentration of described adding is the AgNO of 0.01mol/L ~ 1mol/L
3The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(5 ~ 50); The concentration of described adding is the NaBH of 0.05mol/L ~ 0.5mol/L
4The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(1 ~ 10).
3. a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 1, the mass ratio that it is characterized in that described Ag-Graphene and PVDF resin is 1:(9 ~ 12); The described Ag-Graphene of present embodiment and PVDF resin total mass are 1:(12 ~ 100 with the ratio of N-Methyl pyrrolidone quality).
4. the preparation method of a kind of polyvinylidene fluoride-based composite with high dielectric constant as claimed in claim 1, the preparation method who it is characterized in that a kind of polyvinylidene fluoride-based composite with high dielectric constant finishes according to the following steps: one, preparation Ag-Graphene/N-Methyl pyrrolidone suspension: at first the Ag-Graphene is added in the N-Methyl pyrrolidone, and be ultra-sonic dispersion 30min ~ 60min under 40Hz ~ 250Hz in ultrasonic frequency, obtain Ag-Graphene/N-Methyl pyrrolidone suspension; Two, preparation PVDF resin/N-Methyl pyrrolidone solution: the PVDF resin is added in the N-Methyl pyrrolidone, and be 50 ℃ ~ 60 ℃ lower heating for dissolving 1h ~ 3h in temperature, obtain PVDF resin/N-Methyl pyrrolidone solution; Three, mix: under agitation condition, Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution are mixed, be ultra-sonic dispersion 30min ~ 90min under 40Hz ~ 250Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture; Four, film forming: Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture is watered and casts from the glass substrate, then placing temperature is thermostat container freeze-day with constant temperature 6h ~ 12h of 60 ℃ ~ 120 ℃, namely obtains Ag-Graphene/PVDF three-phase composite material film at glass substrate; Five, moulding: at first Ag-Graphene/PVDF three-phase composite material film is peeled from glass substrate, then fold and put into mould, be that 200 ℃ ~ 240 ℃, pressure are hot pressing 10min ~ 30min under 10MPa ~ 40MPa in temperature again, namely obtain polyvinylidene fluoride-based composite with high dielectric constant; The mass ratio of the Ag-Graphene described in the step 1 and N-Methyl pyrrolidone is 1:(50 ~ 500); The mass ratio of the PVDF resin described in the step 2 and N-Methyl pyrrolidone is 1:(5 ~ 50); In Ag-Graphene described in the step 3/N-Methyl pyrrolidone suspension in Ag-Graphene and the PVDF resin/N-Methyl pyrrolidone solution mass ratio of PVDF resin be 1:(5 ~ 50).
5. the preparation method of a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 4, it is characterized in that the Ag-Graphene described in the step 1 is to adopt following step preparation: at first take Graphite Powder 99 as raw material adopts improved Hummers method make graphite oxide, then be under 40Hz ~ 250Hz graphite oxide to be scattered in the deionized water in ultrasonic frequency, the ultra-sonic dispersion time is 1h ~ 3h, namely obtaining concentration is the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL, then adds the AgNO that concentration is 0.01mol/L ~ 1mol/L
3The aqueous solution, and to continue in ultrasonic frequency be to adopt heating in water bath that mixed solution is warming up to 60 ℃ ~ 100 ℃ water-baths from room temperature under 40Hz ~ 250Hz behind ultrasonic 30min ~ 60min, then dropwise adds the NaBH that concentration is 0.05mol/L ~ 0.5mol/L
4The aqueous solution, obtain mixed solution, and be 60 ℃ ~ 100 ℃ lower back flow reaction 2h ~ 8h at bath temperature, after finishing, reaction adopts the Büchner funnel suction filtration, the solid that obtains adopts first distilled water wash 3 ~ 5 times, adopt washing with alcohol 3 ~ 5 times, the solid after the washing is 60 ℃ ~ 80 ℃ lower vacuum-drying 12h ~ 24h in temperature, obtains the Ag-Graphene again; The concentration of described adding is the AgNO of 0.01mol/L ~ 1mol/L
3The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(5 ~ 50); The concentration of described adding is the NaBH of 0.05mol/L ~ 0.5mol/L
4The aqueous solution and concentration are that the volume ratio of the graphene oxide dispersion liquid of 0.01g/mL ~ 0.1g/mL is 1:(1 ~ 10).
6. the preparation method of a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 4 is characterized in that in the step 1 in ultrasonic frequency being ultra-sonic dispersion 40min ~ 50min under 80Hz ~ 200Hz.
7. the preparation method of a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 4 is characterized in that the Ag-Graphene described in the step 1 and the ratio of N-Methyl pyrrolidone quality are 1:(100 ~ 400).
8. the preparation method of a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 4, the mass ratio that it is characterized in that the PVDF resin described in the step 2 and N-Methyl pyrrolidone is 1:(10 ~ 40).
9. the preparation method of a kind of polyvinylidene fluoride-based composite with high dielectric constant according to claim 4, it is characterized in that the step 3 low whipping speed is under 300r/min ~ 700r/min Ag-Graphene/N-Methyl pyrrolidone suspension and PVDF resin/N-Methyl pyrrolidone solution to be mixed, be ultra-sonic dispersion 40min ~ 80min under 80Hz ~ 200Hz in ultrasonic frequency behind the mixing, namely obtain Ag-Graphene/PVDF resin/N-Methyl pyrrolidone mixture.
10. according to claim 4, the preparation method of 5,6,7,8 or 9 described a kind of polyvinylidene fluoride-based composite with high dielectric constants, it is characterized in that in the Ag-Graphene described in the step 3/N-Methyl pyrrolidone suspension that the mass ratio of PVDF resin is 1:(9 ~ 12 in the Ag-Graphene and PVDF resin/N-Methyl pyrrolidone solution).
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| CN108963069A (en) * | 2018-06-28 | 2018-12-07 | 江苏大学 | A kind of preparation method of 3D printing poly meta fluoroethylene piezoelectric film |
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| CN103500654A (en) * | 2013-10-11 | 2014-01-08 | 张孝彬 | Nitrogen-doped graphene/PVDF (Polyvinylidene Fluoride) composite dielectric film and preparation method thereof |
| CN103951915A (en) * | 2014-04-29 | 2014-07-30 | 上海交通大学 | Lightweight flexible polymer-based high-energy-density material and preparation method thereof |
| CN103951917A (en) * | 2014-04-29 | 2014-07-30 | 上海交通大学 | Flexible high-dielectric polymer composite material and preparation method thereof |
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| CN105833742A (en) * | 2016-04-26 | 2016-08-10 | 上海应用技术学院 | Preparation method for hydrophilic polyvinylidene fluoride (PVDF) antibacterial ultrafiltration membrane |
| CN108963069A (en) * | 2018-06-28 | 2018-12-07 | 江苏大学 | A kind of preparation method of 3D printing poly meta fluoroethylene piezoelectric film |
| CN108963069B (en) * | 2018-06-28 | 2022-01-11 | 上海凸申科技有限公司 | Preparation method of 3D printed polyvinylidene fluoride piezoelectric film |
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