CN105838001B - A kind of preparation method of the polyvinylidene fluoride-based composite of high-k - Google Patents
A kind of preparation method of the polyvinylidene fluoride-based composite of high-k Download PDFInfo
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- CN105838001B CN105838001B CN201610270745.9A CN201610270745A CN105838001B CN 105838001 B CN105838001 B CN 105838001B CN 201610270745 A CN201610270745 A CN 201610270745A CN 105838001 B CN105838001 B CN 105838001B
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005453 pelletization Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 17
- 239000004567 concrete Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 229910001199 N alloy Inorganic materials 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 6
- 230000005415 magnetization Effects 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 43
- 239000011259 mixed solution Substances 0.000 abstract description 14
- -1 makes Kynoar Chemical compound 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000945 filler Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical compound [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- C08K9/04—Ingredients treated with organic substances
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
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- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a kind of preparation method of the polyvinylidene fluoride-based composite of high-k, its step is：A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in N, in N dimethyl formamide solutions solution one, the Fe-N Alloyses of 15 parts of weights and 15 parts of heavy CNTs are scattered in N, N solvent dimethylformamides obtain solution two；Solution one, solution two are mixed into obtain mixed solution；Mixed solution, which is poured into distilled water, makes Kynoar, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains three-phase composite material；Three-phase composite material is put into vacuum drying oven heating, drying again, obtains Kynoar/Fe-N Alloyses/carbon nanotube masterbatch；B, melt blending：The masterbatch that A is walked to obtain enters trip temperature for 190 DEG C in miniature extruder, and the time is 6 10min extruding pelletization, is produced.Composite dielectric constant prepared by this method is high, while dielectric loss is low；And its technique is simple, be advantageous to mass produce.
Description
Technical field
The present invention relates to a kind of preparation method of the polyvinylidene fluoride-based composite of high-k.
Technical background
The exploitation of new dielectric material with high-k is the important research neck of current electronic material industry
Domain.In the electronics industry, high-k, miniaturization, easy processing are required for for example high energy-storage capacitor of electronic device
And the requirement such as excellent in mechanical performance.But traditional dielectric material is the predominantly ferroelectric material based on one-component material, metal oxygen
Compound, nitride etc., although dielectric properties are excellent, processing difficulties are difficult to take into account good mechanical property simultaneously.Common height
Molecularly Imprinted Polymer has the advantages that light, dielectric loss is low and easy to process, but dielectric constant is generally relatively low.If prepare poly-
Compound base dielectric material, it the advantage is that one side polymeric material is light, meet electronic device lightweight requirements；The opposing party
Face, for inorganic material, polymeric material easy processing, and excellent in mechanical performance.The polymer-based dielectric applied now
Material, mostly to add based on ceramic particle, but ceramic particle can not build good polarization networks, addition in material internal
Larger, so as to cause material that fragility is presented, processing is very difficult.Therefore, in order to realize that material internal polarizes on a large scale, we
Wish to build polarization networks toward the conductive filler of the few content of addition inside polymeric material.Relative to other organic polymers,
Kynoar has polymorphic microstructure, thus has more excellent dielectric, piezoelectricity, ferroelectricity and pyroelectric.And carbon
Nanotube is a kind of extraordinary conductive filler, electric charge can the free movement on one-dimensional CNT, therefore CNT pole
Easily help polymer composites that interfacial polarization occurs after filler network has been built.
In recent years, as the further development of nanometer technology, polymer nanocomposite dielectric are of great interest.Polymerization
Thing nanometer dielectric is that inorganic filler is dispersed in the compound system formed in polymer with nanoscale.But existing polymerization
Although the dielectric constant of thing nanometer dielectric composite is higher, its dielectric loss is higher, seriously constrains its development and answers
With.So it is desirable that on the basis of polymer/conductive filler compound system, its dielectric loss is further reduced, is improved multiple
The application prospect of condensation material.Without good electric conductivity while ceramic packing has preferable dielectric properties, therefore I
Propose, by adding ceramic particle come dispersed electro-conductive filler, allow conductive filler dispersed hair in polymeric matrix
Raw polarization causes big Leakage Current without being mutually overlapped to form network.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the polyvinylidene fluoride-based composite of high-k, the party
Composite dielectric constant prepared by method is high, while dielectric loss is low；And its technique is simple, be advantageous to mass produce.
The technical scheme adopted by the invention for realizing the object of the invention is that a kind of polyvinylidene fluoride of high-k is answered
The preparation method of condensation material, its step are：
A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in N,N-dimethylformamide solution
Solution one, by 1-5 parts weight Fe-N Alloyses and 1-5 parts weight CNT be scattered in DMF solvent obtain it is molten
Liquid two；Solution one, solution two are mixed into obtain mixed solution；Mixed solution, which is poured into distilled water, makes N,N-dimethylformamide molten
In distilled water, and Kynoar, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains polyvinylidene fluoride
Alkene/CNT/Fe-N Alloyses three-phase composite material；
Kynoar/CNT/Fe-N Alloyses three-phase composite material is put into vacuum drying oven heating, drying again, obtained
Kynoar/Fe-N Alloyses/carbon nanotube masterbatch；Described Fe-N Alloyses Fe(2‐19)N alloy powders；
B, melt blending：Kynoar/Fe-N Alloyses/carbon nanotube masterbatch that A is walked to obtain is in miniature extruder
Enter trip temperature for 190 DEG C, the time is 6-10min extruding pelletization, is produced.
Compared with prior art, the beneficial effects of the invention are as follows：
First, preparation method of the present invention is secondary operation blend method (solution and melting), and preparation method is simple,
It can effectively ensure that filler is dispersed in matrix material simultaneously, while can also promote to interpenetrate expansion between filler
Dissipate so that the two kinds of filler Fe-N Alloyses and CNT of 1-5 part weights, can be effective in 100 parts heavy of Kynoar matrix
Form dielectric Percolation network structure；Meanwhile the mutual overlap joint of Fe-N Alloyses energy destroying carbon nanometer tube, it can not be formed effectively
Conductive network, but micro- capacitance structure still can be formed between adjacent CNT, therefore, while dielectric constant is improved,
Dielectric loss is set substantially to reduce.Material produced by the present invention, the dielectric constant values that it is measured are more than 150, and dielectric loss
Below 1.
2nd, for the present invention using Fe-N Alloyses and CNT as filler, both rigidity are high, and modulus is big, fill and gather inclined fluorine
Composite modulus prepared by ethene increases substantially, therefore the excellent combination property of composite.
3rd, raw materials of the present invention are CNT, Fe-N Alloyses and Kynoar, wherein CNT and poly- inclined
PVF raw material sources are extensive, and cost is low, simple and easy to get.Preparation process is that (solution and melting) is blended in secondary operation, its condition
Gently, Device-General, preparation cost is low, is advantageous to large-scale promotion.
Further, CNT of the invention is diameter 0.5-200nm, the acidifying single of 100nm-50 μm of length
Pipe or acidifying multi-walled carbon nanotube.
The acidifying single-walled carbon nanotube or acidifying multi-walled carbon nanotube of this diameter and length, can be with by carboxyl grafting
Ensure that CNT has more preferable dispersion effect inside polymeric matrix, avoid CNT inside polymeric matrix
Accumulation occurs and larger leakage current occurs.
Further, Fe of the invention(2‐19)The specific surface area of N alloy powders is 1.58m2/ g, saturation magnetization are
80emu/g, a diameter of 300-400nm of powder.
Further, 100 parts of heavy Kynoar are dissolved in DMF solution and obtain solution by the present invention
One concrete operations are：Solution temperature is 55-80 DEG C, dissolution time 20-40min, and with 50-100r/min stirring.
In this manner it is ensured that Kynoar can be solved homogeneously in DMF solvent, formed and gather inclined fluorine
Ethene/N,N-dimethylformamide solution.
Further, the CNT of the Fe-N Alloyses of 1-5 parts weight and 1-5 parts weight is scattered in N, N- dimethyl methyls by the present invention
The concrete operations that amide solvent obtains solution two are：Temperature is 55-80 DEG C, jitter time 20-40min, and with 50-100r/
Min stirring.
So, be advantageous to Fe-N Alloyses alloy powder and CNT quickly to spread in DMF solution
And it is dispersed, obtain Fe-N Alloyses and CNT suspension dispersed in DMF.
Further, the present invention by solution one, solution two mix the concrete operations of mixed solution are：At a temperature of 55-80 DEG C,
30min is stirred, then at room temperature, ultrasonic disperse 1-2h.
So, it can guarantee that Kynoar will not be precipitated out due to the reduction of temperature from solvent, in the stir speed (S.S.)
Under the time, be advantageous to mixed solution and be more uniformly distributed, and the phase counterdiffusion contributed between filler and infiltration.
With reference to embodiment, the present invention is described in further detail.
Embodiment
Embodiment one
A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in DMF solution
Solution one, solution temperature during dissolving are 55 DEG C, dissolution time 20min, and with 50r/min stirring；
It is 1.58m by specific surface area2/ g, saturation magnetization 80emu/g, 1 part of a diameter of 300-400nm heavy
Fe(2‐19)N alloy powders and diameter 0.5-200nm, 1 part heavy of acidifying single-walled carbon nanotube of 100nm-50 μm of length are scattered in
N,N-dimethylformamide solvent obtains solution two；Concrete operations when scattered are：Temperature is 55 DEG C, jitter time 20min, and
With 50r/min stirring
Solution one, solution two are mixed into obtain mixed solution；Concrete operations during mixing are：At a temperature of 55 DEG C, stirring
30min, then at room temperature, ultrasonic disperse 1h.
Then, mixed solution is poured into distilled water makes DMF be dissolved in distilled water, and polyvinylidene fluoride
Alkene, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains Kynoar/CNT/Fe-N Alloyses three
Phase composite materials；
Kynoar/CNT/Fe-N Alloyses three-phase composite material is put into vacuum drying oven heating, drying again, obtained
Kynoar/Fe-N Alloyses/carbon nanotube masterbatch.
B, melt blending：Kynoar/Fe-N Alloyses/carbon nanotube masterbatch is entered into trip temperature in miniature extruder is
190 DEG C, the time is 6min extruding pelletization, is produced.
The dielectric constant values of Kynoar/Fe-N Alloyses/carbon nano tube compound material made from this example are 152, dielectric
Loss value is 0.2.
Embodiment two
A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in DMF solution
Solution one, solution temperature during dissolving are 65 DEG C, dissolution time 30min, and with 70r/min stirring；
It is 1.58m by specific surface area2/ g, saturation magnetization 80emu/g, 1 part of a diameter of 300-400nm heavy
Fe(2‐19)N alloy powders and diameter 0.5-200nm, 2 parts heavy of acidifying single-walled carbon nanotube of 100nm-50 μm of length are scattered in
N,N-dimethylformamide solvent obtains solution two；Concrete operations when scattered are：Temperature is 55 DEG C, jitter time 20min, and
With 70r/min stirring
Solution one, solution two are mixed into obtain mixed solution；Concrete operations during mixing are：At a temperature of 55 DEG C, stirring
30min, then at room temperature, ultrasonic disperse 1.5h.
Then, mixed solution is poured into distilled water makes DMF be dissolved in distilled water, and polyvinylidene fluoride
Alkene, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains Kynoar/CNT/Fe-N Alloyses three
Phase composite materials；Kynoar/CNT/Fe-N Alloyses three-phase composite material is put into vacuum drying oven heating, drying again,
Obtain Kynoar/Fe-N Alloyses/carbon nanotube masterbatch；
B, melt blending：Kynoar/Fe-N Alloyses/carbon nanotube masterbatch is entered into trip temperature in miniature extruder is
190 DEG C, the time is 10min extruding pelletization, is produced.
The dielectric constant values of Kynoar/Fe-N Alloyses/carbon nano tube compound material made from this example are 168, dielectric
Loss value is 0.19.
Embodiment three
A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in DMF solution
Solution one, solution temperature during dissolving are 80 DEG C, dissolution time 40min, and with 90r/min stirring；
It is 1.58m by specific surface area2/ g, saturation magnetization 80emu/g, 2 parts of a diameter of 300-400nm heavy
Fe(2‐19)N alloy powders and diameter 0.5-200nm, 5 parts heavy of acidifying single-walled carbon nanotube of 100nm-50 μm of length are scattered in
N,N-dimethylformamide solvent obtains solution two；Concrete operations when scattered are：Temperature is 55 DEG C, jitter time 30min, and
With 60r/min stirring
Solution one, solution two are mixed into obtain mixed solution；Concrete operations during mixing are：At a temperature of 70 DEG C, stirring
30min, then at room temperature, ultrasonic disperse 1.5h.
Then, mixed solution is poured into distilled water makes DMF be dissolved in distilled water, and polyvinylidene fluoride
Alkene, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains Kynoar/CNT/Fe-N Alloyses three
Phase composite materials；Kynoar/CNT/Fe-N Alloyses three-phase composite material is put into vacuum drying oven heating, drying again,
Obtain Kynoar/Fe-N Alloyses/carbon nanotube masterbatch；
B, melt blending：Kynoar/Fe-N Alloyses/carbon nanotube masterbatch is entered into trip temperature in miniature extruder is
190 DEG C, the time is 8min extruding pelletization, is produced.
The dielectric constant values of Kynoar/Fe-N Alloyses/carbon nano tube compound material made from this example are 231, dielectric
Loss value is 0.26.
Example IV
A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in DMF solution
Solution one, solution temperature during dissolving are 70 DEG C, dissolution time 35min, and with 100r/min stirring；
It is 1.58m by specific surface area2/ g, saturation magnetization 80emu/g, 5 parts of a diameter of 300-400nm heavy
Fe(2‐19)N alloy powders and diameter 0.5-200nm, 5 parts heavy of acidifying multi-walled carbon nanotube of 100nm-50 μm of length are scattered in
N,N-dimethylformamide solvent obtains solution two；Concrete operations when scattered are：Temperature is 80 DEG C, jitter time 40min, and
With 100r/min stirring
Solution one, solution two are mixed into obtain mixed solution；Concrete operations during mixing are：At a temperature of 80 DEG C, stirring
30min, then at room temperature, ultrasonic disperse 2h.
Then, mixed solution is poured into distilled water makes DMF be dissolved in distilled water, and polyvinylidene fluoride
Alkene, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains Kynoar/CNT/Fe-N Alloyses three
Phase composite materials；Kynoar/CNT/Fe-N Alloyses three-phase composite material is put into vacuum drying oven heating, drying again,
Obtain Kynoar/Fe-N Alloyses/carbon nanotube masterbatch；
B, melt blending：Kynoar/Fe-N Alloyses/carbon nanotube masterbatch is entered into trip temperature in miniature extruder is
190 DEG C, the time is 7min extruding pelletization, is produced.
The Fe that the present invention uses(2-19)N alloy powders can be by (2016) 115- of document Materials and Design 90
121“Preparation of high performance bulk Fe–N alloy by spark plasma
The method that sintering " is recorded is made.
Table 1 is the embodiment of the present invention one, embodiment two, embodiment three, and Kynoar prepared by example IV/iron nitrogen closes
The dielectric constant values of gold/carbon nano-tube composite.
1 Kynoar of table/Fe-N Alloyses/carbon nano tube compound material dielectric constant values
| Component | Embodiment one | Embodiment two | Embodiment three |
| Dielectric constant | 152 | 168 | 231 |
Table 2 is Kynoar/iron nitrogen prepared by the embodiment of the present invention one, embodiment two, embodiment three and example IV
The dielectric loss value of alloy/carbon nanometer tube composite.
2 Kynoar of table/Fe-N Alloyses/carbon nano tube compound material dielectric loss value
| Component | Embodiment one | Embodiment two | Embodiment three |
| Dielectric loss | 0.2 | 0.19 | 0.26 |
As can be seen from Table 1 and Table 2, dielectric constant, pure polyvinylidene fluoride is greatly improved in the addition of CNT
Alkene dielectric constant is only 8, and the dielectric constant of the composite of the present invention is maintained at more than 150；And the addition of Fe-N Alloyses,
The effective dielectric loss for limiting material, its dielectric loss is below 0.26.It can be seen that composite of the invention have it is higher
Dielectric constant, while dielectric loss is low, effectively increases the combination property of material, has widened the application of material.
Claims (5)
1. a kind of preparation method of the polyvinylidene fluoride-based composite of high-k, its step are：
A, coprecipitation prepares masterbatch：100 parts of heavy Kynoar are dissolved in N,N-dimethylformamide solution must be molten
Liquid one, the CNT of the Fe-N Alloyses of 1-5 parts weight and 1-5 parts weight is scattered in into DMF solvent to suspend
Liquid；Solution one, suspension are mixed into obtain mixed liquor；Mixed liquor, which is poured into distilled water, makes N,N-dimethylformamide be dissolved in distillation
In water, and Kynoar, CNT, Fe-N Alloyses are co-precipitated in distilled water, and precipitation obtains Kynoar/carbon and received
Mitron/Fe-N Alloyses three-phase composite material；
Kynoar/CNT/Fe-N Alloyses three-phase composite material is put into vacuum drying oven heating, drying again, obtained poly- inclined
PVF/Fe-N Alloyses/carbon nanotube masterbatch；Described Fe-N Alloyses are Fe(2‐19)N alloy powders, its specific surface area are
1.58m2/ g, saturation magnetization 80emu/g, a diameter of 300-400nm of powder,
B, melt blending：A Kynoar/Fe-N Alloyses/the carbon nanotube masterbatches for walking to obtain are carried out in miniature extruder
Temperature is 190 DEG C, and the time is 6-10min extruding pelletization, is produced.
2. a kind of preparation method of the polyvinylidene fluoride-based composite of high-k according to claim 1, it is special
Sign is：Described CNT is diameter 0.5-200nm, and the acidifying single-walled carbon nanotube of 100nm-50 μm of length or acidifying are more
Wall carbon nano tube.
3. a kind of preparation method of the polyvinylidene fluoride-based composite of high-k according to claim 1, it is special
Sign is：The described Kynoar by 100 parts of weights, which is dissolved in N,N-dimethylformamide solution, obtains the specific of solution one
Operate and be：Solution temperature is 55-80 DEG C, dissolution time 20-40min, and with 50-100r/min stirring.
4. a kind of preparation method of the polyvinylidene fluoride-based composite of high-k according to claim 1, it is special
Sign is：The described CNT by the Fe-N Alloyses of 1-5 parts weight and 1-5 parts weight is scattered in N,N-dimethylformamide solvent
The concrete operations of suspension are：Temperature is 55-80 DEG C, jitter time 20-40min, and stirring with 50-100r/min
Mix.
5. a kind of preparation method of the polyvinylidene fluoride-based composite of high-k according to claim 1, it is special
Sign is：It is described solution one, suspension are mixed the concrete operations of mixed liquor are：At a temperature of 55-80 DEG C, 30min is stirred,
Again at room temperature, ultrasonic disperse 1-2h.
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