CN108998893A - A kind of gradient-structure Kynoar based composite dielectric and preparation method thereof - Google Patents
A kind of gradient-structure Kynoar based composite dielectric and preparation method thereof Download PDFInfo
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- CN108998893A CN108998893A CN201810820695.6A CN201810820695A CN108998893A CN 108998893 A CN108998893 A CN 108998893A CN 201810820695 A CN201810820695 A CN 201810820695A CN 108998893 A CN108998893 A CN 108998893A
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- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002033 PVDF binder Substances 0.000 claims abstract description 47
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 47
- 238000007731 hot pressing Methods 0.000 claims abstract description 24
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 22
- 238000011049 filling Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 11
- 239000003989 dielectric material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 21
- 230000015556 catabolic process Effects 0.000 abstract description 16
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000002121 nanofiber Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 6
- 229920013657 polymer matrix composite Polymers 0.000 abstract description 3
- 239000011160 polymer matrix composite Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 29
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/16—Organic dielectrics of fibrous material, e.g. paper
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Insulating Materials (AREA)
- Insulating Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of gradient-structure Kynoar based composite dielectric and preparation method thereof, the complex media is mutually combined with PVDF by BZCT NFs filling, and the BZCT NFs filling is mutually arranged in complex media in concentration gradients multilayer.The techniques such as present invention combination sol-gel method, electrostatic spinning technique and hot pressing are prepared for big L/D ratio inorganic nano-fiber filling phase and Kynoar based coextruded film medium, and above-mentioned nanofiber/polymer matrix laminated film medium is subjected to high temperature hot pressing and quenching treatment, obtain fine and close laminated film.Multilayered structure/the polymer-matrix composite dielectric with 1-dimention nano filling phase concentration gradients prepared by the present invention is with flexibility is good, at low cost, breakdown strength is high, energy-storage property is excellent, the distortion of high-content inorganic fill phase bring internal field can be buffered, and then its energy-storage property is improved, to produce high performance energy storage device.
Description
Technical field
The invention belongs to dielectric capacitor field, it is related to a kind of polymer-based dielectric nanocomposite and its preparation side
A kind of method, and in particular to multilayered structure/polymer-matrix composite dielectric and its system with 1-dimention nano filling phase concentration gradients
Preparation Method.
Background technique
In contemporary aerospace, automobile manufacture and national defense industry, polymer-matrix composite dielectric material plays act foot
The effect of weight.Although polymer dielectric material relative dielectric constant itself is low, the lesser problem of energy storage density constrains it
In the practical application of medium energy storage field, however its low production cost, easy preparation process, excellent flexibility and good
Good resistance to sparking energy, so that it becomes the common excellent candidate material for preparing required matrix in composite dielectric material.In addition,
For the energy-storage property for improving complex media, it usually needs introducing, there is the inorganic ceramic of high dielectric constant to fill phase, will certainly
Introduce as partial dielectric difference it is excessive and caused by internal field distort, this will will lead to complex media breakdown decline, into
And make the operating voltage of complex media relatively low, limit its discharge energy storage capacity.
Summary of the invention
Mutually partial dielectric is poor between polymeric matrix in order to improve high-content inorganic ceramic filling in composite material by the present invention
The excessive problem of different and local electric field distortion, while solving that the resistance to breakdown strength of dielectric capacitor material is relatively low at this stage and energy
The lower problem of storage density, provide it is a kind of it is high breakdown high energy storage density gradient-structure Kynoar based composite dielectric and
Preparation method.Multilayered structure/polymer matrix compound electric prepared by the present invention with 1-dimention nano filling phase concentration gradients is situated between
Matter has the characteristics that flexibility is good, at low cost, breakdown strength is high, energy-storage property is excellent, can buffer high-content inorganic fill phase
The distortion of bring internal field, and then its energy-storage property is improved, to produce high performance energy storage device, in dielectric
Energy storage field has broad prospect of application, can promote the development of the industries such as aerospace, automobile manufacture and national defense industry.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of gradient-structure Kynoar based composite dielectric is filled out by one-dimensional barium calcium zirconate titanate nanofiber (BZCT NFs)
Fill what phase was combined with PVDF, the BZCT NFs filling is mutually in complex media in the arrangement of concentration gradients multilayer, BZCT
NFs accounts for 1~10vol% of composite dielectrics total volume, the volume content of each layer BZCT NFs be respectively 0vol%,
2.5vol%, 5vol%, 7.5vol%, 10vol%, 10vol%, 7.5vol%, 5vol%, 2.5vol%, 0vol%；Or it is
10vol%, 7.5vol%, 5vol%, 2.5vol%, 0vol%, 0vol%, 2.5vol%, 5vol%, 7.5vol%,
10vol%.
A kind of preparation method of above-mentioned gradient-structure Kynoar based composite dielectric, includes the following steps:
Step 1: preparing gradient-structure Kynoar based coextruded film:
(1) BZCT NFs fills phase ultrasound and is dispersed in N,N-dimethylformamide solution；
(2) be added Kynoar powder (PVDF), dose volume score be 0vol%, 2.5vol%, 5vol%,
The mixed solution of 7.5vol%, 10vol%；
(3) by the resulting mixed solution inhalation syringe of step (2), according to each layer BZCT NFs volume content sequence into
Row low velocity electrostatic spinning obtains gradient-structure polyvinylidene fluoride compounded wet film；
(4) compounded wet film after spinning is placed in vacuum drying oven and is dried, it is compound to obtain gradient-structure polyvinylidene fluoride
Film；
Step 2: preparing complex media:
Using hot pressing and quenching technical, hot pressing is carried out to gradient-structure Kynoar based coextruded film, obtains densification
Gradient-structure Kynoar based composite dielectric.
In the present invention, BZCT NFs filling phase the preparation method is as follows:
(1) by barium hydroxide octahydrate and calcium hydroxide dissolution acetic acid, it is stirred at a temperature of 50~70 DEG C to clear
It is cooled to room temperature after clear solution；
(2) acetylacetone,2,4-pentanedione and acetylacetone,2,4-pentanedione zirconium is added, continues to stir to clarify；
(3) butyl titanate is added dropwise, stirs at room temperature, obtains BZCT precursor solution, control the chemistry of Ba:Ca:Zr:Ti
Metering is than being 0.05~1.00:0.05~0.30:0.01~0.20:0.50~2.00；
(4) into BZCT precursor solution be added polyvinylpyrrolidone (PVP), control PVP additional amount be 0.1~
4.5g/5~100mL；
(5) electrostatic spinning will be carried out in the sucking injection of step (4) acquired solution；
(6) after electrostatic spinning, fiber is placed in Muffle furnace and is sintered, it is final to obtain BZCT NFs filling
Phase.
In the present invention, during the electrostatic spinning, the fltting speed of syringe is set as 0.1~0.3mm/min, receives
The revolving speed of device roller is set as 80~140r/min, and syringe to receiver distance is 10~30cm, and syringe needle and roller are applied simultaneously
Add V+=8~18kV, the voltage of V-=8~18kV, temperature is 10~40 DEG C, and relative humidity is 10~50%.
It is described to be sintered to gradient sintering in the present invention: 100~400 DEG C of 1~5h of heat preservation of first stage；Second stage 600~
2~5h is sintered at a temperature of 900 DEG C；Phase III is furnace-cooled to room temperature.
In the present invention, in the low velocity electrostatic spinning process, the revolving speed of receiver roller is set as 60~140r/min, note
The fltting speed of emitter is set as 0.1~0.3mm/min, and syringe to receiver distance is 10~30cm, and syringe needle and roller are same
When apply V+=8~18kV, the voltage of V-=8~18kV, temperature be 10~40 DEG C, relative humidity be 10~50%.
In the present invention, the drying temperature be 50~90 DEG C, the time be 8~for 24 hours.
In the present invention, the hot-pressing processing is gradient hot-pressing processing: 90~150 DEG C of first stage hot pressing temperature, 3~
5~15min of pressure maintaining under 10MPa；Second stage carry out release exhaust bubble processing, and after release in 150~180 DEG C keep the temperature 20~
40min is to remove the residual stress that laminated film media interior is introduced due to electrostatic spinning；Phase III hot pressing temperature 170~
190 DEG C, 15~30min of pressure maintaining at 14~19MPa；The temperature of laminated film is rapidly decreased to 0 finally by water cooling plant~
20 DEG C, 1~8min of pressure maintaining at 1~10MPa.
In the present invention, the thickness of the gradient-structure Kynoar based composite dielectric is about 10~40 μm.
Compared with the prior art, the present invention has the advantage that
1, the BZCT/PVDF complex media dielectric constant with higher and the good energy of resistance to breakdown of different gradient-structures
Power, this can promote the dielectric constant and disruptive field intensity of PVDF complex media entirety；The especially BZCT/ of 0-10-0 gradient-structure
PVDF laminated film, this ability with homogenizing internal field, effectively inhibits the formation of media interior conductive path, further
The resistance to breakdown capability for promoting medium, effectively reduces its breakdown probability.
2, preparation process flow of the present invention is easy, reduces the production cost of full stress-strain medium, is suitable for large-scale production.
3,0-10-0 type BCZT/PVDF gradient composite medium prepared by the present invention has excellent breakdown strength, compared with
Low loss, conductivity and leakage current density, and maintain the excellent electrical isolation of polymeric matrix itself and mechanical performance.Cause
This, can be in energy storage device until application.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum and scanning electron microscope (SEM) photograph of one-dimensional BZCT NFs, three kinds of BZCT/PVDF based composite dielectrics
X ray diffracting spectrum；
Fig. 2 is scanning electron microscope (SEM) photograph (a) PVDF, (b) 0-10-0, (c) 10-0-10 of three kinds of BZCT/PVDF based composite dielectrics；
Fig. 3 is three kinds of BZCT/PVDF based composite dielectric dielectric constants and loss；
Fig. 4 is three kinds of BZCT/PVDF based composite dielectric breakdown strength Weibull distribution figures；
Fig. 5 is three kinds of BZCT/PVDF based composite dielectric energy-storage properties.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this
Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
Within the protection scope of the present invention.
Specific embodiment 1: the gradient-structure Kynoar based composite dielectric that present embodiment provides is by one-dimensional zirconium titanium
What sour barium calcium nanofiber (BZCT NFs) filling was mutually combined with PVDF, the BZCT NFs filling is mutually in complex media
It arranges in concentration gradients multilayer, BZCT NFs accounts for 1~10vol% of composite dielectrics total volume.
The preparation method of above-mentioned gradient-structure Kynoar based composite dielectric, in conjunction with sol-gel method, electrostatic spinning skill
The techniques such as art and hot pressing are prepared for big L/D ratio inorganic nano-fiber filling phase and Kynoar based coextruded film medium, and
Above-mentioned nanofiber/polymer matrix laminated film medium is subjected to high temperature hot pressing and quenching treatment, obtains fine and close THIN COMPOSITE
Film.Specific step is as follows:
Step 1: by barium hydroxide octahydrate and calcium hydroxide dissolution acetic acid, it is stirred at a temperature of 50~70 DEG C
It is cooled to room temperature after to clear solution；Acetylacetone,2,4-pentanedione and acetylacetone,2,4-pentanedione zirconium is then added, continues to stir to clarify；Last slowly drop
Add butyl titanate, stir at room temperature, obtain BZCT precursor solution, the stoichiometric ratio for controlling Ba:Ca:Zr:Ti is 0.05
~1.00:0.05~0.30:0.01~0.20:0.50~2.00；For the viscosity for adjusting spinning solution, appropriate polyethylene need to be added
Base pyrrolidones (PVP), the additional amount of PVP are 0.1~4.5g/5~100mL.
Step 2: in step 1 acquired solution inhalation syringe, will be ready for spinning, and electrostatic spinning process is by syringe
Fltting speed be set as 0.1~0.3mm/min, the revolving speed of receiver roller is set as 80~140r/min, and syringe is to connecing
Receiving device distance is 10~30cm, and syringe needle and roller apply V+=8~18kV, the voltage of V-=8~18kV simultaneously, temperature is 10~
40 DEG C, relative humidity is 10~50%；After electrostatic spinning, fiber is placed on progress gradient increased temperature sintering in Muffle furnace,
100~400 DEG C of 1~5h of heat preservation of first stage；2~5h is sintered at a temperature of 600~900 DEG C of second stage；Phase III is furnace-cooled to
Room temperature, it is final to obtain BZCT NFs.
Step 3: BZCT NFs ultrasound obtained by step 2 is dispersed in N,N-dimethylformamide solution；Then
Be added Kynoar powder (PVDF), obtain according to a certain ratio volume fraction be 0vol% (be free of BZCT NFs),
The mixed solution of 2.5vol%, 5vol%, 7.5vol%, 10vol% (NFs containing BZCT)；Then the technique for copying step 2,
It is wet that the pure PVDF that BZCT NFs volume fraction is 0vol% is obtained first using low speed (60~140r/min) electrostatic spinning technique
Film, then every kind of solution take appropriate solution according to 0vol% (pure PVDF), 2.5vol%, 5vol%, 7.5vol%,
It is quiet that the sequence of 10vol%, 10vol%, 7.5vol%, 5vol%, 2.5vol%, 0vol% carry out low speed (60~140r/min)
Electrospun can get graded composite wet film (0-10-0)；Similarly, then from 5 kinds of solution respectively take appropriate solution, according to 10vol%,
The sequence of 7.5vol%, 5vol%, 2.5vol%, 0vol%, 0vol%, 2.5vol%, 5vol%, 7.5vol%, 10vol%
Carrying out low speed (60~140r/min) electrostatic spinning can be obtained graded composite wet film (10-0-10)；It will be compound wet after spinning
Film is placed in vacuum drying oven at a temperature of 50~90 DEG C drying 8~for 24 hours, obtains three kinds of PVDF based coextruded films.
Step 4: using hot pressing and quenching technical, carries out hot pressing to three kinds of PVDF based coextruded films, carries out gradient increased temperature heat
Pressure processing: 90~150 DEG C of first stage hot pressing temperature, 5~15min of pressure maintaining at 3~10MPa；Second stage carries out unloading pressure
Bubble processing, and after release in 150~180 DEG C of 20~40min of heat preservation to remove laminated film media interior due to Static Spinning
Silk and introduce residual stress；170~190 DEG C of phase III hot pressing temperature, 15~30min of pressure maintaining at 14~19MPa；Finally
The temperature of laminated film is rapidly decreased to 0~20 DEG C by water cooling plant, 1~8min of pressure maintaining obtains densification at 1~10MPa
PVDF based composite dielectric, thickness are about 10~40 μm.
Present embodiment preparation process flow is easy, and the inorganic nano-fiber with concentration gradients structure of preparation/poly- is partially
Fluoride-based laminated film medium has excellent breakdown strength and good energy storage density and energy storage efficiency, maintains simultaneously
The excellent electrical isolation of polymer itself and mechanical performance.
Specific embodiment 2: the gradient-structure Kynoar based composite dielectric that present embodiment provides is by one-dimensional zirconium titanium
What sour barium calcium nanofiber (BZCT NFs) filling was mutually combined with PVDF, the BZCT NFs filling is mutually in complex media
It arranges in concentration gradients multilayer, BZCT NFs accounts for the 5vol% of composite dielectrics total volume.
The preparation step of above-mentioned gradient-structure Kynoar based composite dielectric is as follows:
Step 1: by barium hydroxide octahydrate and calcium hydroxide dissolution acetic acid, it is stirred at 50 °C to clear
It is cooled to room temperature after clear solution；Acetylacetone,2,4-pentanedione and acetylacetone,2,4-pentanedione zirconium is then added, continues to stir to clarify；Titanium is finally slowly added dropwise
Sour four butyl esters, stir at room temperature, obtain BZCT precursor solution, and the stoichiometric ratio for controlling Ba:Ca:Zr:Ti is 0.85:
0.15:0.10:0.90；For the viscosity for adjusting spinning solution, appropriate polyvinylpyrrolidone (0.2g/20mL) need to be added.
Step 2: by the sucking injection of step 1 acquired solution, being ready for spinning, and electrostatic spinning process is by syringe
Fltting speed is set as 0.1mm/min, and the revolving speed of receiver roller is set as 140r/min, and syringe to receiver distance is
15cm, syringe needle and roller apply V+=16kV, the voltage of V-=16kV simultaneously, and temperature is 25 DEG C, relative humidity 18%；Electrostatic
After spinning, fiber is placed on progress gradient increased temperature sintering, 300 DEG C of heat preservation 2h of first stage in Muffle furnace；Second stage
3h is sintered at a temperature of 700 DEG C；Phase III is furnace-cooled to room temperature, final to obtain BZCT NFs.
Step 3: BZCT NFs ultrasound obtained by step 2 is dispersed in N,N-dimethylformamide solution；Then
Be added Kynoar powder (PVDF), obtain according to a certain ratio volume fraction be 0vol% (be free of BZCT NFs),
The mixed solution of 2.5vol%, 5vol%, 7.5vol%, 10vol% (NFs containing BZCT)；Then step 2 technique is copied, benefit
The pure PVDF wet film that BZCT NFs volume fraction is 0vol% is obtained first with low speed (120r/min) electrostatic spinning technique, then
Every kind of solution take appropriate solution according to 0vol% (pure PVDF), 2.5vol%, 5vol%, 7.5vol%, 10vol%,
The sequence of 10vol%, 7.5vol%, 5vol%, 2.5vol%, 0vol% carry out electrostatic spinning, can get graded composite wet film
(0-10-0)；Similarly, then from 5 kinds of solution respectively take appropriate solution, according to 10vol%, 7.5vol%, 5vol%, 2.5vol%,
The sequence of 0vol%, 0vol%, 2.5vol%, 5vol%, 7.5vol%, 10vol% carry out low speed (120r/min) Static Spinning
Silk can be obtained graded composite wet film (10-0-10)；Compounded wet film after spinning is placed in vacuum drying oven at a temperature of 60 DEG C and is dried
Dry 12h.
Step 4: using hot pressing and quenching technical, carries out hot pressing to three kinds of PVDF based coextruded films, carries out gradient increased temperature heat
Pressure processing: 150 DEG C of first stage hot pressing temperature, the pressure maintaining 15min at 10MPa；Second stage carries out release exhaust bubble processing, and
180 DEG C of heat preservation 30min are after release to remove the residual stress that laminated film media interior is introduced due to electrostatic spinning；Third
175 DEG C of stage hot pressing temperature, the pressure maintaining 20min at 15MPa；The temperature of laminated film is rapidly decreased to finally by water cooling plant
20 DEG C, pressure maintaining 7min obtains fine and close PVDF based composite dielectric at 5MPa, and thickness is about 20 μm.
The X ray diffracting spectrum and scanning electron microscope (SEM) photograph of the one-dimensional BZCT NFs of gained in present embodiment, as a result such as Fig. 1 institute
Show.According to XRD spectrum it is found that BZCT NFs crystallization completely, belongs to perovskite structure, meanwhile, detect inorganic fill phase BZCT
The diffraction maximum of NFs and matrix PVDF；By scanning electron microscope it is found that this fiber surface is smooth, have compared with big L/D ratio (> 30).
Fig. 2 is the scanning electron microscope (SEM) photograph of three kinds of BZCT/PVDF based composite dielectrics.It can be seen that three kinds of films according to SEM result
Thickness is than about 20 μm.Meanwhile according to fig. 2 (b) and (c) as can be seen that gradient multilayer 0-10-0 and 10-0-10 complex media at
The defects of point slice gradient is obvious, and interface compatibility is good, no cracking, tomography；Equally, BZCT NFs is in PVDF matrix
Random arrangement is presented.
Fig. 3 is complex media dielectric constant and loss map.As seen from Figure 3, in 10Hz, the BZCT/ of 10-0-10
The BZCT/PVDF complex media dielectric constant that PVDF graded composite media dielectric constant is up to 25.6,0-10-0 take second place (for
23.8), PVDF thin film 9.3；Since BZCT NFs has biggish dipole polarization intensity, so complex media dielectric constant
It is significantly raised.Meanwhile opposite 10-0-10BZCT/PVDF complex media, the dielectric loss of 0-10-0BZCT/PVDF complex media
It is lower, there is great influence to the raising of its breakdown strength and energy-storage property.
Fig. 4 is three kinds of BZCT/PVDF based composite dielectric breakdown strength Weibull distribution figures.Figure 4, it is seen that 0-
The breakdown electric field of the BZCT/PVDF gradient MULTILAYER COMPOSITE medium of 10-0 is apparently higher than other two media films；Meanwhile illustrating 0-
The BZCT/PVDF graded and multilayered structure of 10-0 plays the role of hindering conductive path formation, so that its receiving breakdown with higher
Ability, disruptive field intensity are up to 332MV/m.
Fig. 5 is three kinds of BZCT/PVDF based composite dielectric energy-storage property maps.From Fig. 5 it is observed that compared to PVDF
With 10-0-10 complex media, the BZCT/PVDF gradient MULTILAYER COMPOSITE medium resistance to electric field with higher of 0-10-0 ability (~
310kV/mm), energy storage density (~9.8J/cm3) and energy storage efficiency (~52%).
Prepared 1-dimention nano can be made to fill with present embodiment preparation method it can be seen from Fig. 5 by Fig. 3, Fig. 4 mutually to contain
The BZCT/PVDF gradient MULTILAYER COMPOSITE medium for measuring gradient 0-10-0 has more excellent dielectric constant and lower dielectric loss,
Resistance to breakdown capability with higher simultaneously.Present embodiment fills the multilayer knot of phase concentration gradients by rationally designing 1-dimention nano
Structure improves disruptive field intensity, the discharge energy density, efficiency for charge-discharge of complex media, reduces the energy loss of complex media,
The good flexibility of polymeric matrix is maintained simultaneously, provides a kind of preparation side with excellent energy-storage property complex media
Method.
Claims (10)
1. a kind of gradient-structure Kynoar based composite dielectric, it is characterised in that the complex media fills phase by BZCT NFs
It is combined with PVDF, the BZCT NFs filling is mutually arranged in complex media in concentration gradients multilayer.
2. gradient-structure Kynoar based composite dielectric according to claim 1, it is characterised in that the BZCT NFs
Account for 1~10vol% of composite dielectrics total volume.
3. gradient-structure Kynoar based composite dielectric according to claim 1, it is characterised in that the BZCT NFs
The volume content of each layer be respectively 0vol%, 2.5vol%, 5vol%, 7.5vol%, 10vol%, 10vol%,
7.5vol%, 5vol%, 2.5vol%, 0vol%.
4. gradient-structure Kynoar based composite dielectric according to claim 1, it is characterised in that the BZCT NFs
The volume content of each layer be respectively 10vol%, 7.5vol%, 5vol%, 2.5vol%, 0vol%, 0vol%,
2.5vol%, 5vol%, 7.5vol%, 10vol%.
5. the preparation method of gradient-structure Kynoar based composite dielectric described in a kind of claim 1-4 any claim,
It is characterized in that the method comprises the following steps:
Step 1: preparing gradient-structure Kynoar based coextruded film:
(1) BZCT NFs fills phase ultrasound and is dispersed in N,N-dimethylformamide solution；
(2) PVDF is added, dose volume score is that the mixing of 0vol%, 2.5vol%, 5vol%, 7.5vol%, 10vol% are molten
Liquid；
(3) it by the resulting mixed solution inhalation syringe of step (2), is carried out according to the volume content sequence of each layer BZCT NFs low
Fast electrostatic spinning obtains gradient-structure polyvinylidene fluoride compounded wet film；
(4) compounded wet film after spinning is placed in vacuum drying oven and is dried, obtain gradient-structure Kynoar based coextruded film；
Step 2: preparing complex media:
Using hot pressing and quenching technical, hot pressing is carried out to gradient-structure Kynoar based coextruded film, obtains fine and close gradient
Structural polyvinylidene fluoride based composite dielectric.
6. the preparation method of gradient-structure Kynoar based composite dielectric according to claim 5, it is characterised in that institute
State BZCT NFs filling phase the preparation method is as follows:
(1) by barium hydroxide octahydrate and calcium hydroxide dissolution acetic acid, it is stirred to clarify at a temperature of 50~70 DEG C molten
It is cooled to room temperature after liquid；
(2) acetylacetone,2,4-pentanedione and acetylacetone,2,4-pentanedione zirconium is added, continues to stir to clarify；
(3) butyl titanate is added dropwise, stirs at room temperature, obtains BZCT precursor solution, control the stoichiometry of Ba:Ca:Zr:Ti
Than for 0.05~1.00:0.05~0.30:0.01~0.20:0.50~2.00；
(4) PVP is added into BZCT precursor solution, the additional amount for controlling PVP is 0.1~4.5g/5~100mL；
(5) electrostatic spinning will be carried out in the sucking injection of step (4) acquired solution；
(6) after electrostatic spinning, fiber is placed in Muffle furnace and is sintered, the final BZCT NFs that obtains fills phase.
7. the preparation method of gradient-structure Kynoar based composite dielectric according to claim 6, it is characterised in that institute
During stating electrostatic spinning, the fltting speed of syringe is set as 0.1~0.3mm/min, and the revolving speed of receiver roller is set as
80~140r/min, syringe to receiver distance are 10~30cm, and syringe needle and roller apply V+=8~18kV, V-=8 simultaneously
The voltage of~18kV, temperature are 10~40 DEG C, and relative humidity is 10~50%；It is described to be sintered to gradient sintering: the first stage 100
~400 DEG C of 1~5h of heat preservation；2~5h is sintered at a temperature of 600~900 DEG C of second stage；Phase III is furnace-cooled to room temperature.
8. the preparation method of gradient-structure Kynoar based composite dielectric according to claim 5, it is characterised in that institute
It states in low velocity electrostatic spinning process, the revolving speed of receiver roller is set as 60~140r/min；The drying temperature is 50~90
DEG C, the time be 8~for 24 hours.
9. the preparation method of gradient-structure Kynoar based composite dielectric according to claim 5, it is characterised in that institute
Stating hot-pressing processing is gradient hot-pressing processing: 90~150 DEG C of first stage hot pressing temperature, 5~15min of pressure maintaining at 3~10MPa；
Second stage carry out release exhaust bubble processing, and after release in 150~180 DEG C of 20~40min of heat preservation to remove laminated film
The residual stress that media interior is introduced due to electrostatic spinning；170~190 DEG C of phase III hot pressing temperature, at 14~19MPa
15~30min of pressure maintaining；The temperature of laminated film is rapidly decreased to 0~20 DEG C finally by water cooling plant, is protected at 1~10MPa
Press 1~8min.
10. the preparation method of gradient-structure Kynoar based composite dielectric according to claim 5, it is characterised in that institute
State gradient-structure Kynoar based composite dielectric with a thickness of 10~40 μm.
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