CN108570201A - dielectric composite material and preparation method thereof - Google Patents
dielectric composite material and preparation method thereof Download PDFInfo
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- CN108570201A CN108570201A CN201810441260.0A CN201810441260A CN108570201A CN 108570201 A CN108570201 A CN 108570201A CN 201810441260 A CN201810441260 A CN 201810441260A CN 108570201 A CN108570201 A CN 108570201A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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Abstract
The present invention relates to a kind of dielectric composite materials and preparation method thereof.The preparation method and dielectric composite material of above-mentioned dielectric composite material, hydroxylating processing is carried out to barium titanate particles surface, it adds fluorochemical monomer initiation polymerization and obtains the modified barium carbonate with nucleocapsid, it prepares modified barium carbonate and vinylidene fluoride hexafluoropropylene copolymer to obtain electrostatic spinning solvent again, the technique of electrostatic spinning is recycled to obtain dielectric composite material.Barium titanate particles have very high dielectric constant and vinylidene fluoride hexafluoropropylene copolymer has good breakdown performance, introduce fluorochemical monomer, it is similar with matrix polymer PVDF HFP that a certain number of fluorine atoms are carried on this kind of monomer molecule chain, this one kind monomer is coated on particle surface, play the effect of mild transition, the compatibility between particle and matrix can be increased, so that the dispersibility that particle has had, so that dielectric composite material is with high-k, high breakdown field strength and low-dielectric loss.
Description
Technical field
The present invention relates to dielectric material preparing technical fields, more particularly to dielectric composite material and preparation method thereof.
Background technology
Dielectric material has good insulation performance, and its most important purposes is the preparation for capacitor.Capacitor
Principle be, to allow it to generate electric polarization response, to achieve the purpose that store energy among dielectric material is placed in electric field.It utilizes
This feature of dielectric material can be widely used in medical instrument, new-energy automobile, pulse weapon, filter, period energy storage
Etc. all various aspects.For a kind of dielectric material, it is desirable to obtain preferable practical effect, then it must be to have high dielectric normal
Number simultaneously, will also possess high breakdown strength, low dielectric loss is also a necessary factors.But in real process, but it is difficult
Realize that three is unified, this is because for Inorganic Dielectric Material, although it is relatively low to possess high dielectric constant breakdown strength,
Such as the dielectric constant of BTO can reach 102-104, disruptive field intensity only has 3kV/mm, polymer material then just in contrast,
If the dielectric constant of PVDF only has 10 or so, and disruptive field intensity can reach 600kv/mm, and how by the two, respectively advantage combines
Get up to become people and improves the key that material property is explored.The inorganic method with organic composite can preferably unite this three
It comes together, by the combination of inorganic filler and polymeric matrix, inorganic high-k had not only been utilized, but also have polymer
High breakdown field strength, then by certain methods adjust reduce composite material dielectric loss, thereby realize dielectric material
The fine promotion of performance.But during the experiment, small size inorganic particle is mainly added to polymer in the form of filler
Particle since the size of particle is generally in tens Nano grades, thus is simply added directly into polymer, particle by matrix
Since specific surface area is too big, in order to reduce self-energy, agglomeration can be spontaneously formed, the result of generation of reuniting may result in pair
Material apply electric field when, can reunion region formed electric field accumulation, cause loss fast lifting and disruptive field intensity it is apparent
Decline.
Composite material has many advantages, such as, but has actually implemented many more formidable places, wherein the most
More main is exactly the scattering problem of filler, and particle agglomeration can be such that material property greatly reduces, and is produced with the material preparation
Electronic device can not use at all, and in order to solve to be influenced caused by dispersibility, researcher has carried out all in this regard
It is explore more, and had certain achievement.Processing mode the simplest is to handle particle with hydrogen peroxide, is allowed
Grain surface carries a certain number of hydroxyls (- OH), can improve particle dispersion to a certain extent, but effect is not obvious.
The Emmanuel P.Giannelis of Kang Naer universities of the U.S. are taught utilized siloxanes by the modified addition in the surfaces BTO in 2003
Into epoxy resin, the dielectric constant of composite material reaches 45, is higher than the 4 of epoxy resin, but is lost compared to not being modified
BTO composite materials for, but have raising, there is certain negative influence.The Frank G.Shi of University of California utilize phosphorus
After hydrochlorate modifies BTO surfaces, by compound with P (VDF-CTFE), 37 dielectric constant is realized, but breakdown strength occurs
It reduces.Therefore, the evenly dispersed problem of inorganic filler in the polymer is resolved, it is normal to become the high dielectric of composite material acquisition
The key of number, high breakdown field strength, low-dielectric loss.
Invention content
Based on this, it is necessary to it is difficult to have both high-k, high breakdown field strength and low-dielectric loss for dielectric material, and
Organic filler is difficult to realize the problem of preferable dispersibility when being used to improve the dielectric properties of dielectric material, it is multiple to provide a kind of dielectric
Condensation material and preparation method thereof.
A kind of preparation method of dielectric composite material, includes the following steps：
Surface hydroxylation processing is carried out to barium titanate particles；
It will be scattered in solvent by the barium titanate particles of surface hydroxylation processing, and fluorochemical monomer and initiator be added,
So that on barium titanate particles surface polymerisation, which occurs, for fluorochemical monomer obtains the modified barium carbonate with nucleocapsid；
It prepares the modified barium carbonate and vinylidene difluoride-hexafluoropropylene copolymer to obtain colloidal sol；And
The colloidal sol is molded to obtain the dielectric composite material.
In a wherein embodiment, surface hydroxylation processing is carried out to the barium titanate particles using hydrogen peroxide；Institute
The temperature for stating surface hydroxylation processing is 30 DEG C~100 DEG C, and the time of the surface hydroxylation processing is 100min~400min.
In a wherein embodiment, the grain size of the barium titanate particles is 5nm~200nm.
In a wherein embodiment, the solvent is n,N-Dimethylformamide；
And/or the fluorochemical monomer is selected from least one of trifluoro ethyl ester, hexafluoro butyl ester and ten difluoro heptyl esters；
And/or the initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile.
In a wherein embodiment, the fluorochemical monomer and the barium titanate particles handled by surface hydroxylation
Molar ratio be 5:1~9:1；
And/or the molar ratio of the fluorochemical monomer and the initiator is 200:1~400:1.
In a wherein embodiment, the fluorochemical monomer barium titanate particles surface occur polymerisation after with acetone
It is mixed to get reaction solution, then the reaction solution and the vinylidene difluoride-hexafluoropropylene copolymer are mixed to get the colloidal sol；
The volume ratio of the acetone and the solvent is 9:1~1:9.
In a wherein embodiment, the modified barium carbonate particle is copolymerized with the vinylidene fluoride-hexafluoropropene
Object and the mass ratio of the total amount of the modified barium carbonate particle are 1:100~20:200.
In a wherein embodiment, the step of being molded the colloidal sol to obtain the dielectric composite material, specifically wraps
It includes：The colloidal sol is molded by the way of electrostatic spinning to obtain composite fibre silk；And hot pressing is carried out to the composite fibre silk
Obtain the dielectric composite material.
It is described to be molded the colloidal sol to obtain composite fibre by the way of electrostatic spinning in a wherein embodiment
In the step of silk, the voltage of the electrostatic spinning is 2kV~15kV, and the speed of injecting of the colloidal sol is 0.05mL/h~0.2mL/
H, spinning distance are 5cm~40cm, and drum rotation speed is 100rpm~1000rpm；
And/or in described the step of obtaining the dielectric composite material to composite fibre silk progress hot pressing, hot pressing temperature
Degree is 50 DEG C~300 DEG C, and hot pressing pressure is 2MPa~15MPa, and hot pressing time is 10min~60min.
A kind of dielectric composite material is prepared according to the preparation method of above-mentioned dielectric composite material.
The preparation method and dielectric composite material of above-mentioned dielectric composite material first carry out hydroxylating to barium titanate particles surface
Processing adds the modified barium carbonate that fluorochemical monomer obtains having nucleocapsid in barium titanate particles surface initiation polymerization, then will
Modified barium carbonate is prepared to obtain electrostatic spinning solvent with vinylidene difluoride-hexafluoropropylene copolymer, recycles the work of electrostatic spinning
Dielectric composite material is prepared in skill and heat pressing process.Barium titanate particles have very high dielectric constant and vinylidene fluoride-
Hexafluoropropylene copolymer has good breakdown performance, in order to reduce the excessive caused shadow of dielectric properties difference between the two
It rings, introduces fluorochemical monomer, a certain number of fluorine atoms and matrix polymer PVDF-HFP are carried on this kind of monomer molecule chain
It is similar, this one kind monomer is coated on particle surface, the effect of mild transition is played, the phase between particle and matrix can be increased
Capacitive, so that the dispersibility that particle has had, so that the dielectric composite material being prepared is normal with high dielectric
Number, high breakdown field strength and low-dielectric loss.
Description of the drawings
Fig. 1 is the process flow chart of the preparation method of the dielectric composite material of an embodiment；
Fig. 2 is the transmission electron microscope photo for the modified barium carbonate being prepared in embodiment 1；
Fig. 3 is the stereoscan photograph of the section for the dielectric composite material being prepared in embodiment 1；
Fig. 4 is the infrared spectrogram for the dielectric composite material that Examples 1 to 3 is prepared；
Fig. 5 is the dielectric constant curve for the dielectric composite material that Examples 1 to 3 is prepared；
Fig. 6 is the polarization curve for the dielectric composite material that Examples 1 to 3 is prepared.
Specific implementation mode
Dielectric composite material and preparation method thereof is done below in conjunction with specific implementation mode and attached drawing further detailed
Explanation.
Referring to Fig. 1, the preparation method of the dielectric composite material of an embodiment includes the following steps：
S110, hydroxylating processing is carried out to barium titanate particles surface.
In a wherein embodiment, hydroxylating processing is carried out to barium titanate (BTO) particle surface using hydrogen peroxide.Into
One step, barium titanate particles are mixed with hydrogen peroxide and is stirred and heats.
In a wherein embodiment, the rotating speed being stirred is that 300rpm~700rpm is further stirred
Rotating speed can also be 500rpm；The temperature for carrying out hydroxylating processing is 30 DEG C~100 DEG C, further, is carried out at hydroxylating
The temperature of reason can also be 70 DEG C；The time for carrying out hydroxylating processing is 100min~400min, further, carries out hydroxylating
The time of processing can also be 200min, 250min or 300min.
In a wherein embodiment, the grain size of barium titanate particles is 5nm~200nm, further, barium titanate particles
Grain size be 20nm, 50nm or 100nm.Particle size it is smaller, specific surface area is bigger, in this way in the inside of dielectric composite material
More interfacial polarizations can be contributed, and interfacial polarization has bigger polarization to contribute the polarization performance of dielectric material, because
This, the grain size of preferred barium titanate particles is 5nm~50nm.However, after particle becomes smaller, surface energy increases, and is easy to be formed and reunite,
This is also one of the problem that the application can overcome.
In a wherein embodiment, the mass concentration of hydrogen peroxide is 30%, further, barium titanate particles and dioxygen
The mass volume ratio of water is 0.05g/mL~0.2g/mL, and further, the mass volume ratio of barium titanate particles and hydrogen peroxide may be used also
To be 0.1g/mL or 0.15g/mL.
S120, the barium titanate particles by surface hydroxylation processing are washed and is dried.
In a wherein embodiment, washed being added to the water by the barium titanate particles of surface hydroxylation processing
It washs, further, the number of washing is 3 times~5 times.By after the barium titanate particles that surface hydroxylation is handled are added to the water again
Centrifugal treating is carried out, the rotating speed of centrifugal treating is 6000rpm~12000rpm, and further, the rotating speed of centrifugal treating can be with
It is 10000rpm；The time of centrifugal treating is 5min~30min, and further, the time of centrifugal treating is 20min.
Supernatant is removed in a wherein embodiment, after centrifugal treating and the barium titanate particles of lower layer are dried
The temperature of processing, drying process is 50 DEG C~100 DEG C, and the time of drying process is 10h~30h；Further, drying process
Temperature is 90 DEG C, and the time of drying process is 12h.
S130, it will be scattered in solvent by the barium titanate particles of surface hydroxylation processing, and fluorochemical monomer be added and draws
Send out agent so that fluorochemical monomer occurs polymerisation on barium titanate particles surface and obtains the modified barium carbonate with nucleocapsid.
In a wherein embodiment, solvent is n,N-Dimethylformamide (DMF).Further, by surface hydroxyl
The mass percentage of the barium titanate particles of baseization processing in a solvent is 10%~16%.
In a wherein embodiment, it will be needed when being scattered in solvent by the barium titanate particles of surface hydroxylation processing
Ultrasonication is carried out, the power of ultrasonication is 100W~400W, and the time of ultrasonication is 5min~40min；
Further, the power of ultrasonication can also be 200W, and the time of ultrasonication can also be 20min.
In a wherein embodiment, fluorochemical monomer is selected from trifluoro ethyl ester (TFEMA), hexafluoro butyl ester (HFBMA) and ten
At least one of difluoro heptyl ester (DFHMA).
In a wherein embodiment, the molar ratio of fluorochemical monomer and the barium titanate particles by surface hydroxylation processing
It is 5:1~9:1.Further, the molar ratio of fluorochemical monomer and the barium titanate particles by surface hydroxylation processing can also be
7:1。
In a wherein embodiment, initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile.
Further, the molar ratio of fluorochemical monomer and initiator is 200:1~400:1, further, fluorochemical monomer and initiator rub
You can also be 300 by ratio:1.
In a wherein embodiment, temperature when fluorochemical monomer carries out polymerisation is 0~100 DEG C, further,
The temperature of polymerisation can also be 60 DEG C.The time for carrying out polymerisation is that 2h~5h further carries out polymerisation
Time can also be 3h.
In a wherein embodiment, carry out also needing to be stirred when polymerisation, stir speed (S.S.) 400rpm
~700rpm, further, stir speed (S.S.) can also be 500rpm.
S140, it prepares modified barium carbonate and vinylidene difluoride-hexafluoropropylene copolymer to obtain colloidal sol.
In a wherein embodiment, the product and the acetone that are obtained to step S140 are mixed to get reaction solution, then will be anti-
Liquid is answered to be mixed to get colloidal sol with vinylidene difluoride-hexafluoropropylene copolymer (PVDF-HFP).
In a wherein embodiment, the volume ratio of acetone and solvent is 9:1~1:9.Further, acetone and solvent
Volume ratio can also be 7:3.Acetone can play the role of terminating polymerisation progress, and acetone can play adjusting reaction
The effect of the viscosity of liquid.
In a wherein embodiment, in colloidal sol obtained above, modified barium carbonate particle and vinylidene fluoride-six
Fluoropropene copolymer and the mass ratio of the total amount of modified barium carbonate particle are 1:100~20:100.Further, modified barium carbonate
Particle and the mass ratio of vinylidene difluoride-hexafluoropropylene copolymer and the total amount of modified barium carbonate particle can also be 15:100.
It is understood that in other embodiments, first modified barium carbonate can also be detached from reaction solution, into one
Step, the mode that centrifugation may be used detaches modified barium carbonate particle, then is washed and be dried to obtain using water and changed
Property barium titanate particles, then modified barium carbonate particle is scattered in dispersion liquid and obtains modified barium carbonate dispersion liquid, by inclined difluoro second
Alkene-hexafluoropropylene copolymer mixes to obtain electrostatic spinning solvent with modified barium carbonate dispersion liquid.
S150, colloidal sol is molded to obtain dielectric composite material.
In a wherein embodiment, the step of solvent molding is obtained dielectric composite material, specifically includes：
S151, colloidal sol is molded by the way of electrostatic spinning to obtain composite fibre silk.
In a wherein embodiment, the voltage of electrostatic spinning is 2kV~15kV, further, the electricity of electrostatic spinning
Pressure can also be 6kV, 10kV or 12kV；The speed of injecting of colloidal sol is 0.05mL/h~0.2mL/h, further, electrostatic spinning
Speed of injecting can also be 0.1mL/h or 0.15mL/h；Spinning distance is 5cm~40cm, and further, spinning distance may be used also
To be 20cm, 25cm or 30cm；Drum rotation speed is 100rpm~1000rpm, and further, drum rotation speed can also be
400rpm, 600rpm or 800rpm.
S152, dielectric composite material is obtained to the progress hot pressing of composite fibre silk.
In a wherein embodiment, hot pressing temperature is 50 DEG C~300 DEG C；Hot pressing pressure is 2MPa~15MPa, into one
Step, hot pressing pressure can also be 10MPs；Hot pressing time is 10min~60min.
In a wherein embodiment, hot-pressing processing is carried out to composite fibre silk by the way of being segmented hot pressing, first
Hot pressing 15min~30min is carried out at 80 DEG C~120 DEG C, and hot pressing 15min~30min is then carried out at 130 DEG C~170 DEG C,
Hot pressing 15min~30min is finally carried out at 220 DEG C~240 DEG C.
The preparation method of above-mentioned dielectric composite material first carries out hydroxylating processing to barium titanate particles surface, adds and contain
The modified barium carbonate that fluorine monomer obtains having nucleocapsid in barium titanate particles surface initiation polymerization, then by modified barium carbonate and partially
Difluoroethylene-hexafluoropropylene copolymer is prepared to obtain electrostatic spinning solvent, recycles the technique and heat pressing process system of electrostatic spinning
It is standby to obtain dielectric composite material.Barium titanate particles have very high dielectric constant and vinylidene difluoride-hexafluoropropylene copolymer
There is good breakdown performance, in order to reduce the excessive caused influence of dielectric properties difference between the two, introduces fluorine-containing
Monomer, it is similar with matrix polymer PVDF-HFP to carry a certain number of fluorine atoms on this kind of monomer molecule chain, this is a kind of
Monomer is coated on particle surface, plays the effect of mild transition, can increase the compatibility between particle and matrix, so that
The dispersibility that particle has had so that the dielectric composite material being prepared with do intersection point constant, high breakdown fields
Strong and low-dielectric loss.
In addition, it is necessary to explanation, the surface initiation polymerization using fluorochemical monomer in barium titanate particles has to be formed
How much the modified barium carbonate of nucleocapsid, can be by controlling monomer, and preferable control cladding thickness can also realize uniform cladding
Effect.In addition, in general, the grain size for reducing barium titanate particles is conducive to improve its specific surface area, to compound in dielectric
The contributions internal of material goes out more interfacial polarizations, and second interface polarization has the polarization performance of dielectric composite material bigger tribute
It offers, however, the grain size of barium titanate particles is smaller, is more unfavorable for the dispersion in polymeric substrate, and in the application, use is fluorine-containing
Monomer coats barium titanate particles surface, can realize point of the barium titanate particles compared with small particle in polymeric substrate
It dissipates.
It should be noted that in other embodiments, step S120 can also be omitted.
A kind of dielectric composite material is prepared by the preparation method of above-mentioned dielectric composite material.Jie being prepared
Composite with high-k, high breakdown field strength and low-dielectric loss, and barium titanate particles have in the substrate compared with
Good dispersibility.
It is the explanation of specific embodiment below, following embodiment unless otherwise specified, is not then contained except inevitably miscellaneous
The component pointed out is not known in other other than matter.
Embodiment 1
The BTO particle 15g that grain size is 50nm are weighed, are added in the 150ml round-bottomed flasks with rotor, 30wt% is measured
H2O280ml pours into round-bottomed flask, and condensation reflux unit is accessed on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, oil
Bath temperature sets 70 DEG C, and 500rpm is stirred at reflux 5h, and solution is poured into 150ml centrifuge tubes, the centrifugation of 10000rpm rotating speeds
20min, be washed with deionized repeatedly three times, take out lower sediment particle, be put into the dry 12h of 90 DEG C of vacuum drying oven obtain by
The BTO particles of hydroxylating processing store for future use.
The BTO particles that 1g passes through hydroxylating processing are weighed, are added in the 20ml round-bottomed flasks with rotor, 7ml is measured
DMF solvent pours into round-bottomed flask, and 200W ultrasonic disperse 20min measure 4.27ml TFEMA (0.03mol) monomer, pour into dispersion
In solution afterwards, 300rpm sealing stirrings 20min makes to be uniformly mixed, and weighs initiator A IBN 0.0164g and is slowly added into round bottom
Flask accesses condensation reflux unit on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, and oil bath temperature sets 60 DEG C,
500rpm is stirred at reflux 3h and obtains the modified barium carbonate with nucleocapsid, and 3ml acetone is then added, and terminates reaction.Room temperature item
5.75g PVDF-HFP, 400rpm are added under part and stirs 4h, draws colloidal sol obtained by 5ml with 10ml needle tubings, uses electrostatic spinning apparatus
Carry out the preparation of fabric nonwoven cloth, the setting of spinning condition：Voltage is 12kV, and the speed of injecting of syringe pump is 0.1ml/h, spinning
Distance setting 20cm, reception device drum rotation speed set 400rpm, and the spinning time is set as 60min.Non-woven fabrics is removed, is put
Under the pressure of 10MP then 100 DEG C of hot pressing 20min anneal among clamping plate, then 150 DEG C of hot pressing 20min annealing, most
200 DEG C of hot pressing 20min are put into rapidly progress cold quenching processing in ice water afterwards.
Embodiment 2
The BTO particle 15g that grain size is 50nm are weighed, are added in the 150ml round-bottomed flasks with rotor, 30wt% is measured
H2O280ml pours into round-bottomed flask, and condensation reflux unit is accessed on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, oil
Bath temperature sets 70 DEG C, and 500rpm is stirred at reflux 5h, and solution is poured into 150ml centrifuge tubes, the centrifugation of 10000rpm rotating speeds
20min, be washed with deionized repeatedly three times, take out lower sediment particle, be put into the dry 12h of 90 DEG C of vacuum drying oven obtain by
The BTO particles of hydroxylating processing store for future use.
The BTO particles that 1g passes through hydroxylating processing are weighed, are added in the 20ml round-bottomed flasks with rotor, 7ml is measured
DMF solvent pours into round-bottomed flask, and 200W ultrasonic disperse 20min measure 5.6ml HFBMA (0.03mol) monomer, after pouring into dispersion
Solution in, 300rpm sealing stirring 20min make to be uniformly mixed, weigh initiator A IBN 0.0164g be slowly added into round bottom burning
Bottle, condensation reflux unit is accessed on round-bottomed flask, sealing, which is placed in oil bath, opens stirring, and oil bath temperature sets 60 DEG C,
500rpm is stirred at reflux 3h and obtains the modified barium carbonate with nucleocapsid, and 3ml acetone is then added, and terminates reaction.Room temperature item
5.75g PVDF-HFP, 400rpm are added under part and stirs 4h, draws colloidal sol obtained by 5ml with 10ml needle tubings, uses electrostatic spinning apparatus
Carry out the preparation of fabric nonwoven cloth, the setting of spinning condition：Voltage is 12kV, and the speed of injecting of syringe pump is 0.1ml/h, spinning
Distance setting 20cm, reception device drum rotation speed set 400rpm, and the spinning time is set as 60min.Non-woven fabrics is removed, is put
Under the pressure of 10MP then 100 DEG C of hot pressing 20min anneal among clamping plate, then 150 DEG C of hot pressing 20min annealing, most
200 DEG C of hot pressing 20min are put into rapidly progress cold quenching processing in ice water afterwards.
Embodiment 3
The BTO particle 15g that grain size is 50nm are weighed, are added in the 150ml round-bottomed flasks with rotor, 30wt% is measured
H2O280ml pours into round-bottomed flask, and condensation reflux unit is accessed on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, oil
Bath temperature sets 70 DEG C, and 500rpm is stirred at reflux 5h, and solution is poured into 150ml centrifuge tubes, the centrifugation of 10000rpm rotating speeds
20min, be washed with deionized repeatedly three times, take out lower sediment particle, be put into the dry 12h of 90 DEG C of vacuum drying oven obtain by
The BTO particles of hydroxylating processing store for future use.
The BTO particles that 1g passes through hydroxylating processing are weighed, are added in the 20ml round-bottomed flasks with rotor, 7ml is measured
DMF solvent pours into round-bottomed flask, and 200W ultrasonic disperse 20min measure 7.56ml DFHMA (0.03mol) monomer, pour into dispersion
In solution afterwards, 300rpm sealing stirrings 20min makes to be uniformly mixed, and weighs initiator A IBN 0.0164g and is slowly added into round bottom
Flask accesses condensation reflux unit on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, and oil bath temperature sets 60 DEG C,
500rpm is stirred at reflux 3h and obtains the modified barium carbonate with nucleocapsid, and 3ml acetone is then added, and terminates reaction.Room temperature item
5.75g PVDF-HFP, 400rpm are added under part and stirs 4h, draws colloidal sol obtained by 5ml with 10ml needle tubings, uses electrostatic spinning apparatus
Carry out the preparation of fabric nonwoven cloth, the setting of spinning condition：Voltage is 12kV, and the speed of injecting of syringe pump is 0.1ml/h, spinning
Distance setting 20cm, reception device drum rotation speed set 400rpm, and the spinning time is set as 60min.Non-woven fabrics is removed, is put
Under the pressure of 10MP then 100 DEG C of hot pressing 20min anneal among clamping plate, then 150 DEG C of hot pressing 20min annealing, most
200 DEG C of hot pressing 20min are put into rapidly progress cold quenching processing in ice water afterwards.
Embodiment 4
The BTO particle 15g that grain size is 20nm are weighed, are added in the 150ml round-bottomed flasks with rotor, 30wt% is measured
H2O2100ml pours into round-bottomed flask, and condensation reflux unit is accessed on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, oil
Bath temperature sets 80 DEG C, and 500rpm is stirred at reflux 250min, and solution is poured into 150ml centrifuge tubes, the centrifugation of 8000rpm rotating speeds
30min, be washed with deionized repeatedly three times, take out lower sediment particle, be put into 80 DEG C of dryings of vacuum drying oven obtain for 24 hours by
The BTO particles of hydroxylating processing store for future use.
The BTO particles that 1g passes through hydroxylating processing are weighed, are added in the 20ml round-bottomed flasks with rotor, 9ml is measured
DMF solvent pours into round-bottomed flask, and 200W ultrasonic disperse 20min measure 7.17ml TFEMA (0.05mol) monomer, pour into dispersion
In solution afterwards, 300rpm sealing stirrings 20min makes to be uniformly mixed, and weighs initiator A IBN 0.0256g and is slowly added into round bottom
Flask accesses condensation reflux unit on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, and oil bath temperature sets 60 DEG C,
500rpm is stirred at reflux 3h and obtains the modified barium carbonate with nucleocapsid, and 3ml acetone is then added, and terminates reaction.Room temperature item
8.75g PVDF-HFP, 400rpm are added under part and stirs 4h, draws colloidal sol obtained by 5ml with 10ml needle tubings, uses electrostatic spinning apparatus
Carry out the preparation of fabric nonwoven cloth, the setting of spinning condition：Voltage is 12kV, and the speed of injecting of syringe pump is 0.1ml/h, spinning
Distance setting 20cm, reception device drum rotation speed set 400rpm, and the spinning time is set as 60min.Non-woven fabrics is removed, is put
Under the pressure of 10MP then 100 DEG C of hot pressing 20min anneal among clamping plate, then 150 DEG C of hot pressing 20min annealing, most
200 DEG C of hot pressing 20min are put into rapidly progress cold quenching processing in ice water afterwards.
Embodiment 5
The BTO particle 15g that grain size is 50nm are weighed, are added in the 150ml round-bottomed flasks with rotor, 30wt% is measured
H2O280ml pours into round-bottomed flask, and condensation reflux unit is accessed on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, oil
Bath temperature sets 70 DEG C, and 500rpm is stirred at reflux 5h, and solution is poured into 150ml centrifuge tubes, the centrifugation of 10000rpm rotating speeds
20min, be washed with deionized repeatedly three times, take out lower sediment particle, be put into the dry 12h of 90 DEG C of vacuum drying oven obtain by
The BTO particles of hydroxylating processing store for future use.
The BTO particles that 1g passes through hydroxylating processing are weighed, are added in the 20ml round-bottomed flasks with rotor, 7ml is measured
DMF solvent pours into round-bottomed flask, and 200W ultrasonic disperses 20min, 300rpm sealing stirring 20min makes to be uniformly mixed, room temperature condition
Lower addition 5.75g PVDF-HFP, 400rpm stir 4h, with 10ml needle tubings draw 5ml obtained by colloidal sol, with electrostatic spinning apparatus into
The preparation of row fabric nonwoven cloth, the setting of spinning condition：Voltage is 12kV, and the speed of injecting of syringe pump is 0.1ml/h, spinning away from
From setting 20cm, reception device drum rotation speed sets 400rpm, and the spinning time is set as 60min.Non-woven fabrics is removed, is placed it in
Under the pressure of 10MP then 100 DEG C of hot pressing 20min anneal among clamping plate, then 150 DEG C of hot pressing 20min annealing, finally
200 DEG C of hot pressing 20min are put into rapidly progress cold quenching processing in ice water.
Embodiment 6
The BTO particles (grain size 50nm) for weighing 1g are added in the 20ml round-bottomed flasks with rotor, measure 7ml
DMF solvent pours into round-bottomed flask, and 200W ultrasonic disperse 20min measure 4.27ml TFEMA (0.03mol) monomer, pour into dispersion
In solution afterwards, 300rpm sealing stirrings 20min makes to be uniformly mixed, and weighs initiator A IBN 0.0164g and is slowly added into round bottom
Flask accesses condensation reflux unit on round-bottomed flask, and sealing, which is placed in oil bath, opens stirring, and oil bath temperature sets 60 DEG C,
500rpm is stirred at reflux 3h, and 3ml acetone is then added, and terminates reaction.5.75g PVDF-HFP, 400rpm are added under room temperature
4h is stirred, colloidal sol obtained by 5ml is drawn with 10ml needle tubings, the preparation of fabric nonwoven cloth, spinning condition is carried out with electrostatic spinning apparatus
Setting：Voltage is 12kV, and the speed of injecting of syringe pump is 0.1ml/h, spinning distance setting 20cm, reception device drum rotation speed
400rpm is set, the spinning time is set as 60min.Non-woven fabrics is removed, is placed it among clamping plate 100 DEG C under the pressure of 10MP
Then hot pressing 20min anneals, then 150 DEG C of hot pressing 20min annealing, last 200 DEG C of hot pressing 20min are put into ice water rapidly
Carry out cold quenching processing.
Transmissioning electric mirror test is carried out to the modified barium carbonate being prepared in embodiment 1, the results are shown in Figure 2, wherein thoroughly
The test of radio mirror uses the transmission electron microscope instrument of Japan Electronics producer JEM-2100F models.From figure 2 it can be seen that in barium titanate
Fluorochemical monomer is added in dispersion liquid and causes polymerization, the polymer of generation is coated on particle table by nuclearing centre of barium titanate particles
Face, to obtain the modified barium carbonate particle with nucleocapsid.
The section for the dielectric composite material that embodiment 1 is prepared is scanned Electronic Speculum test, and the results are shown in Figure 3,
Wherein, sem test uses the scanning electron microscope instrument of 500 models of Zeiss producer GEMINISEM.As can be seen from Figure 3 thin
Film thickness uniformity is good, and after modified BTO particles are added in polymeric matrix, apparent agglomeration does not occur, plays very well
Dispersion effect.
Infrared spectrum analysis is carried out to the dielectric composite material that Examples 1 to 3 is prepared, the results are shown in Figure 4,
In, infrared spectrum analysis uses the infrared spectrometric analyzer of producer of Nai Chi companies X70 models.As can be seen from Figure 4 for not
With the BTO particles after monomer modified, infrared spectrum can detect the characteristic peak of corresponding modified monomer, this also demonstrates cladding knot
Fruit is successful (1655cm-1 (- C=O), 2800-3000cm-1 (- CH2 ,-CH3), 1100-1200cm-1and 1400cm-1
(C-F))。
The dielectric constant for the dielectric composite material that Examples 1 to 3 is prepared is tested, and the results are shown in Figure 5,
In, dielectric constant is tested to obtain using the ferroelectricity measuring and analysing meter of Radiant producers Premier II models.It can be with from Fig. 5
Find out that monomer modified rear filling can bring the promotion of dielectric constant, as surface cladding monomer fluorine atom amount increases, dielectric is normal
Number increases therewith, this is because as the molecule growth of cladding monomer and fluorine atom amount increase, modified BTO particle tables
Face increases with matrix interaction so that filler improves with matrix compatibility, finally brings performance boost.
The polarization performance for the dielectric composite material that Examples 1 to 3 is prepared is tested, and the results are shown in Figure 6,
In, polarization performance use is that the testing impedance instrument of Deco skill producer E4990A models is tested to obtain.As can be seen from Figure 6 with
It surface cladding monomer fluorine atom amount to increase, preparing the polarization of obtained laminated film can increase, this and front dielectric constant
Increase caused by reason it is identical, be because cladding monomer molecule segment and fluorine atom increase, filler is compatible with matrix
Property improves caused contribution.
The energy storage density and energy storage efficiency for the dielectric composite material that Examples 1 to 6 is prepared are tested, as a result such as
Shown in table 1, wherein energy storage density and energy storage efficiency use the ferroelectricity measuring and analysing meter of Radiant producers Premier II models
Test obtains, and test condition is：Frequency 10Hz.BTO particles after modification as can be seen from Table 1, are added to matrix
In after, energy storage density and energy storage efficiency to material play larger promotion effect, also, with cladding monomer molecule segment
Upper fluorine atom amount increases, and performance can be promoted further, this is because increasing with fluorine atom, be more nearly with matrix properties, this
Sample increases compatibility between particle and matrix, and particle dispersion improves, and therefore, material property is centainly promoted.
Table 1
| Energy storage density (J/cm3) | Energy storage efficiency (%) | |
| Embodiment 1 | 7.3 | 74 |
| Embodiment 2 | 7.7 | 79 |
| Embodiment 3 | 8.2 | 83 |
| Embodiment 4 | 7.0 | 73 |
| Embodiment 5 | 6.8 | 69 |
| Embodiment 6 | 6.0 | 68 |
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of dielectric composite material, which is characterized in that include the following steps：
Surface hydroxylation processing is carried out to barium titanate particles；
It will be scattered in solvent by the barium titanate particles of surface hydroxylation processing, and fluorochemical monomer and initiator be added so that
Fluorochemical monomer occurs polymerisation on barium titanate particles surface and obtains the modified barium carbonate with nucleocapsid；
It prepares the modified barium carbonate and vinylidene difluoride-hexafluoropropylene copolymer to obtain colloidal sol；And
The colloidal sol is molded to obtain the dielectric composite material.
2. the preparation method of dielectric composite material according to claim 1, which is characterized in that using hydrogen peroxide to the titanium
Sour titanate particle carries out surface hydroxylation processing；The temperature of the surface hydroxylation processing is 30 DEG C~100 DEG C, the surface hydroxyl
The time for changing processing is 100min~400min.
3. the preparation method of dielectric composite material according to claim 1, which is characterized in that the grain of the barium titanate particles
Diameter is 5nm~200nm.
4. the preparation method of dielectric composite material according to claim 1, which is characterized in that the solvent is N, N- diformazans
Base formamide；
And/or the fluorochemical monomer is selected from least one of trifluoro ethyl ester, hexafluoro butyl ester and ten difluoro heptyl esters；
And/or the initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile.
5. the preparation method of dielectric composite material according to claim 1, which is characterized in that the fluorochemical monomer with it is described
The molar ratio of the barium titanate particles handled by surface hydroxylation is 5:1~9:1；
And/or the molar ratio of the fluorochemical monomer and the initiator is 200:1~400:1.
6. the preparation method of dielectric composite material according to claim 1, which is characterized in that the fluorochemical monomer is in metatitanic acid
Titanate particle surface occurs to be mixed to get reaction solution with acetone after polymerisation, then by the reaction solution and the vinylidene fluoride-
Hexafluoropropylene copolymer is mixed to get the colloidal sol；The volume ratio of the acetone and the solvent is 9:1~1:9.
7. the preparation method of dielectric composite material according to claim 1, which is characterized in that the modified barium carbonate particle
It is 1 with the vinylidene difluoride-hexafluoropropylene copolymer and the mass ratio of the total amount of the modified barium carbonate particle:100~20:
200。
8. the preparation method of dielectric composite material according to claim 1, which is characterized in that the colloidal sol to be molded to obtain
The step of dielectric composite material, specifically includes：It is molded the colloidal sol to obtain composite fibre by the way of electrostatic spinning
Silk；And hot pressing is carried out to the composite fibre silk and obtains the dielectric composite material.
9. the preparation method of dielectric composite material according to claim 1, which is characterized in that described using electrostatic spinning
In the step of mode is molded the colloidal sol to obtain composite fibre silk, the voltage of the electrostatic spinning is 2kV~15kV, described molten
Glue inject speed be 0.05mL/h~0.2mL/h, spinning distance be 5cm~40cm, drum rotation speed be 100rpm~
1000rpm；
And/or in described the step of obtaining the dielectric composite material to composite fibre silk progress hot pressing, hot pressing temperature is
50 DEG C~300 DEG C, hot pressing pressure is 2MPa~15MPa, and hot pressing time is 10min~60min.
10. a kind of dielectric composite material, which is characterized in that according to claim 1~9 any one of them dielectric composite material
Preparation method is prepared.
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| CN109942996A (en) * | 2019-04-03 | 2019-06-28 | 西安交通大学 | A kind of composite material and preparation method thereof and composite material |
| CN110437563A (en) * | 2019-07-10 | 2019-11-12 | 厦门珉瑶贸易有限公司 | A kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism |
| CN114536912A (en) * | 2022-01-13 | 2022-05-27 | 中国海洋大学 | Method for synergistically improving breakdown strength and dielectric constant of polymer dielectric |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109942996A (en) * | 2019-04-03 | 2019-06-28 | 西安交通大学 | A kind of composite material and preparation method thereof and composite material |
| CN109942996B (en) * | 2019-04-03 | 2020-08-25 | 西安交通大学 | Composite material preparation method and composite material |
| CN110437563A (en) * | 2019-07-10 | 2019-11-12 | 厦门珉瑶贸易有限公司 | A kind of poly- (biasfluoroethylene-hexafluoropropylene) organic and inorganic insulating composite material and preparation method thereof of magnetism |
| CN114536912A (en) * | 2022-01-13 | 2022-05-27 | 中国海洋大学 | Method for synergistically improving breakdown strength and dielectric constant of polymer dielectric |
| CN114536912B (en) * | 2022-01-13 | 2023-03-10 | 中国海洋大学 | Method for synergistically improving breakdown strength and dielectric constant of polymer dielectric |
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