CN108587007B - 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
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- CN108587007B CN108587007B CN201810042683.5A CN201810042683A CN108587007B CN 108587007 B CN108587007 B CN 108587007B CN 201810042683 A CN201810042683 A CN 201810042683A CN 108587007 B CN108587007 B CN 108587007B
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- 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
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- 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 fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) and sheet Al2O3, wherein with volume percentage, the proportion of the two is (100-x) %P (VDF-co-HFP)-x%Al2O3, 0 < x≤7, second dielectric layer contains ferroelectric polymers.Laminated construction ferroelectric polymers based dielectric film of the 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 technique
Compared with the energy storage device based on electrochemistry such as supercapacitor 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 ceramic-like dielectric is restricted in some application fields,
And polymer-based dielectric film then has the characteristics that flexible, small in size, is adapted to future device miniaturization, integrated etc. and wants
It asks.
It is equal to develop high-power high-capacity capacitor in traditional high dielectric ceramic material and single polymer thin-film material
There are in the case where 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 for being greater 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: Z.C.Zhang et al., should using P (VDF-co-CTFE) film of solwution method preparation
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 during the 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.
Summary of the invention
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.Ferroelectric polymers based dielectric film of the invention has high breakdown field strength, high energy storage density and high energy storage efficiency, preparation
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 proportion of person is (100-x) %P (VDF-co-HFP)-x%Al2O3, 0 < x≤7, second dielectric layer contains ferroelectric polymer
Object preferably comprises vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP).
Laminated construction ferroelectric polymers based dielectric film according to the present invention, the film with a thickness of 5~30 μm, it is 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 Al2O3Partial 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, revolving 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, in 0 DEG C of progress cold quenching.
A kind of purposes of laminated construction ferroelectric polymers based dielectric film according to the present invention in electrical component.
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 lesser 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.
Detailed description of the invention
The structural schematic diagram of Fig. 1 polymer-based dielectric capacitor；
Fig. 2 polymer-based dielectric film multi-layer structures schematic diagram；
The inorganic matter Al prepared in Fig. 3 embodiment 12O3SEM figure；
The inorganic matter Al prepared in Fig. 4 embodiment 12O3XRD diagram；
The section SEM of the polymer-based dielectric film prepared in Fig. 5 embodiment 1 schemes；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 6 embodiment 1 and comparative example 1；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 7 embodiment 2 and comparative example 1；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 8 embodiment 3 and comparative example 1；
The energy-storage property figure of the polymer-based dielectric film prepared in Fig. 9 embodiment 4 and comparative example 1.
Description of symbols
1: dielectric capacitor；2: electrode；3: polymer-based dielectric film；
31: the first dielectric layers；32: the second dielectric layers.
Specific embodiment
The present invention provides a kind of laminated construction ferroelectric polymers based dielectric film, the film have 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 proportion 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).
Compared with other ferroelectric polymers, such as PVDF etc., after monomer hexafluoropropene HFP and vinylidene VDF combined polymerization
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 passes through addition 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 laminated construction ferroelectric polymers based dielectric film of the 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 that film can also be regulated and controled, can achieve improve energy storage efficiency and
The purpose of energy storage density.
Second dielectric layer of the 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), polycarbonate (PC), poly- naphthalene two
Formic acid ethylene glycol (PEN), polyphenylene sulfide (PPS), polyamide (PA), polyimides (PI), polyetherimide (PEI), cyano tree
Rouge etc., or the above 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), help to obtain energy storage density and the higher thin dielectric film of energy storage efficiency.
Laminated construction ferroelectric polymers based dielectric film of the invention, wherein the film with a thickness of 5~30 μm,
Preferably 6~20 μm, the thickness range and the equipment for producing thin film of existing industry maturation and the matching of technique are preferable.
Ferroelectric polymers based dielectric film of the 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:
First dielectric layer/the second dielectric layer .../the second dielectric layer/the first dielectric layer, or
Second dielectric layer/the first dielectric layer .../the second dielectric layer/the first dielectric layer, or
Second dielectric layer/the first dielectric layer .../the first dielectric layer/the second dielectric layer.
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 effective the resistance to of enhanced film hit
Wear performance.
Laminated construction ferroelectric polymers based dielectric film of the invention, wherein in first dielectric layer, x be 1~
7, preferably 3~7, within the above range, ferroelectric polymers has 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.
Laminated construction ferroelectric polymers based dielectric film of the 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 Al2O3Partial 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.Inorganic matter Al can be regulated and controled by regulation spinning technique and heat pressing process2O3In
Lamination distribution in ferroelectric polymers, to realize the adjustability of energy storage density and disruptive field intensity.
The energy storage density of laminated construction ferroelectric polymers based dielectric film of the invention at room temperature is greater 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 laminated construction ferroelectric polymers based dielectric film of the invention, wherein the sheet Al2O3
It can be made by following steps: the alkaline solution of pH >=8 comprising Al salt being 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 carries 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
Crystal phase there is no particular limitation.
The preparation method of laminated construction ferroelectric polymers based dielectric film of the 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 can satisfy 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 laminated construction ferroelectric polymers based dielectric film of the invention, wherein in the step 1), be
It is uniformly mixed, is stirred 12~24 hours.
The preparation method of laminated construction ferroelectric polymers based dielectric film of the 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 laminated construction ferroelectric polymers based dielectric film of the invention, wherein high in the step 2)
Press positive and negative voltage difference >=6.5kV of electrostatic spinning, revolving 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 between 1:4.3~1:7.9.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 spinning body of above-mentioned multilayer is carried out hot pressing in the present invention to be integrally formed, obtains the ferroelectric polymer for having laminated construction
Object based dielectric film.
The preparation method of laminated construction ferroelectric polymers based dielectric film of the 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 biggish deformation occur.
The preparation method of laminated construction ferroelectric polymers based dielectric film of the 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 solution gradually slowly instills 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 repeated flushing sediment, until pH value is in neutrality, the high-temperature process at 650 DEG C of the sediment after drying is obtained
Two-dimensional sheet nanometer powder Al2O3, according to 99vol%P (VDF-co-HFP) -1vol%Al2O3(x=1) ingredient is carried out,
In the corresponding 5 milliliters of mixed solvents of every gram of solid powder ratio, 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 ratio are 2:3.
According to the ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, acetone and N, N- is added in P (VDF-co-HFP)
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
Are as follows: positive and negative voltage difference 6.5kV；285 revs/min of idler wheel revolving speed；Solution fltting speed 1mL per hour；Spinning solution 1 and spinning solution 2
Alternately spinning, the spinning layer of spinning solution 1 are contact electrode layer, and the spinning layer of spinning solution 2 is noncontacting electrode layer, eventually forms 3
Layer spinning lamination.
After spinning, at 200 DEG C, 500dpi is depressed hot pressing 60 minutes 3 layers of spinning layer, 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 as follows: 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 solution gradually slowly instills 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 repeated flushing sediment, until pH value is in neutrality, the high-temperature process at 600 DEG C of the sediment after drying is obtained
The two-dimensional sheet nanometer powder Al arrived2O3, according to 99vol%P (VDF-co-HFP) -1vol%Al2O3(x=1) ingredient is carried out,
The wherein ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, 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 ratio are 2:3.
According to the ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, acetone and N, N- is added in P (VDF-co-HFP)
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
Are as follows: positive and negative voltage difference 6.5kV；285 revs/min of idler wheel revolving speed；Solution fltting speed 1mL per hour；Spinning solution 1 and spinning solution 2
Alternately spinning, the spinning layer of spinning solution 1 are contact electrode layer, and the spinning layer of spinning solution 2 is noncontacting electrode layer, eventually forms 5
Layer spinning lamination.
After spinning, at 210 DEG C, 520dpi is depressed hot pressing 60 minutes 3 layers of spinning layer, 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 as follows: hit
Wearing field strength is 837kV/mm, energy storage efficiency 63%, energy storage density 26J/cm3。
Embodiment 3
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solution gradually slowly instills 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 repeated flushing sediment, until pH value is in neutrality, the high-temperature process at 650 DEG C of the sediment after drying is obtained
The two-dimensional sheet nanometer powder Al arrived2O3, according to 97vol%P (VDF-co-HFP) -3vol%Al2O3(x=3) ingredient is carried out,
The wherein ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, 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 ratio are 2:3.
According to the ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, acetone and N, N- is added in P (VDF-co-HFP)
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
Are as follows: positive and negative voltage difference 6.7kV；300 revs/min of idler wheel revolving speed；Solution fltting speed 1ml per hour；Spinning solution 1 and spinning solution 2
Alternately spinning, the spinning layer of spinning solution 1 are noncontacting electrode layer, and the spinning layer of spinning solution 2 is contact electrode layer, eventually form 3
Layer spinning lamination.
After spinning, at 205 DEG C, 510dpi is depressed hot pressing 60 minutes 3 layers of spinning layer, 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 as follows: hit
Wearing field strength is 732kV/mm, energy storage efficiency 71%, energy storage density 23.8J/cm3。
Embodiment 4
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solution gradually slowly instills 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 repeated flushing sediment, until pH value is in neutrality, the high-temperature process at 650 DEG C of the sediment after drying is obtained
The two-dimensional sheet nanometer powder Al arrived2O3, according to 93vol%P (VDF-co-HFP) -7vol%Al2O3(x=7) ingredient is carried out,
The wherein ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, 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 ratio are 2:3.
According to the ratio of the corresponding 5 milliliters of mixed solvents of every gram of solid powder, acetone and N, N- is added in P (VDF-co-HFP)
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
Are as follows: positive and negative voltage difference 6.7kV；300 revs/min of idler wheel revolving speed；Solution fltting speed 1ml per hour；Spinning solution 1 and spinning solution 2
Alternately spinning, the spinning layer of spinning solution 1 are noncontacting electrode layer, and the spinning layer of spinning solution 2 is contact electrode layer, eventually form 3
Layer spinning lamination.
After spinning, at 200 DEG C, 500dpi is depressed hot pressing 30 minutes 3 layers of spinning layer, 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 as follows: breakdown field
It is by force 879kV/mm, energy storage efficiency 71%, energy storage density 29.6J/cm3。
Comparative example 1
By P (VDF-co-HFP) powder of purchase according to every gram of solute corresponding 5 milliliters of mixed organic solvents (acetone and diformazans
The mixture of base formamide (DMF)) mixing after, at room temperature stir 12-24 hours, dissolve it sufficiently.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 are as follows: 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 as follows: breakdown field
It is by force 400KV/mm, energy storage efficiency 56.7%, energy storage density 7.8J/cm3。
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: ferroelectricity tester (Radiant Tech., PrecisionPremier are used
II it) is tested, energy storage density and energy storage efficiency are calculated by ferroelectric hysteresis loop and obtained.
Claims (12)
1. a kind of laminated construction ferroelectric polymers based dielectric film, which is characterized in that the film have 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 proportion of the two is
(100-x) %P (VDF-co-HFP)-x%Al2O3, 0 < x≤7,
Second dielectric layer contains vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP),
The Al2O3Partial size be 20~100nm.
2. laminated construction ferroelectric polymers based dielectric film according to claim 1, which is characterized in that the film
With a thickness of 5~30 μm.
3. laminated construction ferroelectric polymers based dielectric film according to claim 2, which is characterized in that the film
With a thickness of 6~20 μm.
4. described in any item laminated construction ferroelectric polymers based dielectric films according to claim 1~3, which is characterized in that
In first dielectric layer, x is 1~7.
5. laminated construction ferroelectric polymers based dielectric film according to claim 4, which is characterized in that first electricity
In dielectric layer, x is 3~7.
6. described in any item laminated construction ferroelectric polymers based dielectric films according to claim 1~3, which is characterized in that
The Al2O3Pattern be two-dimensional sheet.
7. described in any item laminated construction ferroelectric polymers based dielectric films according to claim 1~3, which is characterized in that
The Al2O3Partial size be 20~60nm.
8. a kind of preparation side of laminated construction ferroelectric polymers based dielectric films described in any item according to claim 1~7
Method, which comprises the steps of:
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.
9. the preparation method of laminated construction ferroelectric polymers based dielectric film according to claim 8, which is characterized in that
In the step 2), positive and negative voltage difference >=6.5kV of high-voltage electrostatic spinning, revolving speed >=270 rev/min of collecting wheel, solution pushed away
Into speed >=1mL/h.
10. the preparation method of laminated construction ferroelectric polymers based dielectric film according to claim 8 or claim 9, feature
Be, in the step 3), by the non-woven fabric-like spinning body under 190~220 DEG C, 400~600dpi pressure hot pressing 30~
70 minutes.
11. the preparation method of laminated construction ferroelectric polymers based dielectric film according to claim 8 or claim 9, feature
It is, the non-woven fabric-like spinning body is subjected to hot pressing, after cooled to room temperature, keeps the temperature 1~20 minute at 190~240 DEG C
Afterwards, in 0 DEG C of progress cold quenching.
12. a kind of laminated construction ferroelectric polymers based dielectric films described in any item according to claim 1~7 are in electrical member
Purposes in part.
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