CN108587007A - A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application - Google Patents
A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application Download PDFInfo
- Publication number
- CN108587007A CN108587007A CN201810042683.5A CN201810042683A CN108587007A CN 108587007 A CN108587007 A CN 108587007A CN 201810042683 A CN201810042683 A CN 201810042683A CN 108587007 A CN108587007 A CN 108587007A
- Authority
- CN
- China
- Prior art keywords
- ferroelectric polymers
- laminated construction
- dielectric film
- polymers based
- based dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 103
- 238000010276 construction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 29
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims description 73
- 238000010041 electrostatic spinning Methods 0.000 claims description 31
- 238000007731 hot pressing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 238000003475 lamination Methods 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 46
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 239000010408 film Substances 0.000 description 87
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 78
- 239000000243 solution Substances 0.000 description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000012046 mixed solvent Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 239000013049 sediment Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 229910017920 NH3OH Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 229940113088 dimethylacetamide Drugs 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910002706 AlOOH Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YXIDSOCDWLQVAZ-UHFFFAOYSA-N ethane-1,2-diol;formic acid Chemical compound OC=O.OCCO YXIDSOCDWLQVAZ-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The present invention relates to a kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application.The film have at least one first dielectric layer and with alternately stacked second dielectric layer of first dielectric layer, first dielectric layer contains vinylidene hexafluoropropylene copolymer P (VDF co HFP) and sheet Al2O3, wherein with volume percentage, the proportioning of the two is (100 x) %P (VDF co HFP)-x%Al2O3, 0<X≤7, second dielectric layer contain ferroelectric polymers.The laminated construction ferroelectric polymers based dielectric film of the present invention has high breakdown field strength, high energy storage density and a high energy storage efficiency, and leadless environment-friendly, with excellent energy-storage property, be suitable for high density energy storage field.
Description
Technical field
The present invention relates to a kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application, belong to
Dielectric substance field.
Background technology
Compared with the energy storage device based on electrochemistry such as ultracapacitor and lithium battery, based on dielectric capacitor
Energy storage device, have many advantages, such as higher power density, more low-loss and more high working voltage.Therefore, dielectric capacitor is not
The basic storage of be only important base electronic element, while being also widely used in electric power systems, energy resource system etc.
It can device.
The energy storage density of current commercialized polymer-based dielectric material such as BOPP only~2J/cm3, with electrochemistry electricity
Container or battery are compared to one or two low order of magnitude.The lower energy storage density of polymer becomes what it further developed and applied
Bottleneck.Ceramic-like dielectric has big dielectric constant and higher disruptive field intensity, but compared with thin polymer film dielectric,
Its disruptive field intensity is still not high enough, and volume is big, non-flexible so that and ceramic-like dielectric is restricted in some application fields,
And polymer-based dielectric film then has the characteristics that flexible, small, is adapted to future device miniaturization, integrated etc. and wants
It asks.
It is equal in traditional high dielectric ceramic material and single polymer thin-film material development high-power high-capacity capacitor
In the case of several drawbacks, people have turned to sight using polymer as matrix, using inorganic matter as the polymer nano of filler
Rice composite dielectric material.Therefore, the research hotspot that the composite dielectrics with high energy storage density is this field is explored.
The 2J/cm more than commercial BOPP film is had been realized in polymer-based dielectric film at present3Energy storage it is close
Degree.Wherein representative material is such as：P (VDF-co-CTFE) film that Z.C.Zhang et al. is prepared using solwution method, should
Energy storage density of the material under 400MV/m field strength about 7~10J/cm3, M.R.Gadinski and B.Chu et al. pass through list respectively
Axis pulling method improves the disruptive field intensity of such film to 600~700MV/m, while energy storage density is improved to 20J/cm3Left and right.
But the solwution method that these materials use in preparation process is suitable for application in large-scale production.Therefore, exploitation has height
Disruptive field intensity, high energy storage density and polymer-based dielectric thin film dielectric material easy to produce become the current urgency in this field
Compel task.
Invention content
Problems to be solved by the invention
The object of the present invention is to provide a kind of laminated construction ferroelectric polymers based dielectric film, and preparation method thereof and use
On the way.The ferroelectric polymers based dielectric film of the present invention has high breakdown field strength, high energy storage density and high energy storage efficiency, prepares
Method simple possible, it is easy to produce.
The solution to the problem
The present invention provides a kind of laminated construction ferroelectric polymers based dielectric film, which is characterized in that the film has
At least one first dielectric layer and with alternately stacked second dielectric layer of first dielectric layer, first dielectric
Layer contains vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) and sheet Al2O3, wherein with volume percentage, two
The proportioning of person is (100-x) %P (VDF-co-HFP)-x%Al2O3, 0<X≤7, second dielectric layer contain ferroelectric polymer
Object preferably comprises vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP).
The thickness of laminated construction ferroelectric polymers based dielectric film according to the present invention, the film is 5~30 μm, excellent
It is selected as 6~20 μm.
Laminated construction ferroelectric polymers based dielectric film according to the present invention, in first dielectric layer, x is 1~
7, preferably 3~7.
Laminated construction ferroelectric polymers based dielectric film according to the present invention, the Al2O3Pattern be two-dimensional sheet.
Laminated construction ferroelectric polymers based dielectric film according to the present invention, the Al2O3Grain size be nanoscale, it is excellent
It is selected as 20~100nm, more preferably 20~60nm.
The present invention also provides a kind of preparation method of laminated construction ferroelectric polymers based dielectric film according to the present invention,
Include the following steps：
Step 1), by the sheet Al2O3With the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) by matching
Than mixing in organic solvent, electrostatic spinning liquid 1 is obtained；The ferroelectric polymers is dissolved in organic solvent, obtains electrostatic
Spinning solution 2；
Step 2), by the electrostatic spinning liquid 1 and the alternately high-voltage electrostatic spinning of the electrostatic spinning liquid 2, folded
The non-woven fabric-like spinning body of layer structure；
The non-woven fabric-like spinning body of the laminated construction is carried out hot pressing by step 3), is carried out after cooled to room temperature cold
It quenches, obtains laminated construction ferroelectric polymers based dielectric film.
The preparation method of laminated construction ferroelectric polymers based dielectric film according to the present invention is high in the step 2)
Press positive and negative voltage difference >=6.5kV of electrostatic spinning, rotating speed >=270 rev/min of collecting wheel, solution fltting speed >=1mL/h.
The preparation method of laminated construction ferroelectric polymers based dielectric film according to the present invention will in the step 3)
Non-woven fabric-like spinning body hot pressing 30~70 minutes under 190~220 DEG C, 400~600dpi pressure.
The preparation method of laminated construction ferroelectric polymers based dielectric film according to the present invention, the non-woven fabric-like is spun
Filament carries out hot pressing, after cooled to room temperature, keep the temperature 1 at 190~240 DEG C~after twenty minutes, cold quenching is carried out at 0 DEG C.
A kind of purposes of laminated construction ferroelectric polymers based dielectric film according to the present invention in electrical equipment.
The effect of invention
Laminated construction ferroelectric polymers based dielectric film provided by the present invention has high breakdown field strength, high energy storage close
Degree and high energy storage efficiency, and leadless environment-friendly, with excellent energy-storage property, be suitable for high density energy storage.Meanwhile institute of the present invention
The laminated construction ferroelectric polymers based dielectric film of offer has both smaller dielectric loss, is that one kind can be applied to a variety of electricity
The material in the fields such as gas element, such as embedded capacitor, electrostatic energy storage component, pulse power element.
Description of the drawings
The structural schematic diagram of Fig. 1 polymer-based dielectric capacitors；
Fig. 2 polymer-based dielectric film multi-layer structures schematic diagrames；
The inorganic matter Al prepared in Fig. 3 embodiments 12O3SEM figure；
The inorganic matter Al prepared in Fig. 4 embodiments 12O3XRD diagram；
The section SEM of the polymer-based dielectric film prepared in Fig. 5 embodiments 1 schemes；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 6 embodiments 1 and comparative example 1；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 7 embodiments 2 and comparative example 1；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 8 embodiments 3 and comparative example 1；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 9 embodiments 4 and comparative example 1.
Reference sign
1：Dielectric capacitor；2：Electrode；3：Polymer-based dielectric film；
31：First dielectric layer；32：Second dielectric layer.
Specific implementation mode
The present invention provides a kind of laminated construction ferroelectric polymers based dielectric film, and the film has at least one first
Dielectric layer and with alternately stacked second dielectric layer of first dielectric layer, first dielectric layer contains inclined fluorine second
Alkene-hexafluoropropylene copolymer P (VDF-co-HFP) and sheet Al2O3, wherein with volume percentage, the proportioning of the two is
(100-x) %P (VDF-co-HFP)-x%Al2O3, 0<X≤7, second dielectric layer contain ferroelectric polymers, preferably comprise
Vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP).
Compared with other ferroelectric polymers, such as PVDF etc., after monomer hexafluoropropene HFP and vinylidene VDF combined polymerizations
The P (VDF-co-HFP) of generation has longer and narrower ferroelectric hysteresis loop, is the excellent substitute of fluorine-containing ferroelectric polymers PVDF.
The present invention is by adding sheet Al2O3Improve the breakdown environment inside ferroelectric polymers, raising iron can be reached
The purpose of electric polymer disruptive field intensity.The breakdown field of the laminated construction ferroelectric polymers based dielectric film of the present invention at room temperature
By force >=600kV/mm, when x is preferably 1≤x≤7, the breakdown of ferroelectric polymers based dielectric film of the invention at room temperature
Field strength >=700kV/mm.Meanwhile sheet Al2O3The laminated construction of film can also be regulated and controled, can reach improve energy storage efficiency and
The purpose of energy storage density.
The second dielectric layer of the present invention contains the group of ferroelectric polymers or ferroelectric polymers and other resin combinations
It closes, the ferroelectric polymers can be the ferroelectric polymers that arbitrarily can be used in thin dielectric film in this field.Second electricity is situated between
Matter layer contains for example：Vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP), polyvinylidene fluoride (PVDF), polytetrafluoroethyl-ne
Alkene (PTFE), polyvinyl chloride (PVC), polystyrene (PS), polysulfones (PSF), polyarylsulfone (PAS) (PASF), polyether sulfone (PES) polypropylene
(PP), polyethylene (PE), crosslinked polyethylene (PEX), polyethylene terephthalate (PET), makrolon (PC), poly- naphthalene two
Formic acid ethylene glycol (PEN), polyphenylene sulfide (PPS), polyamide (PA), polyimides (PI), polyetherimide (PEI), cyano tree
Fat etc., or more ferroelectric polymers or resin copolymer or combinations thereof.Further, the second dielectric layer preferably comprises inclined fluorine second
Alkene-hexafluoropropylene copolymer P (VDF-co-HFP) is conducive to obtain energy storage density and the higher thin dielectric film of energy storage efficiency.
The laminated construction ferroelectric polymers based dielectric film of the present invention, wherein the thickness of the film is 5~30 μm,
Preferably 6~20 μm, the thickness range and the equipment for producing thin film of existing industrial quarters maturation and the matching of technique are preferable.
The ferroelectric polymers based dielectric film of the present invention has multilayer, can have one or more first electricity
Dielectric layer and one or more second dielectric layer, the first dielectric layer and the second dielectric layer are alternately laminated.Specifically
For, laminated construction as follows can be enumerated：
The dielectric layer of the dielectric layer of the dielectric layer ... of first dielectric layer/second/second/first, or
The dielectric layer of the dielectric layer of the dielectric layer ... of second dielectric layer/first/second/first, or
The dielectric layer of the dielectric layer of the dielectric layer ... of second dielectric layer/first/first/second.
The number of plies upper limit of dielectric layer is not required particularly, as long as production technology can be realized.Dielectric
When the number of plies is more than or equal to 3 layers, multilayered structure can effectively improve the energy storage efficiency of the film.
Wherein, the thickness of each layer of dielectric layer does not require particularly, can be the same or different.First dielectric
The total thickness ratio of layer total thickness and the second dielectric layer is 1:12~1:1, the thickness than can effectively the resistance to of enhanced film hit
Wear performance.
The present invention laminated construction ferroelectric polymers based dielectric film, wherein in first dielectric layer, x be 1~
7, preferably 3~7, within the above range, ferroelectric polymers have good flexibility.It should be noted that in the present invention, no
Al in the first same dielectric layer2O3Content can be the same or different.It is excellent from industrial convenience angle
Select Al in each first dielectric layer2O3Content it is identical.
The laminated construction ferroelectric polymers based dielectric film of the present invention, wherein in the film, the Al2O3Pattern
Preferably two-dimensional sheet, which is conducive to improve the disruptive field intensity of film, to increase energy storage density.The Al2O3Grain size is excellent
It is selected as nanoscale, more preferably 20~100nm, further preferably 20~60nm, nano particle is easier in polymer electrolytic
It is uniformly distributed in matter layer, improves the quality of film.It can regulate and control inorganic matter Al by regulating and controlling spinning technique and heat pressing process2O3
Lamination distribution in ferroelectric polymers, to realize the adjustability of energy storage density and disruptive field intensity.
The energy storage density of the laminated construction ferroelectric polymers based dielectric film of the present invention at room temperature is more than 5J/cm3, excellent
It is selected as 15~35J/cm3.It is added to inorganic matter Al2O3Polymer dielectric constant it is lower than pure ferroelectric polymers, be situated between simultaneously
Electrical loss is held essentially constant, i.e. dielectric loss is below 0.05 under 1KHz.
The present invention also provides a kind of preparations of laminated construction ferroelectric polymers based dielectric film according to the present invention
Method, wherein include the following steps：
Step 1), by the sheet Al2O3With the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) by matching
Than mixing in organic solvent, electrostatic spinning liquid 1 is obtained；The ferroelectric polymers is dissolved in organic solvent, obtains electrostatic
Spinning solution 2；
Step 2), by the electrostatic spinning liquid 1 and the alternately high-voltage electrostatic spinning of the electrostatic spinning liquid 2, folded
The non-woven fabric-like spinning body of layer structure；
The non-woven fabric-like spinning body of the laminated construction is carried out hot pressing by step 3), is carried out after cooled to room temperature cold
It quenches, obtains laminated construction ferroelectric polymers based dielectric film.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention, wherein the sheet Al2O3
It can be made by following steps：The alkaline solution of pH >=8 comprising Al salt is subjected to hydro-thermal reaction, obtains sheet AlOOH, then
The AlOOH is subjected to the heat treatment higher than 400 DEG C.
According to above-described sheet Al2O3Preparation method, wherein the pH of the alkaline solution is preferred>8, the pH value
Range is conducive to the formation of the two-dimensional appearance of inorganic matter AlOOH, and then is more advantageous to the Al for obtaining two-dimensional sheet2O3.And it is described
The temperature and time of hydro-thermal reaction does not influence the pattern of AlOOH significantly, such as is carried out at 150~240 DEG C, heat preservation 2
~24 hours.After hydro-thermal reaction, reaction product is washed to neutrality and dried.The AlOOH is at by the warm higher than 400 DEG C
It manages thermal decomposition and generates Al2O3, according to the difference of heat treatment temperature, out of phase Al can be generated2O3, and to Al in the present invention2O3
Crystalline phase there is no particular limitation.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention uses method of electrostatic spinning, the party
Method is conducive to prepare the polymer-based films of laminated construction.
It is not special for the mode of electrostatic spinning as long as disclosure satisfy that the requirement that fibre diameter is made in the present invention
Requirement, can be electrostatic spinning mode commonly used in the art, specifically, by biasfluoroethylene-hexafluoropropylene in the present invention
Copolymer p (VDF-co-HFP) and/or Al2O3It is dissolved in suitable solvent, is prepared into certain density solution.According to the above institute
Two kinds of spinning solutions are alternately spinned using electrostatic spinning technique, obtain the stepped construction that nanofiber is formed by the spinning sequence stated
Dielectric layer, the form of fiber is non-woven fabric-like spinning body.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention, wherein in the step 1), be
It is uniformly mixed, is stirred 12~24 hours.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention, wherein in the step 1)
Organic solvent is acetone, N,N-dimethylformamide (DMF) or DMAC N,N' dimethyl acetamide (DMA).It is spun to obtain high quality
Filament, it is preferred that wherein the ratio of acetone and n,N-Dimethylformamide (DMF) or n,N-dimethylacetamide (DMA) is 1:4
~6:7.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention, wherein high in the step 2)
Press positive and negative voltage difference >=6.5kV of electrostatic spinning, rotating speed >=270 rev/min of collecting wheel, solution fltting speed >=1mL/h.It is molten
The proportional region of matter (gram) and solution (milliliter) is 1:4.3~1:Between 7.9.According to the difference of concentration of dope, selection is closed
Suitable specific spinning technology parameter, such as voltage difference, solution fltting speed etc..
The progress hot pressing of the spinning body of above-mentioned multilayer is integrally formed in the present invention, obtains the ferroelectric polymer for having laminated construction
Object based dielectric film.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention, wherein, will in the step 3)
Non-woven fabric-like spinning body hot pressing 30~70 minutes under 190~220 DEG C, 400~600dpi pressure.This is advantageously ensured that respectively
Good interface cohesion is realized between layer spinning body, and each layer is avoided larger deformation occur.
The preparation method of the laminated construction ferroelectric polymers based dielectric film of the present invention, wherein by the non-woven fabric-like
Spinning body carries out hot pressing, after cooled to room temperature, film keeps the temperature at 190~240 DEG C to 1~after twenty minutes, it is cold in 0 DEG C of progress
It quenches, is conducive to polymer and obtains preferable energy storage density.
The present invention also provides a kind of laminated construction ferroelectric polymers based dielectric films of the present invention in electric elements
In purposes.The electric elements are embedded capacitor, electrostatic energy storage component or pulse power element.
Embodiment
Embodiment 1
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions gradually slowly instill AlCl3In solution, solution is transferred to poly- four behind pH value=8 of solution
In the reaction kettle of vinyl fluoride liner, keep the temperature 17 hours in the baking oven at 200 DEG C, sediment obtained after Temperature fall, spend from
Sub- water and ethyl alcohol rinse sediment repeatedly, and until pH value is in neutrality, the high-temperature process at 650 DEG C of the sediment after drying obtains
Two-dimensional sheet nanometer powder Al2O3, according to 99vol%P (VDF-co-HFP) -1vol%Al2O3(x=1) dispensing is carried out,
In every gram of solid powder correspond to the ratios of 5 milliliters of mixed solvents, with acetone and n,N-dimethylacetamide (DMA) be mix it is molten
Agent, it is spare that spinning solution 1 is made after 10 hours in stirring, and in the mixed solvent acetone and DMA ratios are 2:3.
Acetone and N, N- is added in P (VDF-co-HFP) by the ratio that 5 milliliters of mixed solvents are corresponded to according to every gram of solid powder
The in the mixed solvent of dimethylformamide (DMF), spinning solution 2 is made after 12 hours in stirring spare, in the mixed solvent acetone and DMF
Ratio is 2:3.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6.5kV；285 revs/min of idler wheel rotating speed；Solution fltting speed 1mL per hour；Spinning solution 1 and spinning solution 2
The spinning layer of alternately spinning, spinning solution 1 is contact electrode layer, and the spinning layer of spinning solution 2 is noncontacting electrode layer, eventually forms 3
Layer spinning lamination.
After spinning, for 3 layers of spinning layer at 200 DEG C, 500dpi depresses hot pressing 60 minutes, is then naturally cooling to room temperature.
Film after hot pressing keeps the temperature the cold quenching at 0 DEG C after ten minutes in the environment of 240 DEG C, and it is thin to obtain ferroelectric polymers based dielectric
Film is denoted as film 1.
About 9.4 μm of the thickness of obtained film 1, the performance of the polymer-based dielectric film at 25 DEG C are：Breakdown
Field strength is 745kV/mm, and energy storage efficiency 70%, energy storage density is about 22.7J/cm3。
Embodiment 2
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions gradually slowly instill AlCl3In solution, solution is transferred to behind pH value=9.2 of solution poly-
In the reaction kettle of tetrafluoroethene liner, 20 hours are kept the temperature in the baking oven at 200 DEG C, sediment is obtained after Temperature fall, is spent
Ionized water and ethyl alcohol rinse sediment repeatedly, and until pH value is in neutrality, the high-temperature process at 600 DEG C of the sediment after drying obtains
The two-dimensional sheet nanometer powder Al arrived2O3, according to 99vol%P (VDF-co-HFP) -1vol%Al2O3(x=1) dispensing is carried out,
Wherein every gram of solid powder corresponds to the ratio of 5 milliliters of mixed solvents, is that mixing is molten with acetone and n,N-Dimethylformamide (DMF)
Agent, it is spare that spinning solution 1 is made after 10 hours in stirring, and in the mixed solvent acetone and DMF or DMA ratios are 2:3.
Acetone and N, N- is added in P (VDF-co-HFP) by the ratio that 5 milliliters of mixed solvents are corresponded to according to every gram of solid powder
The in the mixed solvent of dimethylformamide (DMF), spinning solution 2 is made after 12 hours in stirring spare, in the mixed solvent acetone and DMF
Ratio is 2:3.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6.5kV；285 revs/min of idler wheel rotating speed；Solution fltting speed 1mL per hour；Spinning solution 1 and spinning solution 2
The spinning layer of alternately spinning, spinning solution 1 is contact electrode layer, and the spinning layer of spinning solution 2 is noncontacting electrode layer, eventually forms 5
Layer spinning lamination.
After spinning, for 3 layers of spinning layer at 210 DEG C, 520dpi depresses hot pressing 60 minutes, is then naturally cooling to room temperature.
Film after hot pressing keeps the temperature the cold quenching at 0 DEG C after ten minutes in the environment of 240 DEG C, and it is thin to obtain ferroelectric polymers based dielectric
Film is denoted as film 2.
About 10.69 μm of the thickness of obtained film 2, the performance of the polymer-based dielectric film at 25 DEG C are：It hits
It is 837kV/mm, energy storage efficiency 63%, energy storage density 26J/cm to wear field strength3。
Embodiment 3
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions gradually slowly instill AlCl3In solution, solution is transferred to behind pH value=8.6 of solution poly-
In the reaction kettle of tetrafluoroethene liner, 19 hours are kept the temperature in the baking oven at 200 DEG C, sediment is obtained after Temperature fall, is spent
Ionized water and ethyl alcohol rinse sediment repeatedly, and until pH value is in neutrality, the high-temperature process at 650 DEG C of the sediment after drying obtains
The two-dimensional sheet nanometer powder Al arrived2O3, according to 97vol%P (VDF-co-HFP) -3vol%Al2O3(x=3) dispensing is carried out,
Wherein every gram of solid powder corresponds to the ratio of 5 milliliters of mixed solvents, is that mixing is molten with acetone and n,N-Dimethylformamide (DMF)
Agent, it is spare that spinning solution 1 is made after 15 hours in stirring, and in the mixed solvent acetone and DMF ratios are 2:3.
Acetone and N, N- is added in P (VDF-co-HFP) by the ratio that 5 milliliters of mixed solvents are corresponded to according to every gram of solid powder
The in the mixed solvent of dimethylformamide (DMF), spinning solution 2 is made after 12 hours in stirring spare, in the mixed solvent acetone and DMF
Ratio is 2:3.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6.7kV；300 revs/min of idler wheel rotating speed；Solution fltting speed 1ml per hour；Spinning solution 1 and spinning solution 2
The spinning layer of alternately spinning, spinning solution 1 is noncontacting electrode layer, and the spinning layer of spinning solution 2 is contact electrode layer, eventually forms 3
Layer spinning lamination.
After spinning, for 3 layers of spinning layer at 205 DEG C, 510dpi depresses hot pressing 60 minutes, is then naturally cooling to room temperature.
Film after hot pressing keeps the temperature the cold quenching at 0 DEG C after ten minutes in the environment of 240 DEG C, and it is thin to obtain ferroelectric polymers based dielectric
Film is denoted as film 3.
About 10.83 μm of the thickness of obtained film 3, the performance of the polymer-based dielectric film at 25 DEG C are：It hits
It is 732kV/mm, energy storage efficiency 71%, energy storage density 23.8J/cm to wear field strength3。
Embodiment 4
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions gradually slowly instill AlCl3In solution, solution is transferred to behind pH value=8.6 of solution poly-
In the reaction kettle of tetrafluoroethene liner, 19 hours are kept the temperature in the baking oven at 200 DEG C, sediment is obtained after Temperature fall, is spent
Ionized water and ethyl alcohol rinse sediment repeatedly, and until pH value is in neutrality, the high-temperature process at 650 DEG C of the sediment after drying obtains
The two-dimensional sheet nanometer powder Al arrived2O3, according to 93vol%P (VDF-co-HFP) -7vol%Al2O3(x=7) dispensing is carried out,
Wherein every gram of solid powder corresponds to the ratio of 5 milliliters of mixed solvents, is that mixing is molten with acetone and n,N-Dimethylformamide (DMF)
Agent, it is spare that spinning solution 1 is made after 15 hours in stirring, and in the mixed solvent acetone and DMF ratios are 2:3.
Acetone and N, N- is added in P (VDF-co-HFP) by the ratio that 5 milliliters of mixed solvents are corresponded to according to every gram of solid powder
The in the mixed solvent of dimethylformamide (DMF), spinning solution 2 is made after 12 hours in stirring spare, in the mixed solvent acetone and DMF
Ratio is 2:3.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6.7kV；300 revs/min of idler wheel rotating speed；Solution fltting speed 1ml per hour；Spinning solution 1 and spinning solution 2
The spinning layer of alternately spinning, spinning solution 1 is noncontacting electrode layer, and the spinning layer of spinning solution 2 is contact electrode layer, eventually forms 3
Layer spinning lamination.
After spinning, for 3 layers of spinning layer at 200 DEG C, 500dpi depresses hot pressing 30 minutes, is then naturally cooling to room temperature.
Film after hot pressing keeps the temperature the cold quenching at 0 DEG C after ten minutes in the environment of 240 DEG C, and it is thin to obtain ferroelectric polymers based dielectric
Film is denoted as film 4.
About 14 μm of the thickness of obtained film 4, the performance of the polymer-based dielectric film at 25 DEG C are：Breakdown field
It is 879kV/mm, energy storage efficiency 71%, energy storage density 29.6J/cm by force3。
Comparative example 1
P (VDF-co-HFP) powders of purchase are corresponded into 5 milliliters of mixed organic solvents (acetone and diformazans according to every gram of solute
The mixture of base formamide (DMF)) mixing after, at room temperature stir 12-24 hours, so that it is fully dissolved.It is spun using high-pressure electrostatic
Silk prepares the uniform spinning body of polymer nanocomposite silk.The parameter of the high-voltage electrostatic spinning is：Positive and negative voltage difference 6kV；Idler wheel turns
300 revs/min of speed, solution fltting speed 1mL per hour.After spinning, for spinning layer at 200 DEG C, 500dpi depresses hot pressing 60
Minute, then it is naturally cooling to room temperature.Film after hot pressing keeps the temperature the cold quenching at 0 DEG C after ten minutes in the environment of 240 DEG C, obtains
To ferroelectric polymers based dielectric film, it is denoted as film 4.
About 10 μm of the thickness of obtained film 4, the performance of the polymer-based dielectric film at 25 DEG C are：Breakdown field
It is 400KV/mm, energy storage efficiency 56.7%, energy storage density 7.8J/cm by force3。
Performance test
Round metal electrode is prepared by vacuum deposition method on sample thin film 1~4, and tests its properties.
Dielectric properties：It is tested using impedance analyzer (Agilent company of the U.S., E4990A)
Disruptive field intensity and ferroelectric hysteresis loop：Using ferroelectricity tester (Radiant Tech., PrecisionPremier
II it) is tested, energy storage density and energy storage efficiency are calculated by ferroelectric hysteresis loop and obtained.
Claims (10)
1. a kind of laminated construction ferroelectric polymers based dielectric film, which is characterized in that the film has at least one first
Dielectric layer and with alternately stacked second dielectric layer of first dielectric layer, first dielectric layer contains inclined fluorine second
Alkene-hexafluoropropylene copolymer P (VDF-co-HFP) and sheet Al2O3, wherein with volume percentage, the proportioning of the two is
(100-x) %P (VDF-co-HFP)-x%Al2O3, 0<X≤7,
Second dielectric layer contains ferroelectric polymers, preferably comprises vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-
HFP)。
2. laminated construction ferroelectric polymers based dielectric film according to claim 1, which is characterized in that the film
Thickness is 5~30 μm, preferably 6~20 μm.
3. laminated construction ferroelectric polymers based dielectric film according to claim 1 or 2, which is characterized in that described
In one dielectric layer, x is 1~7, preferably 3~7.
4. according to claims 1 to 3 any one of them laminated construction ferroelectric polymers based dielectric film, which is characterized in that
The Al2O3Pattern be two-dimensional sheet.
5. according to Claims 1 to 4 any one of them laminated construction ferroelectric polymers based dielectric film, which is characterized in that
The Al2O3Grain size be nanoscale, preferably 20~100nm, more preferably 20~60nm.
6. a kind of preparation side according to Claims 1 to 5 any one of them laminated construction ferroelectric polymers based dielectric film
Method, which is characterized in that include the following steps：
Step 1), by the sheet Al2O3Exist according to the ratio with the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP)
It is mixed in organic solvent, obtains electrostatic spinning liquid 1；The ferroelectric polymers is dissolved in organic solvent, obtains electrostatic spinning
Liquid 2；
Step 2), by the electrostatic spinning liquid 1 and the alternately high-voltage electrostatic spinning of the electrostatic spinning liquid 2, obtain lamination knot
The non-woven fabric-like spinning body of structure；
The non-woven fabric-like spinning body of the laminated construction is carried out hot pressing by step 3), is carried out cold quenching after cooled to room temperature, is obtained
To laminated construction ferroelectric polymers based dielectric film.
7. the preparation method of laminated construction ferroelectric polymers based dielectric film according to claim 6, which is characterized in that
In the step 2), positive and negative voltage difference >=6.5kV of high-voltage electrostatic spinning, rotating speed >=270 rev/min of collecting wheel, solution pushes away
Into speed >=1mL/h.
8. the preparation method of the laminated construction ferroelectric polymers based dielectric film described according to claim 6 or 7, feature exist
In, in the step 3), the hot pressing 30~70 under 190~220 DEG C, 400~600dpi pressure by the non-woven fabric-like spinning body
Minute.
9. according to the preparation method of claim 6~8 any one of them laminated construction ferroelectric polymers based dielectric film,
It is characterized in that, the non-woven fabric-like spinning body is subjected to hot pressing, after cooled to room temperature, 1~20 is kept the temperature at 190~240 DEG C
After minute, cold quenching is carried out at 0 DEG C.
10. it is a kind of according to Claims 1 to 5 any one of them laminated construction ferroelectric polymers based dielectric film in electrical member
Purposes in part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810042683.5A CN108587007B (en) | 2018-01-17 | 2018-01-17 | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810042683.5A CN108587007B (en) | 2018-01-17 | 2018-01-17 | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108587007A true CN108587007A (en) | 2018-09-28 |
| CN108587007B CN108587007B (en) | 2019-10-29 |
Family
ID=63608415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810042683.5A Expired - Fee Related CN108587007B (en) | 2018-01-17 | 2018-01-17 | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108587007B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112695462A (en) * | 2020-12-25 | 2021-04-23 | 湖北科技学院 | Composite dielectric material with multilayer gradient structure and preparation method thereof |
| CN116770511A (en) * | 2023-05-17 | 2023-09-19 | 哈尔滨理工大学 | Polyether sulfone/polyetherimide high-temperature energy storage composite medium and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702856A (en) * | 2014-11-26 | 2016-06-22 | 华为技术有限公司 | Memristor device based on organic ferroelectric film material and preparation method thereof |
| EP2624333B1 (en) * | 2012-02-06 | 2017-10-18 | Samsung SDI Co., Ltd. | Lithium secondary battery |
-
2018
- 2018-01-17 CN CN201810042683.5A patent/CN108587007B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2624333B1 (en) * | 2012-02-06 | 2017-10-18 | Samsung SDI Co., Ltd. | Lithium secondary battery |
| CN105702856A (en) * | 2014-11-26 | 2016-06-22 | 华为技术有限公司 | Memristor device based on organic ferroelectric film material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 查俊伟等: "《铁电聚合物基纳米复合电介质储能材料研究进展》", 《高电压技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112695462A (en) * | 2020-12-25 | 2021-04-23 | 湖北科技学院 | Composite dielectric material with multilayer gradient structure and preparation method thereof |
| CN116770511A (en) * | 2023-05-17 | 2023-09-19 | 哈尔滨理工大学 | Polyether sulfone/polyetherimide high-temperature energy storage composite medium and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108587007B (en) | 2019-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107705985B (en) | A kind of high energy storage efficiency ferroelectric polymers based dielectric film, and its preparation method and application | |
| Li et al. | Enhanced energy storage performance of ferroelectric polymer nanocomposites at relatively low electric fields induced by surface modified BaTiO3 nanofibers | |
| Liu et al. | Nanostructured graphene composite papers for highly flexible and foldable supercapacitors | |
| TWI619611B (en) | Porous membranes and multilayer porous membranes | |
| KR102335587B1 (en) | Separator for secondary battery and secondary battery | |
| CN107925036B (en) | Battery separator | |
| CN106633153A (en) | Polymer-based dielectric energy storage nanocomposite material in three-layer structure and preparation method thereof | |
| CN107901303A (en) | A kind of sandwich structure high energy storage density polymer-based dielectric composite material and preparation method thereof | |
| CN111433940B (en) | Porous film, secondary battery separator, and secondary battery | |
| CN107571586B (en) | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application | |
| Gong et al. | Thermosensitive polyacrylonitrile/polyethylene oxide/polyacrylonitrile membrane separators for prompt and safer thermal lithium-ion battery shutdown | |
| CN108587007B (en) | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application | |
| CN110722854A (en) | Composite dielectric material with alternating multilayer structure and preparation method thereof | |
| CN108559114A (en) | Composite dielectrics film and preparation method thereof | |
| CN105038045A (en) | Preparation method for graphene oxide/polyvinylidene fluoride composite film | |
| CN110010824B (en) | Polyolefin lithium ion battery diaphragm modification method | |
| CN106898720A (en) | A kind of lithium ion battery separator and preparation method thereof | |
| Harami et al. | Mixed Matrix Membranes for Sustainable Electrical Energy‐Saving Applications | |
| CN111446404A (en) | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery | |
| CN110341205A (en) | A kind of multiple layer polymer nanocomposite and preparation method thereof | |
| CN113903597A (en) | Carbon quantum dot/polymer dielectric composite material and preparation method and application thereof | |
| CN107230803B (en) | Sandwich structure multilayer gel polymer electrolyte for lithium ion battery and preparation method thereof | |
| CN107652588B (en) | Ferroelectric polymer based dielectric film, preparation method and application thereof | |
| Chen et al. | Fabrication and application of TiO2-modified PMIA separators with strong mechanical properties in lithium-ion batteries | |
| Zhang et al. | Structure, dielectric, ferroelectric, and energy density properties of polyethersulfone-based composite for energy storage application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |