CN108638616A - Layered dielectric material and preparation method thereof - Google Patents
Layered dielectric material and preparation method thereof Download PDFInfo
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- CN108638616A CN108638616A CN201810440998.5A CN201810440998A CN108638616A CN 108638616 A CN108638616 A CN 108638616A CN 201810440998 A CN201810440998 A CN 201810440998A CN 108638616 A CN108638616 A CN 108638616A
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004744 fabric Substances 0.000 claims abstract description 179
- 239000000835 fiber Substances 0.000 claims abstract description 170
- 229920001577 copolymer Polymers 0.000 claims abstract description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 72
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- 238000009987 spinning Methods 0.000 claims description 61
- 238000007731 hot pressing Methods 0.000 claims description 31
- 238000012545 processing Methods 0.000 claims description 30
- 238000010791 quenching Methods 0.000 claims description 29
- 230000000171 quenching effect Effects 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000010041 electrostatic spinning Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002759 woven fabric Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 38
- 230000010287 polarization Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000007788 liquid Substances 0.000 description 22
- 239000012046 mixed solvent Substances 0.000 description 20
- 239000002033 PVDF binder Substances 0.000 description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 238000011160 research Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010013142 Disinhibition Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
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- 239000002135 nanosheet Substances 0.000 description 1
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- 229920006254 polymer film Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/16—Organic dielectrics of fibrous material, e.g. paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0223—Vinyl resin fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/16—Capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention relates to a kind of layered dielectric materials and preparation method thereof, including the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth being stacked, first fiber non-woven layer of cloth is vinylidene hexafluoropropylene copolymer layer, second fiber non-woven layer of cloth is vinylidene trifluoro-ethylene chlorine fluoride copolymers layer, and total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is 2~30 layers.Above-mentioned layered dielectric material and preparation method thereof, vinylidene hexafluoropropylene copolymer layer has high breakdown performance, and vinylidene trifluoro-ethylene chlorine fluoride copolymers Cen has high polarization performance and high energy storage efficiency, and by being layered on top of each other vinylidene hexafluoropropylene copolymer layer and vinylidene trifluoro-ethylene chlorine fluoride copolymers layer to control the inside mesoscopic structure of stratiform dielectric material, be conducive to inhibit conductance loss and the f-e loss inside stratiform dielectric material, so that layered dielectric material has both high energy storage density and energy storage efficiency simultaneously.
Description
Technical field
The present invention relates to dielectric material preparing technical fields, more particularly to layered dielectric material and preparation method thereof.
Background technology
With the development of modern science and technology, existing as important base electronic element and high-power energy storage device, capacitor
It is obtained in consumer electronics product, communication products, automation control, high-speed railway, new-energy automobile and aviation and military equipment
It is widely applied.Wherein, thin film capacitor obtains scientific research personnel and market because of its high withstand voltage intensity, the advantages such as high power density
More concerns.However, the dielectric constant of commercialization thin dielectric film BOPP (Biaxially oriented polypropylene) is relatively low (2~3), lead to it
Lower energy storage density (~2J/cm3) limits it and widely applies.For example, track magnetic artillery emits needs about every time
The energy input of 100MJ, and the volume of the capacitor of energy is provided usually at 10 cubic metres or so, excessive volume and weight is just
Significantly limit its more efficient use.In order to improve the dielectric constant and energy storage density of dielectric film, scientific research personnel is by mesh
Light has turned to the PVDF based polyalcohols with high polarization ability.2006, Pennsylvania State University of U.S. Zhang Qiming was taught in periodical
Science propositions use P (VDF-CTFE) as dielectric energy storage film, obtain being higher than 10 dielectric constant and higher than 10J/cm3's
Energy storage density is far above the energy storage density of tradition BOPP.Hereafter, scientific research personnel goes to further increase using a variety of different modes
The energy storage density of PVDF based polyalcohols, such as polymer nanocomposites are prepared, build composite material with multi-layer structure
The polymer modifications material etc. such as it is blended, is grafted with preparing.Pass through the effort of more than ten years, the nowadays energy storage of PVDF base polymeric materials
Density can reach 5~15J/cm3, but its energy storage efficiency but only has 50~70%, this means that a large amount of energy is dissipated.
And these energy overwhelming majority to dissipate are converted into useless and harmful thermal energy, due to the intrinsic lower thermal conductivity of polymer material,
So that heat is accumulated in polymeric inner, lead to the internal temperature rise of material and final penalty.Therefore, how to ensure height
The energy storage efficiency of PVDF based polyalcohols is improved while energy storage density just becomes a research hotspot and difficult point.
The low energy storage efficiency of PVDF based polyalcohols is lost of both being mostly derived from：1) f-e loss：PVDF is a kind of non-
Linear ferroelectric material, internal dipole cannot keep up with the variation of extra electric field, there is sluggish phenomenon, this sluggish process can band
The loss for carrying out energy, to generate f-e loss.2) conductance is lost：There are free-moving electronics and ion inside PVDF,
Under the action of external electric field, meeting displacement forms leakage current, to generate conductance loss.In order to inhibit the damage of PVDF based polyalcohols
Consumption, improves the energy storage efficiency of material, scientific research personnel also expands a large amount of research work.2013, Zhang Qiming was taught in P
(VDF-TrFE) large-sized CFE or CTFE monomers are added on, P (VDF-TrFE-CFE) or P (VDF-TrFE- is prepared
CTFE) terpolymer is reduced the large scale ferroelectric domain in original P (VDF-TrFE) polymer by nanometer restriction effect
For the ferroelectric domain of nano-scale, reduce the limitation of domain wall electrode couple overturning so that the dipole of polymeric inner can be powered up externally
Rapid response is made in the variation of field, to reduce f-e loss, improves efficiency.Meanwhile Xi Chu universities of U.S. Zhu Lei professors are in P
(VDF-TrFE-CTFE) it has been grafted polystyrene PS on the basis of, P (VDF-TrFE-CTFE)-g-PS block copolymers are made,
Further suppress the loss of polymer.2010, Xi'an Communications University professor Xu Zhuo had different phase structures by preparation
PVDF has found that α-PVDF and γ-PVDF are lower than the loss of β-PVDF, more efficient.Above research work is mainly from suppression
The angle of f-e loss processed is set out, and also someone goes to set about from the direction for inhibiting conductance to be lost.2012, professor Zhu Lei utilized microbedding
The method of coextrusion is prepared for PVDF/PC (polypropylene) multiple layers of polymeric materials, is moved to charge by layer structure design and interface
It moves and inhibits, preferably control the conductance loss of polymeric inner.2015, Pennsylvania State University of U.S. Wang Qing was taught in periodical
Energy＆Environmental Science propose to go to prepare P (VDF- as filler using BNNS (boron nitride nanosheet)
TrFE-CFE)/BNNS nanocomposites, the experimental results showed that, since the big L/D ratio structure and height of BNNS two-dimensional slices are exhausted
Edge, composite material exhibits go out lower leakage current and higher breakdown performance, and the composite material of preparation has higher energy storage
Density and efficiency.
Although scientific research personnel is made that many effort, the PVDF based polyalcohols being prepared still are difficult to have both height simultaneously
Energy storage density and energy storage efficiency.
Invention content
Based on this, it is necessary to still be difficult to have both asking for high energy storage density and energy storage efficiency simultaneously for PVDF based polyalcohols
Topic provides a kind of layered dielectric material and preparation method thereof.
A kind of layered dielectric material, including the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth that are stacked, institute
It is vinylidene fluoride-hexafluoropropylene copolymer layer to state the first fiber non-woven layer of cloth, and the second fiber non-woven layer of cloth is vinylidene-
Total number of plies of trifluoro-ethylene-chlorine fluoride copolymers layer, the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
It is 2~30 layers.
In a wherein embodiment, total layer of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
Number is 3 layers, and the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth are alternately laminated；
Or, the overlapped way of layered dielectric material is ABA, wherein B represents the first fiber non-woven layer of cloth and institute
One of state in the second fiber non-woven layer of cloth, A represents the first fiber non-woven layer of cloth and second fabric nonwoven cloth
Layer in another.
In a wherein embodiment, total layer of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
Number is odd number, and layered dielectric material includes middle layer and the first alternating layer group for being respectively arranged on two sides of the middle layer
And the second alternating layer group；The middle layer is the first fiber non-woven layer of cloth or the second fiber non-woven layer of cloth, first alternating layer
Group includes alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and the second alternating layer group includes alternating layer
Folded the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and the first alternating layer group and the second alternating layer group
The number of plies is identical；The first alternating layer group is different from the material of the middle layer close to one layer of the middle layer, and described second
Alternating layer group is different from the material of the middle layer close to one layer of the middle layer；
Or, the overlapped way of layered dielectric material is (AB)nA(BA)nOr B (AB)nA(BA)nB, wherein A represents institute
One of state in the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, B represents first fabric nonwoven cloth
Layer and the second fiber non-woven layer of cloth in another；And 1≤n≤7.
In a wherein embodiment, total layer of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
Number is even number, and layered dielectric material includes the first alternating layer group and the second alternating layer for being laminated in the first alternating layer group
Group, the first alternating layer group include alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and described second
Alternating layer group includes alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and the first alternating layer group and
The number of plies of the second alternating layer group is identical；In the first alternating layer group close to one layer of the second alternating layer group with it is described
Close to one layer of material identical of the first alternating layer group in second alternating layer group；
Or, the overlapped way of layered dielectric material is (AB)m(BA)mOr B (AB)m(BA)mB, wherein A represents first
One of in fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, B represents the first fiber non-woven layer of cloth and described
Another in two fiber non-woven layer of cloths；And 1≤m≤7.
The preparation method of above-mentioned layered dielectric material, includes the following steps：
Vinylidene fluoride-hexafluoropropylene copolymer is dissolved in the first solvent and obtains the first solution；
Vinylidene-trifluoro-ethylene-chlorine fluoride copolymers are dissolved in the second solvent and obtain the second solution；
It is molded first solution and second solution to obtain intermediate, the centre by the way of electrostatic spinning
Body includes the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth being layered on top of each other；Wherein, first solution is molded to obtain
First fiber non-woven layer of cloth, second solution are molded to obtain the second fiber non-woven layer of cloth；The first fiber non-woven layer of cloth with
Total number of plies of the second fiber non-woven layer of cloth is 2 layers~30 layers；
Hot-pressing processing is carried out to the intermediate；And
Cold quenching processing is carried out to the intermediate.
In a wherein embodiment, first solvent is selected from the mixed liquor of n,N-Dimethylformamide and acetone,
Wherein, n,N-Dimethylformamide and the volume ratio of acetone are 3:2~5:1；
And/or second solvent is selected from the mixed liquor of n,N-Dimethylformamide and acetone, wherein N, N- dimethyl
The volume ratio of formamide and acetone is 3:2~5:1.
In a wherein embodiment, matter of the vinylidene fluoride-hexafluoropropylene copolymer in first solution
It is 15%~30% to measure percentage；
And/or quality percentage of the vinylidene-trifluoro-ethylene-chlorine fluoride copolymers in second solution
Than being 15%~30%.
In a wherein embodiment, it is described by the way of electrostatic spinning by first solution and described second molten
It is 4kV~15kV that liquid, which is separately formed voltage in the step of obtaining intermediate, and the speed of injecting of syringe pump is 0.1mL/h~2mL/h,
Spinning distance is 5cm~50cm, and drum rotation speed is 100rpm~1000rpm, and the spinning time is 10min~10h.
In a wherein embodiment, hot pressing temperature is 150 DEG C~220 DEG C when the hot-pressing processing, and hot pressing pressure is
2MPa~20MPa, hot pressing time are 15min~120min.
In a wherein embodiment, the step of cold quenching processing, specifically includes：
The intermediate is heated, the temperature of the heat treatment is 180 DEG C~240 DEG C, at the heating
The time of reason is 5min~30min；And
Cooling processing is carried out to the intermediate, the cooling temperature of the cooling processing is 0~100 DEG C, and cool down processing
Time is 2min~15min.
Above-mentioned layered dielectric material and preparation method thereof, using vinylidene fluoride-hexafluoropropylene copolymer layer and vinylidene-
Trifluoro-ethylene-chlorine fluoride copolymers layer stackup, vinylidene fluoride-hexafluoropropylene copolymer layer have high breakdown performance, and inclined fluorine
Ethylene-trifluoroethylene-chlorine fluoride copolymers Cen has high polarization performance and high energy storage efficiency, and by by vinylidene-
Hexafluoropropylene copolymer layer and vinylidene-trifluoro-ethylene-chlorine fluoride copolymers layer are layered on top of each other to control layered dielectric material
The inside mesoscopic structure of material is conducive to inhibit conductance loss and f-e loss inside stratiform dielectric material, so that stratiform
Dielectric material has both high energy storage density and energy storage efficiency simultaneously.
Description of the drawings
Fig. 1 is the process flow chart of the preparation method of the layered dielectric material of an embodiment；
Fig. 2 is the first fiber non-woven layer of cloth (a), the P (VDF- that P (VDF-HFP) electrostatic spinning in embodiment 1 obtains
TrFE-CFE the surface topography (c) and stratiform for the second fiber non-woven layer of cloth (b) and layered dielectric material that) electrostatic spinning obtains are situated between
The stereoscan photograph of the cross-section morphology (d) of electric material；
Fig. 3 is the relative dielectric constant frequency spectrum for the layered dielectric material being prepared in Examples 1 to 5；
Fig. 4 is the potentiometer-electric field curve for the layered dielectric material being prepared in Examples 1 to 5.
Specific implementation mode
Layered dielectric material and preparation method thereof is done below in conjunction with specific implementation mode and attached drawing further detailed
Explanation.
The layered dielectric material of one embodiment, including the first fiber non-woven layer of cloth being stacked and the second fiber non-woven
Layer of cloth.
Further, the first fiber non-woven layer of cloth is vinylidene fluoride-hexafluoropropylene copolymer layer, the second fiber non-woven layer of cloth
For vinylidene-trifluoro-ethylene-chlorine fluoride copolymers layer.Further, the first fiber non-woven layer of cloth and the second fiber non-woven
The thickness of layer of cloth can be adjusted as needed.
Further, the thickness of the thickness of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is identical, certainly, at it
In his embodiment, the thickness of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth can also be different, according to obtained layer
The performance of shape dielectric material is adjusted.
In a wherein embodiment, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is 2 layers
~30 layers.
Further, the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth are alternately laminated, and layered dielectric material
Internal structure is preferably centrosymmetric mode.
In a wherein embodiment, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is 2 layers
When, the overlapped way of layered dielectric material is AB, and wherein A is the first fiber non-woven layer of cloth, and B is the second fiber non-woven layer of cloth.
In a wherein embodiment, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is 3 layers
When, the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth are alternately laminated.For example, the overlapped way of layered dielectric material is
ABA type, wherein B one of is represented in the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and A represents the first fiber
Another in nonwoven layer and the second fiber non-woven layer of cloth.
In a wherein embodiment, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is odd number
Layer.Further, layered dielectric material includes middle layer and the first alternating layer group for being respectively arranged on two sides of middle layer and
Two alternating layer groups.Wherein, middle layer is the first fiber non-woven layer of cloth or the second fiber non-woven layer of cloth；First alternating layer group include according to
Secondary alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, the second alternating layer group include alternately stacked successively
First fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and the number of plies of the first alternating layer group and the second alternating layer group is identical.Into
One step, the first alternating layer group is different from the material of middle layer close to one layer of middle layer, and the second alternating layer group is close to middle layer
One layer it is different from the material of middle layer, that is to say, that when middle layer be the first fiber non-woven layer of cloth when, the first alternating layer group is leaned on
One layer of nearly middle layer and the second alternating layer group are the second fiber non-woven layer of cloth close to one layer of middle layer；When middle layer is the
When two fiber non-woven layer of cloths, the first alternating layer group close to one layer of middle layer and the second alternating layer group close to one layer of middle layer
For the first fiber non-woven layer of cloth.For example, the overlapped way of layered dielectric material is (AB)nA(BA)nOr B (AB)nA(BA)nB,
In, A is the first fiber non-woven layer of cloth or the second fiber non-woven layer of cloth；When A is the first fiber non-woven layer of cloth, B is the second fiber
Nonwoven layer；When A is the second fiber non-woven layer of cloth, B is the first fiber non-woven layer of cloth；And 1≤n≤7.
In a wherein embodiment, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is even
Number.Layered dielectric material includes the first alternating layer group and is laminated in the second alternating layer group of the first alternating layer group.Further,
One alternating layer group includes alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth successively, the second alternating layer group packet
Include alternately stacked first fiber non-woven layer of cloth successively and the second fiber non-woven layer of cloth, and the first alternating layer group and the second alternating layer
The number of plies of group is identical.Further, it is leaned on the second alternating layer group close to one layer of the second alternating layer group in the first alternating layer group
One layer of material identical of nearly first alternating layer group, that is to say, that when the first alternating layer group is close to one layer of the second alternating layer group
For the first fiber non-woven layer of cloth when, the second alternating layer group is also the first fiber non-woven layer of cloth close to one layer of the first alternating layer group；
When the first alternating layer group close to one layer of the second alternating layer group be the second fiber non-woven layer of cloth when, the second alternating layer group is close to first
One layer of alternating layer group is also the second fiber non-woven layer of cloth.For example, the overlapped way of layered dielectric material is (AB)m(BA)mOr B
(AB)m(BA)mB, wherein A is the first fiber non-woven layer of cloth or the second fiber non-woven layer of cloth；When A is the first fiber non-woven layer of cloth
When, B is the second fiber non-woven layer of cloth；When A is the second fiber non-woven layer of cloth, B is the first fiber non-woven layer of cloth；And 1≤m≤7.
Further, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is even number, and the first fiber
Nonwoven layer is suitable with the thickness of the second fiber non-woven layer of cloth, in order to obtain the symmetry of layered dielectric material structure, and layer
Vinylidene fluoride-hexafluoropropylene copolymer component and vinylidene-trifluoro-ethylene-chlorine fluoride copolymers component in shape dielectric material
Volume ratio be 50:50.
Above-mentioned layered dielectric material and preparation method thereof, vinylidene fluoride-hexafluoropropylene copolymer layer have high breakdown performance,
And vinylidene-trifluoro-ethylene-chlorine fluoride copolymers have high polarization performance and high energy storage efficiency, and by by inclined fluorine second
Alkene-hexafluoropropylene copolymer layer and vinylidene-trifluoro-ethylene-chlorine fluoride copolymers layer are layered on top of each other to control layered dielectric
The inside mesoscopic structure of material is conducive to inhibit conductance loss and f-e loss inside stratiform dielectric material, so that layer
Shape dielectric material has both high energy storage density and energy storage efficiency simultaneously.
The reason of symmetrical structure designs is：Dielectric type capacitor usually works under alternating electric field, and symmetrical structure is set
Meter ensures dielectric response having the same when capacitor works under positive voltage and reversed negative voltage.
Also referring to Fig. 1, the preparation method of above-mentioned layered dielectric material includes the following steps：
S110, it vinylidene fluoride-hexafluoropropylene copolymer is dissolved in the first solvent obtains the first solution.
In a wherein embodiment, vinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)) is powder state, P
(VDF-HFP) molecular weight is 100,000~1,000,000, further, the molecular weight of P (VDF-HFP) can also be 200,000,350,000,
470000,600,000 or 750,000.
In a wherein embodiment, the trade mark that P (VDF-HFP) is purchased from France Arkema is the P (VDF- of 2800-01
HFP) powder.
In a wherein embodiment, the first solvent is the mixed liquor of n,N-Dimethylformamide and acetone, and N, N-
The volume ratio of dimethylformamide and acetone is 3:2~5:1, further, the volume ratio of n,N-Dimethylformamide and acetone
It can also be 2:1、3:1 or 4:1.
Compared to traditionally only with single n,N dimethylformamide, on the one hand in the mixed solvent addition acetone increases molten
On the other hand the volatility of agent is conducive to the viscosity for improving solution, these are all conducive to increase P (VDF-HFP) and P (VDF-
TrFE-CFE) the spinnability of polymer fiber.
In a wherein embodiment, mass percents of the P (VDF-HFP) in the first solution is 15%~30%.
Further, mass percents of the P (VDF-HFP) in the first solution can also be 17%, 20%, 25% or 27%, preferably
, mass percents of the P (VDF-HFP) in the first solution is 25%.
In a wherein embodiment, so that vinylidene fluoride-hexafluoropropylene copolymer is fully molten by the way of stirring
Solution is in the first solvent, and stir speed (S.S.) when stirring is 200rpm~500rpm, and the time of stirring is 2h~10h.
S120, it vinylidene-trifluoro-ethylene-chlorine fluoride copolymers is dissolved in the second solvent obtains the second solution.
In a wherein embodiment, vinylidene-trifluoro-ethylene-chlorine fluoride copolymers (P (VDF-TrFE-
CFE)) it is powder state, the molecular weight of P (VDF-TrFE-CFE) is 100,000~1,000,000, further, P (VDF-TrFE-CFE)
Molecular weight can also be 200,000,350,000,450,000,650,000 or 850,000.
In a wherein embodiment, the trades mark of the P (VDF-TrFE-CFE) purchased from France Arkema is Piezotech
P (VDF-TrFE-CFE) powder of RT FS.
In a wherein embodiment, the second solvent is the mixed liquor of n,N-Dimethylformamide and acetone, and N, N-
The volume ratio of dimethylformamide and acetone is 3:2~5:1, further, the volume ratio of n,N-Dimethylformamide and acetone
It can also be 2:1、3:1 or 4:1.
In a wherein embodiment, mass percents of the P (VDF-TrFE-CFE) in the second solution be 15%~
30%.Further, mass percents of the P (VDF-TrFE-CFE) in the second solution can also be 18%, 20%, 25% or
27%, it is preferred that mass percents of the P (VDF-TrFE-CFE) in the second solution is 18%.
In a wherein embodiment, P (VDF-TrFE-CFE) is made to be completely dissolved in second by the way of stirring
In solvent, stir speed (S.S.) when stirring is 200rpm~500rpm, and the time of stirring is 2h~10h.
S130, the first solution and the second solution is molded by the way of electrostatic spinning to obtain intermediate, the intermediate
Including the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth being layered on top of each other.
In a wherein embodiment, the first solvent molding is obtained into the first fiber non-woven by the way of electrostatic spinning
Second solvent molding is obtained the second fiber non-woven layer of cloth by layer of cloth by the way of electrostatic spinning.
Further, total number of plies of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth is 2 layers~30 layers；Using quiet
When the mode of Electrospun prepares intermediate, the overlapped way of the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth can be AB
Type, ABA type, (AB)nA(BA)nType, B (AB)nA(BA)nType B, (AB)m(BA)mType or B (AB)m(BA)mType B.Specifically hereinbefore
It has been had a detailed description that, details are not described herein.
Further, when being molded to obtain intermediate by the way of electrostatic spinning, the voltage of electrostatic spinning be 4kV~
15kV, syringe pump inject speed be 0.1mL/h~2mL/h, spinning distance be 5cm~50cm, drum rotation speed be 100rpm~
1000rpm, spinning time are 10min~10h.Further, the spinning distance of electrostatic spinning is preferably 15cm, and drum rotation speed is excellent
It is selected as 300rpm.The time of spinning is generally according to the thickness tune of the number of plies and the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
It is whole.
S140, hot-pressing processing is carried out to intermediate.
In a wherein embodiment, it is 150 DEG C~220 DEG C to carry out hot pressing temperature when hot-pressing processing, further, heat
Pressure temperature can also be 180 DEG C or 200 DEG C, it is preferred that hot pressing temperature is 200 DEG C.
In a wherein embodiment, hot pressing pressure when carrying out hot-pressing processing is 2MPa~20MPa, further,
Hot pressing pressure can also be 6MPa, 10MPa or 15MPa.
In a wherein embodiment, it is 15min~120min to carry out the hot pressing time that hot-pressing processing is, further
, hot pressing time can also be 30min or 60min.
S150, cold quenching processing is carried out to intermediate.
In a wherein embodiment, the step of intermediate progress cold quenching processing, is specifically included：
S151, intermediate is heated.
In a wherein embodiment, temperature when heating to intermediate is 180 DEG C~240 DEG C, heating
The time of processing is 5min~30min.
S152, cooling processing is carried out to intermediate.
In a wherein embodiment, it is specifically to put into intermediate to cool down that intermediate, which is carried out the step of cooling is handled,
Cold quenching is carried out in liquid.Further, coolant liquid is water.
In a wherein embodiment, the cooling temperature that cooling processing is carried out to intermediate is 0~100 DEG C, Ke Yili
Solution, cooling temperature here is the temperature of coolant liquid, is 0~100 DEG C.Further, cool down processing cooling temperature also
It can be 35 DEG C, 45 DEG C, 60 DEG C or 85 DEG C.
Cold quenching is carried out by the temperature of coolant liquid when control cooling processing, there can be the phase structure for adjusting stratiform dielectric material
Composition, to obtain low-loss while ensure the high polarizability of layered dielectric material.With the raising of cooling temperature, P (VDF-
HFP) and in P (VDF-TrFE-CFE) ingredient of nonpolarity α phases gradually increases.For example, when 0 DEG C of cold quenching, P (VDF-HFP) and P
(VDF-TrFE-CFE) phase structure is that polar beta phase coexists with nonpolarity α phases；When 60 DEG C of cold quenchinges, P (VDF-HFP) and P (VDF-
TrFE-CFE) phase structure is mainly nonpolarity α phases.Since relative to polar beta phase, the f-e loss of nonpolar α phases is lower, so
Cold quenching temperature increases, and nonpolar phase content increases, and f-e loss declines.For P (VDF-HFP), nonpolar phase content
The decline of polarizability can be led to by increasing, and in contrast, for P (VDF-TrFE-CFE), nonpolar phase content increases
The polarizability of itself can be made to increase.So comprehensive two kinds of effects, when carrying out cold quenching processing, setting cooling temperature for 0~
100 DEG C, so that the polarizability of layered dielectric material can be maintained at higher level.
S153, processing is dried to intermediate.
In a wherein embodiment, intermediate after taking out in coolant liquid be dried to the water drying on surface from
And obtain layered dielectric material.
In a wherein embodiment, it is 30 DEG C~60 DEG C that the temperature that processing is, which is dried,.Further, it is done
The temperature of dry processing can also be 45 DEG C.
The preparation method of above-mentioned layered dielectric material, using vinylidene fluoride-hexafluoropropylene copolymer layer and vinylidene-three
Vinyl fluoride-chlorine fluoride copolymers layer stackup, vinylidene fluoride-hexafluoropropylene copolymer layer is with high breakdown performance, and fluorine second partially
Alkene-trifluoro-ethylene-chlorine fluoride copolymers Cen has high polarization performance and high energy storage efficiency, and by by vinylidene-six
Fluoropropene copolymer layer and vinylidene-trifluoro-ethylene-chlorine fluoride copolymers layer are layered on top of each other to control stratiform dielectric material
Inside mesoscopic structure, be conducive to inhibit stratiform dielectric material inside conductance loss and f-e loss so that stratiform be situated between
Electric material has both high energy storage density and energy storage efficiency simultaneously.And the preparation method of above-mentioned layered dielectric material is simple, it is easy to accomplish
Industrialized production.
It should be noted that in other embodiments, step S153 can also be omitted.
It is the explanation of specific embodiment below, following embodiment unless otherwise specified, is not then contained except inevitably miscellaneous
The component pointed out is not known in other other than matter.
Embodiment 1
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 40min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；It pushes away
Note speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 40min.Later, (including above-mentioned using the sequence of ABBA
Carry out AB processes) carry out spinning, obtain the fabric nonwoven cloth intermediate with 4 layers of structure.Carried out hot pressing, temperature
200 DEG C, 10MPa, 30min.After taking-up, on heating platform after 200 DEG C of heating 15min in the water of 60 DEG C of input, cold quenching 5min
Afterwards, it is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtains the finally layered dielectric material with 4 layers of structure.
Embodiment 2
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 20min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；It pushes away
Note speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 20min.Later, using the sequence of ABABBABA (including
Above-mentioned carry out AB processes) spinning is carried out, obtain the fabric nonwoven cloth intermediate with 8 layers of structure.Hot pressing is carried out, temperature
200 DEG C of degree, 10MPa, 30min.After taking-up, on heating platform after 200 DEG C of heating 15min in the water of 60 DEG C of input, cold quenching
It after 5min, is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtains the finally layered dielectric with 8 layers of structure
Material.
Embodiment 3
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 10min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；It pushes away
Note speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 10min.Later, using the suitable of ABABABABBABABABA
Sequence (including above-mentioned carry out AB processes) carries out spinning, obtains the fabric nonwoven cloth intermediate with 16 layers of structure.By its into
Row hot pressing, 200 DEG C of temperature, 10MPa, 30min.After taking-up, 200 DEG C of water for heating 60 DEG C of input after 15min on heating platform
In, it after cold quenching 5min, is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtains finally with 16 layers of structure
Layered dielectric material.
Embodiment 4
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 10min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；It pushes away
Note speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 10min.Later, using the suitable of ABABABABBABABABA
Sequence (including above-mentioned carry out AB processes) carries out spinning, obtains the fabric nonwoven cloth intermediate with 16 layers of structure.By its into
Row hot pressing, 200 DEG C of temperature, 10MPa, 30min.After taking-up, 200 DEG C of water for heating 45 DEG C of input after 15min on heating platform
In, it after cold quenching 5min, is placed in 45 DEG C of baking oven, until the water of film surface is thoroughly dried, obtains that finally there are 16 layers of knot
The layered dielectric material of structure.
Embodiment 5
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 10min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；It pushes away
Note speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 10min.Later, using the suitable of ABABABABBABABABA
Sequence (including above-mentioned carry out AB processes) carries out spinning, obtains the fabric nonwoven cloth intermediate with 16 layers of structure.By its into
Row hot pressing, 200 DEG C of temperature, 10MPa, 30min.After taking-up, 200 DEG C of water for heating 0 DEG C of input after 15min on heating platform
In, it after cold quenching 5min, is placed in 45 DEG C of baking oven, until the water of film surface is thoroughly dried, obtains that finally there are 16 layers of knot
The layered dielectric material of structure.
Embodiment 6
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 6.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 8.8mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 600,000, P (VDF-TrFE-CFE) powder is 650,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 1.5mL/h；Drum rotation speed
300rpm；The time of spinning is 10min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；It pushes away
Note speed 1.67mL/h；The time of drum rotation speed 300rpm, spinning are 10min.Later, using the suitable of ABABABABBABABABA
Sequence (including above-mentioned carry out AB processes) carries out spinning, obtains the fabric nonwoven cloth intermediate with 16 layers of structure.By its into
Row hot pressing, 200 DEG C of temperature, 10MPa, 30min.After taking-up, 200 DEG C of water for heating 45 DEG C of input after 15min on heating platform
In, it after cold quenching 5min, is placed in 45 DEG C of baking oven, until the water of film surface is thoroughly dried, obtains that finally there are 16 layers of knot
The layered dielectric material of structure.
Embodiment 7
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
One solution carries out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 9.5min.Then spinning, spinning condition are carried out with the second solution：Voltage 10kV；Distance 15cm；
Inject speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 9.5min.Later, using ABABABABABABABABA
Sequence (including above-mentioned carry out AB processes) carry out spinning, obtain the fabric nonwoven cloth intermediate with 17 layers of structure,
In, A is P (VDF-HFP) fiber non-woven layer of cloth, and B is P (VDF-TrFE-CFE) fiber non-woven layer of cloth.Carried out hot pressing, temperature
200 DEG C, 10MPa, 30min.After taking-up, on heating platform after 200 DEG C of heating 15min in the water of 60 DEG C of input, cold quenching 5min
Afterwards, it is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtains the finally layered dielectric material with 17 layers of structure
Material.
Embodiment 8
Taking 1g P (VDF-HFP) powder to be dissolved in the in the mixed solvent of 2.4mL DMF and 1.6mL acetone, to obtain first molten
Liquid, separately taking 1g P (VDF-TrFE-CFE) powder to be dissolved in the in the mixed solvent of 3.3mL DMF and 2.2mL acetone, to obtain second molten
Liquid, wherein the molecular weight of P (VDF-HFP) powder is that the molecular weight of 470,000, P (VDF-TrFE-CFE) powder is 850,000.First with
Two solution carry out electrostatic spinning, and spinning condition is：Voltage 10kV；Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed
300rpm；The time of spinning is 9.5min.Then spinning, spinning condition are carried out with the first solution：Voltage 10kV；Distance 15cm；
Inject speed 0.67mL/h；The time of drum rotation speed 300rpm, spinning are 9.5min.Later, using ABABABABABABABABA
Sequence (including above-mentioned carry out AB processes) carry out spinning, obtain the fabric nonwoven cloth intermediate with 17 layers of structure,
In, A is P (VDF-TrFE-CFE) fiber non-woven layer of cloth, and B is P (VDF-HFP) fiber non-woven layer of cloth.Carried out hot pressing, temperature
200 DEG C, 10MPa, 30min.After taking-up, on heating platform after 200 DEG C of heating 15min in the water of 60 DEG C of input, cold quenching 5min
Afterwards, it is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtains the finally layered dielectric material with 17 layers of structure
Material.
Embodiment 9
The in the mixed solvent that 2g P (VDF-HFP) powder is dissolved in 4.8mL DMF and 3.2mL acetone is taken to obtain the first solution
Wherein, the molecular weight of P (VDF-HFP) powder is 470,000.Electrostatic spinning is carried out with the first solution, spinning condition is：Voltage 10kV；
Distance 15cm；Inject speed 0.5mL/h；Drum rotation speed 300rpm；The time of spinning is 160min, is obtained among fabric nonwoven cloth
Body.Carried out hot pressing, 200 DEG C of temperature, 10MPa, 30min.After taking-up, put into after 200 DEG C of heating 15min on heating platform
It in 45 DEG C of water, after cold quenching 5min, is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtains final dielectric material
Material.
Embodiment 10
The in the mixed solvent that 2g P (VDF-TrFE-CFE) powder is dissolved in 6.6mL DMF and 4.4mL acetone is taken to obtain
Two solution, wherein the molecular weight of P (VDF-TrFE-CFE) powder is 850,000.Spinning, spinning condition are carried out with the second solution：Electricity
Press 10kV；Distance 15cm；Inject speed 0.67mL/h；Drum rotation speed 300rpm, time of spinning are 160min, obtain fiber without
Woven fabric intermediate.Carried out hot pressing, 200 DEG C of temperature, 10MPa, 30min.After taking-up, 200 DEG C of heating on heating platform
It puts into 45 DEG C of water after 15min, after cold quenching 5min, is placed in 45 DEG C of baking oven, until the water on surface is thoroughly dried, obtain
Final dielectric material.
The first fiber non-woven layer of cloth (a), the P (VDF-TrFE- that P (VDF-HFP) electrostatic spinning in embodiment 1 is obtained
CFE the surface topography (c) and layered dielectric material for the second fiber non-woven layer of cloth (b) and layered dielectric material that) electrostatic spinning obtains
The cross-section morphology (d) of material is scanned Electronic Speculum test, and the results are shown in Figure 2, wherein uses Zeiss when being scanned Electronic Speculum test
The scanning electron microscope instrument of the MWRLIN compact of company is tested.
The copper electrode of a diameter of 3mm will be deposited on layered dielectric material or dielectric material that Examples 1 to 10 is prepared,
Dielectric properties test is carried out again.
Wherein, stratiform Examples 1 to 5 being prepared using the HP4294A precise impedances analyzer of agilent company
The relative dielectric constant of dielectric material is tested, and obtains relative dielectric constant frequency spectrum as shown in figure 3, the specific parameter tested
For：Bias 1V, frequency range 102~107Hz；
Examples 1 to 5 is prepared into using the Premier II ferroelectricity testers of Radiant Technologies companies
To dielectric displacement-electric field curve of layered dielectric material tested, the results are shown in Figure 4, and the specific parameter of test is：It surveys
Try frequency 10Hz；
Examples 1 to 10 is prepared into using the Premier II ferroelectricity testers of Radiant Technologies companies
To layered dielectric material or the energy storage efficiency and energy storage density of dielectric material tested, the results are shown in Table 1, the tool of test
The parameter of body is：Test frequency 10Hz.
Table 1
Pure P (VDF-TrFE-CFE) energy storage density of itself is can be seen that from the energy storage density of embodiment 10 to only have
7.53J/cm3, this is because P (VDF-TrFE-CFE) breakdown is low, and the energy storage efficiency of embodiment 9 can be seen that pure P (VDF-
HFP energy storage efficiency) only has 77.48%, less than 80%.And by the way of being layered on top of each other, a large amount of sight interfaces that are situated between can be introduced,
This interface can hinder the migration of carrier and the growth of electric branch, so as to inhibit leakage current, improve disruptive field intensity.Institute
To be significantly improved relative to P (VDF-TrFE-CFE) disruptive field intensity, energy storage density also improves.And inhibit leakage current notable
It reduces leakage and leads loss, in addition the cold quenching to different water temperatures can be with the f-e loss of inhibition system, phase to the adjusting of system phase structure
Compared with pure P (VDF-HFP), the sample energy storage efficiency of stacking is also increased to 80% or more.
The mixed solvent using proper ratio is can be seen that from Fig. 2 a, b, P (the VDF-HFP) (figures that electrostatic spinning obtains
2a) and P (VDF-TrFE-CFE) (Fig. 2 b) nanofiber surface is smooth, and does not have the phenomenon that beading to occur.By hot pressing, heat
After processing and cold quenching, obtained layered composite film surface is smooth fine and close (Fig. 2 c), and section thickness is uniform, and dense non-porous
(Fig. 2 c) illustrates the thin polymer film that high quality has been prepared.
Fig. 3 is the relative dielectric constant of Examples 1 to 5 sample with the variation relation figure of frequency.Wherein, Examples 1 to 3
Sample uses identical heat treatment process, and the only internal number of plies is different, and test result can be seen that and see, with the internal number of plies
Increase, the relative dielectric constant of sample is continuously increased, this is because the internal number of plies increases, Jie that can increase system sees interface face
Product, to increase the interfacial polarization of system, improves whole dielectric constant.The sample of comparative example 3~5, the internal number of plies
It is identical, the difference is that using different cold quenching technique, it can be seen that with the decline of the water temperature of cold quenching, the opposite dielectric of system
Constant also declines.This is because when cold quenching water temperature drop, the phase structure of the phase P (VDF-TrFE-CFE) in system is by non-pole
Based on property phase, be changed into nonpolar phase mutually coexists with polarity, and for P (VDF-TrFE-CFE), the idol in nonpolar phase
Pole is easier to issue raw overturning in outer field action, to dielectric constant bigger.
Fig. 4 is the polarization curve of Examples 1 to 5.Comparative example 1~3, it can be seen that identical in heat treatment process
In the case of, the number of plies is more inside system, and the disruptive field intensity of system is higher, and electric polarization value is also high, thus it is close to obtain discharge energy
Degree is also bigger.This is because the sight interface that is situated between is weak electric field area, the growth of electric branch can be inhibited, the system inside number of plies is more, is situated between
Sight interface is more, and stronger to the inhibiting effect of electric branch, the disruptive field intensity of system is also higher.Comparative example 3~5, can be with
Find out, the number of plies is identical inside system, and with the reduction of cold quenching water temperature, the polarization curve of system gradually becomes fat, this
Mean that the dielectric loss of system gradually increases, efficiency continuously decreases.This is because with the decline of cold quenching temperature, the phase of system
Structure is by being changed into the state mutually coexisted with non-polar and polar based on nonpolar phase, and the f-e loss of polarity phase is big, the phase
Increase can increase the dielectric loss of system.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of layered dielectric material, which is characterized in that including the first fiber non-woven layer of cloth for being stacked and the second fiber without
Woven fabric layer, the first fiber non-woven layer of cloth are vinylidene fluoride-hexafluoropropylene copolymer layer, and the second fiber non-woven layer of cloth is
Vinylidene-trifluoro-ethylene-chlorine fluoride copolymers layer, the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
Total number of plies be 2~30 layers.
2. layered dielectric material according to claim 1, which is characterized in that the first fiber non-woven layer of cloth and described
Total number of plies of two fiber non-woven layer of cloths is 3 layers, the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth alternating layer
It is folded；
Or, the overlapped way of layered dielectric material is ABA, wherein B represents the first fiber non-woven layer of cloth and described the
One of in two fiber non-woven layer of cloths, A is represented in the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth
Another.
3. layered dielectric material according to claim 1, which is characterized in that the first fiber non-woven layer of cloth and described
Total number of plies of two fiber non-woven layer of cloths is odd number, and layered dielectric material includes middle layer and is respectively arranged on the middle layer two
The the first alternating layer group and the second alternating layer group of a side；The middle layer is the first fiber non-woven layer of cloth or the second fiber non-woven
Layer of cloth, the first alternating layer group include alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and described
Two alternating layer groups include alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, and the first alternating layer group
And the number of plies of the second alternating layer group is identical；One layer and the middle layer of the first alternating layer group close to the middle layer
Material it is different, the second alternating layer group is different from the material of the middle layer close to one layer of the middle layer；
Or, the overlapped way of layered dielectric material is (AB)nA(BA)nOr B (AB)nA(BA)nB, wherein A represents described
One of in one fiber non-woven layer of cloth and the second fiber non-woven layer of cloth, B represent the first fiber non-woven layer of cloth and
Another in the second fiber non-woven layer of cloth；And 1≤n≤7.
4. layered dielectric material according to claim 1, which is characterized in that the first fiber non-woven layer of cloth and described
Total number of plies of two fiber non-woven layer of cloths is even number, and layered dielectric material includes the first alternating layer group and is laminated in described first
Second alternating layer group of alternating layer group, the first alternating layer group include that alternately stacked first fiber non-woven layer of cloth and second are fine
Nonwoven layer is tieed up, the second alternating layer group includes alternately stacked first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth,
And the number of plies of the first alternating layer group and the second alternating layer group is identical；Close to described second in the first alternating layer group
One layer of alternating layer group and one layer of the material identical close to the first alternating layer group in the second alternating layer group；
Or, the overlapped way of layered dielectric material is (AB)m(BA)mOr B (AB)m(BA)mB, wherein A represents the first fiber
One of in nonwoven layer and the second fiber non-woven layer of cloth, B represents the first fiber non-woven layer of cloth and second fibre
Tie up another in nonwoven layer；And 1≤m≤7.
5. such as the preparation method of Claims 1 to 4 any one of them layered dielectric material, which is characterized in that including following step
Suddenly：
Vinylidene fluoride-hexafluoropropylene copolymer is dissolved in the first solvent and obtains the first solution；
Vinylidene-trifluoro-ethylene-chlorine fluoride copolymers are dissolved in the second solvent and obtain the second solution；
First solution and second solution is molded by the way of electrostatic spinning to obtain intermediate, the intermediate packet
Include the first fiber non-woven layer of cloth and the second fiber non-woven layer of cloth being layered on top of each other；Wherein, first solution is molded to obtain first
Fiber non-woven layer of cloth, second solution are molded to obtain the second fiber non-woven layer of cloth；The first fiber non-woven layer of cloth with it is described
Total number of plies of second fiber non-woven layer of cloth is 2 layers~30 layers；
Hot-pressing processing is carried out to the intermediate；And
Cold quenching processing is carried out to the intermediate.
6. the preparation method of layered dielectric material according to claim 5, which is characterized in that first solvent is selected from N,
The mixed liquor of dinethylformamide and acetone, wherein n,N-Dimethylformamide and the volume ratio of acetone are 3:2~5:1；
And/or second solvent is selected from the mixed liquor of n,N-Dimethylformamide and acetone, wherein N, N- dimethyl formyl
The volume ratio of amine and acetone is 3:2~5:1.
7. the preparation method of layered dielectric material according to claim 5, which is characterized in that the vinylidene-hexafluoro
Mass percent of the propylene copolymer in first solution is 15%~30%；
And/or mass percent of the vinylidene-trifluoro-ethylene-chlorine fluoride copolymers in second solution is
15%~30%.
8. the preparation method of layered dielectric material according to claim 5, which is characterized in that described using electrostatic spinning
Voltage is 4kV~15kV, note in the step of mode is separately formed first solution and second solution to obtain intermediate
The speed of injecting for penetrating pump is 0.1mL/h~2mL/h, and spinning distance is 5cm~50cm, and drum rotation speed is 100rpm~1000rpm,
The spinning time is 10min~10h.
9. the preparation method of layered dielectric material according to claim 5, which is characterized in that the hot pressing when hot-pressing processing
Temperature is 150 DEG C~220 DEG C, and hot pressing pressure is 2MPa~20MPa, and hot pressing time is 15min~120min.
10. the preparation method of layered dielectric material according to claim 5, which is characterized in that the step of the cold quenching processing
Suddenly it specifically includes：
The intermediate is heated, the temperature of the heat treatment is 180 DEG C~240 DEG C, the heat treatment
Time is 5min~30min；And
Cooling processing is carried out to the intermediate, the cooling temperature of the cooling processing is 0~100 DEG C, the time for the processing that cools down
For 2min~15min.
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| CN101356603A (en) * | 2005-12-28 | 2009-01-28 | 宾夕法尼亚州研究基金会 | High electric energy density polymer capacitors with fast discharge speed and high efficiency based on unique poly(vinylidene fluoride) copolymers and terpolymers as dielectric materials |
| CN107705985A (en) * | 2017-10-13 | 2018-02-16 | 清华大学 | A kind of high energy storage efficiency ferroelectric polymers based dielectric film, and its production and use |
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| CN107705985A (en) * | 2017-10-13 | 2018-02-16 | 清华大学 | A kind of high energy storage efficiency ferroelectric polymers based dielectric film, and its production and use |
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