CN109461577A - A kind of preparation method and application of dielectric energy-storage composite material - Google Patents
A kind of preparation method and application of dielectric energy-storage composite material Download PDFInfo
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- CN109461577A CN109461577A CN201811295094.4A CN201811295094A CN109461577A CN 109461577 A CN109461577 A CN 109461577A CN 201811295094 A CN201811295094 A CN 201811295094A CN 109461577 A CN109461577 A CN 109461577A
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000004146 energy storage Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003989 dielectric material Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011229 interlayer Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 54
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 42
- 229960003638 dopamine Drugs 0.000 claims description 21
- 239000002070 nanowire Substances 0.000 claims description 18
- 229910002113 barium titanate Inorganic materials 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920002396 Polyurea Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005034 decoration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 35
- 239000011521 glass Substances 0.000 description 16
- 230000035939 shock Effects 0.000 description 12
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 10
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 4
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 description 4
- 229960004502 levodopa Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 description 2
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000013047 polymeric layer Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
-
- 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
- H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
- H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/60—Composite insulating bodies
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of preparation method and applications of dielectric energy-storage composite material.Preparation method of the present invention includes: by the solution coating containing Inorganic Dielectric Material and polymer on substrate, and under the conditions of vibration, so that Inorganic Dielectric Material settles, be then heating and curing molding；Solidification gained film is removed from substrate, is then bonded two pieces of films as binding face using the one side being in contact with substrate, it is then hot-forming, obtain the dielectric energy-storage composite material of interlayer structure.Without general with traditional preparation methods in the method for the present invention, it needs to prevent the infall process of dielectric material in the solution, the natural subsidence of dielectric material can be utilized instead, to generate the transition zone of dielectric material change of gradient, this not only simplifies preparation flow steps, simultaneously also can be reduced Macroscopic physical interface, and can be avoided each interlayer materials due to difference it is excessive caused by breakdown voltage it is too low the problems such as, be effectively improved the performance of dielectric energy-storage composite material.
Description
Technical field
The present invention relates to Material Fields, in particular to a kind of preparation method and application of dielectric energy-storage composite material.
Background technique
In recent years, flourishing with semicon industry, electronic product is also increasingly towards miniaturization and intelligentized side
To development.For capacitor as one of component part mostly important in electronic product, performance determines electricity to a certain extent
The quality and effect of sub- product, and the dielectric material as capacitor core material, electric property is for capacitor or even electricity
The performance of sub- product is all to have important influence.
Currently, common dielectric material includes traditional Inorganic Dielectric Material and polymer resin material, both materials
Material, which suffers from, to be widely applied.However, since Inorganic Dielectric Material breakdown strength is lower, thus cause its application limited；And gather
Polymer resin material is although easier to process, and with organic circuit board good compatibility, but its dielectric constant is lower, equally also limits
Its use scope.
In order to meet high dielectric constant, resistance to breakdown simultaneously, the characteristics such as easy processing are compound with Inorganic Dielectric Material by polymer
Made of dielectric composite material come into being.And there is lamination/multilayer dielectric composite material, it can even more show high dielectric
The excellent characteristics such as constant, low-dielectric loss, high breakdown field strength and high energy storage density.
In existing method, multilayer high dielectric thin film mostly uses curtain coating or the method for hot pressing to prepare, that is, passes through material in layer
Material pours to form lamination/multilayer dielectric composite material, although prepared dielectric composite material better performances, preparation process is multiple
It is miscellaneous, the sedimentation and reunion that avoid high dielectric filler as far as possible are also needed during the preparation process, it is complicated for operation.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of dielectric energy-storage composite material, and the method for the present invention has
Simple process, and the advantages that material interlayer difference is small, and disruptive field intensity is high.
The second object of the present invention is to provide a kind of dielectric energy-storage composite material.
The third object of the present invention is to provide a kind of application of dielectric energy-storage composite material.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of dielectric energy-storage composite material, the dielectric energy-storage composite material are three-decker, comprising: upper layer and lower layer polymerization
Nitride layer and Inorganic Dielectric Material-polymer composite layer middle layer；The dielectric energy-storage composite material is by two panels double layer material warm
It is molded, wherein every double layer material includes polymeric layer and Inorganic Dielectric Material-polymer composite layer.
Preferably, in dielectric energy-storage composite material of the present invention, the Inorganic Dielectric Material is nano inorganic dielectric
Material；It is furthermore preferred that the nano inorganic dielectric material includes: at least one in nano wire, nanometer sheet and nano particle
Kind；It is furthermore preferred that the inorganic nano dielectric material includes: barium titanate, strontium titanates, barium strontium titanate and nano titania
At least one of material.
Preferably, in dielectric energy-storage composite material of the present invention, upper polymer layer includes: Kynoar, ring
Oxygen resin, polyvinylidene fluoride copolymer, polypropylene, polyester, at least one of polyureas and polyimide layer；And/or lower layer
Polymeric layer includes: Kynoar, and epoxy resin, polyvinylidene fluoride copolymer, polypropylene, polyester, polyureas and polyamides are sub-
At least one of amine layer；It is furthermore preferred that upper polymer layer is identical as the material of lower polymer layer.
Meanwhile the present invention also provides a kind of preparation methods of dielectric energy-storage composite material, comprising: will contain inorganic dielectric
The solution coating of material and polymer under the conditions of vibration, so that Inorganic Dielectric Material settles, is then heating and curing on substrate
Molding；Solidification gained film is removed from substrate, two pieces of films are bonded using the one side being in contact with substrate as binding face,
It is hot-forming, obtain the dielectric energy-storage composite material of interlayer structure.
It preferably, further include redisperse after being surface modified Inorganic Dielectric Material in preparation method of the present invention
Step in solution.
Preferably, in preparation method of the present invention, the step of Inorganic Dielectric Material is surface modified include: by
Inorganic Dielectric Material carries out surface coating decoration with dopamine.
Preferably, in preparation method of the present invention, the Inorganic Dielectric Material is nano inorganic dielectric material；More preferably
, the nano inorganic dielectric material includes: at least one of nano wire, nanometer sheet and nano particle；It is furthermore preferred that
The inorganic nano dielectric material includes: barium titanate, strontium titanates, in barium strontium titanate and titanium dioxide nano material at least
It is a kind of.
Preferably, in preparation method of the present invention, the polymer includes: Kynoar, and epoxy resin gathers inclined fluorine
Ethylene copolymer, polypropylene, polyester, at least one of polyureas and polyimides.
Meanwhile the present invention also provides dielectric energy-storage composite materials of the present invention in capacitor or the preparation of electrostatic accumulator
Using.
Further, present invention provides devices or device comprising dielectric energy-storage composite material of the present invention.
Compared with prior art, the invention has the benefit that
In the present invention, by using the mode of short time vibration sedimentation, the biggish Inorganic Dielectric Material of density can be made
It settles in the solution, obtains the Inorganic Dielectric Material-polymer composite layer for being distributed in film bas, and after being heating and curing, obtain
To the dielectric composite film of " 1.5 " layer, 3 layers of dielectric composite film of sandwich structure are finally prepared using heat pressing process.Thus, with
Traditional handicraft can pass through instead comparatively, without preventing the infall process of dielectric material in the solution in the method for the present invention
The natural subsidence of dielectric material, to generate the transition zone of dielectric material change of gradient, this can not only simplify preparation flow step,
Simultaneously can also avoid each interlayer materials due to difference it is excessive caused by breakdown voltage it is too low the problems such as, be effectively improved dielectric store up
The performance of energy composite material.
Further, since the one side of " 1.5 " layer dielectric composite film patch substrate is flat smooth surface, and ingress of air
There is cell configuration on surface on one side, can guarantee interlayer physical circle that three layers of dielectric composite film is formed by being bonded by this method
Face and laminated film two sides are smooth, conducive to breakdown voltage is further promoted.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is dielectric energy-storage composite material synthesis flow schematic diagram of the present invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The preparation method of dielectric energy-storage composite material provided by the present invention is that one kind is successively poured different from tradition with shape
At the freshly prepared route of laminated construction, for conventional method, can not only simple flow step operation, while can also
Improve the electric property of dielectric energy-storage composite material.
Specifically, preparation method of the present invention mainly applies the following raw material:
(1) nano inorganic dielectric material；
In the present invention, the raw material form of raw material nano Inorganic Dielectric Material is in nano wire, nanometer sheet and nano particle
At least one；
Specifically, inorganic nano dielectric material used includes: barium titanate nano line, barium titanate nano piece, carbon in the present invention
Sour barium nano particle；And strontium titanates nano wire, strontium titanate nanometer piece, strontium titanate nanoparticles；Barium strontium titanate nano wire, metatitanic acid
Strontium barium nano particle, barium strontium titanate nanometer sheet；And titanium dioxide receives line, titanium dioxide nanoplate and nano titania
At least one of particle；
And as above raw material can be marketable material, or is prepared by conventional method in that art.
(2) polymer
Specifically include that Kynoar, epoxy resin, polyvinylidene fluoride copolymer, polypropylene, polyester, polyureas and poly-
At least one of acid imide.
(3) solvent
As to disperse nano inorganic dielectric material and dissolve polymer raw material, the present invention in, preferably with NMP (N-
Methyl pyrrolidone) it is used as solvent, it is the barium titanate in laminated film that NMP, which can slow down curing time due to boiling point height,
Nano wire provides the time sufficiently settled.
Further, the present invention includes as flowed down with the specific steps that raw material as above carries out the preparation of dielectric energy-storage composite material
Journey:
(1) nano inorganic dielectric material surface is modified
In order to improve the dispersibility of nano inorganic dielectric material in a polymer matrix, received in the present invention firstly for inorganic
Rice dielectric material is surface modified cladding, by use modification of the dopamine for nano inorganic dielectric material, with improvement
Its dispersibility in basis material.
It can specifically carry out as follows:
It after the cleaning of nano inorganic dielectric material, is scattered in Dopamine hydrochloride solution, pH to 8.5 is then adjusted with ammonium hydroxide
Left and right, after being stirred, is centrifuged after being mixed with respectively with deionized water and ethanol solution, is then dried in vacuo, obtain table
The nano inorganic dielectric material that face has dopamine to coat.
(2) dielectric energy-storage composite material synthesizes
Firstly, by after surface modification Inorganic Dielectric Material and polymer according to required weight proportion weigh after, be added it is molten
In agent, be sufficiently stirred, and be ultrasonically treated, obtain it is evenly dispersed have Inorganic Dielectric Material, and dissolved with the solution of polymer.
Then, with reference to Fig. 1, carry out including curtain coating, and vibration, removing and hot pressing and etc. specific molding process, specifically
Process can refer to Fig. 1 (following steps (i)-(iv) correspond respectively to 4 processes in Fig. 1).
(i) substrate (preferably glass substrate) cleaning is placed on shock platforms, then by solution coating in substrate
On (solution can be first poured into one end of substrate, then solution is laid on substrate with scraper, and guarantee liquid film thickness
Degree is uniform)；
(ii) shock platforms are opened, amplitude is adjusted as far as possible to reduced levels, and vibration frequency is adjusted to higher level, machinery vibration
It is dynamic, enable Inorganic Dielectric Material natural subsidence in polymer matrix body；
After vibration a period of time (preferably 10min), stops vibration, and substrate is transferred to drying in vacuum drying oven, remove
Residual solvent, film-forming.
This step is main innovation place of the invention, different from being superimposed hot pressing after the layer-by-layer curtain coating in conventional method, and
Control the operation of the sedimentation of casting processes dielectric material.In the present invention, copies in mixed mud work progress and shaken using mixed mud
Device is moved to drive away the technique that wherein bubble keeps mixed mud closely knit with this, using miniature shock platform, slightly larger inorganic of density is allowed to fill out
Expect (the nano inorganic dielectric material of the surface modification of dopamine) sedimentation.
After short time vibration sedimentation, the nanometer dielectric material-polymer that can obtain being distributed in film bas is compound
Layer (solvent gradually evaporates in the process).Moreover, in this layer, the density of inorganic nano dielectric material changes (more in gradient
It is higher close to substrate density)；Meanwhile the upper layer of formed film is the polymerization dielectric material for being practically free of inorganic nano dielectric material
The bed of material.
Further solidify through heating in vacuum, forms polymeric layer-nanometer dielectric material/polymer composite layer double-layer structure
Film.
(iii) formed film is removed from substrate, then, two double-layer structures are film adhered, binding face is pair
Answer film to be in contact with substrate smooth side (since this face is directly contacted with substrate, thus be formed by face be shiny surface, and this
It is also possible that further formed physical interface is smooth after fitting, be conducive to the promotion of breakdown voltage), i.e., so that being deposited with nothing
The side of machine nanometer dielectric material is bonded；
Wherein, the raw materials used inorganic nano dielectric material of two double-layer structure film preparations and raw polymer, can be with
Respectively individually optional is same or different.
(iv) it finally, carry out is hot-forming, obtains poly- with polymerinorganic nanometer dielectric material/polymer composite layer-
Close the dielectric energy-storage composite material of the three-layer sandwich structure of object.
In the dielectric energy-storage composite material as prepared by as above method of the invention, upper and lower level is to be practically free of a nanometer dielectric material
The straight polymer base of material, as breakdown layer；And middle layer is that nanometer dielectric material/polymer composite layer is (compound by two
Lamination is closed and is formed), as high dielectric layer.
Since polymeric base layer and inorganic nano dielectric material/polymeric base layer are generated by way of natural subsidence,
Therefore transition zone is produced, there are depth-gradeds for nano wire concentration, thus the laminated film as obtained by the method for the present invention can be with
It effectively avoids due to the problem that interlayer materials difference is too big and causes breakdown voltage too low.
Meanwhile technique is prepared separately compared to traditional three layers, The present invention reduces preparation steps, and reduce Macroscopic physical
Interface (is optimized for one layer of macroscopic interface from original two macroscopic interfaces), while reducing the environment in preparation or transfer process
The influence of factor.
Using traditional complex method, the breakdown voltage of obtained dielectric composite material is 200-300V/um.And this hair
Bright method can not only simplify experimental procedure, while the breakdown voltage of dielectric composite material can also be promoted to 350-400V/
Um or more.Meanwhile on the basis of guaranteeing that dielectric constant is constant, energy storage density and breakdown electric field are quadratic relationship, therefore this hair
The energy storage density of bright dielectric composite material can at least promote 78% on the basis of original dielectric composite material.
And the dielectric energy-storage composite material as prepared by method as above, due to can be used in good electric property
The preparation of the devices such as capacitor or electrostatic accumulator, and then in all kinds of devices.
The preparation of 1 barium titanate nano line composite three-layer dielectric energy-storage composite material of embodiment
1. preparing secondary Hydrothermal Growth preparation BaTiO3Nano wire, the filler component as multilayer high dielectric thin film.Tool
Body includes:
(i) by TiO2Nanometer powder is added in NaOH solution, is mixed into the water heating kettle of polytetrafluoroethyllining lining after stirring 2h
It tightens, places it in hydro-thermal reaction 72h in 200 DEG C of environment, obtain white powder Na2Ti3O7, filter with deionized water clear
It washes, and 90 DEG C of drying.
(ii) by gained Na2Ti3O7Powder is slowly added to Ba (OH)2·8H22h is stirred in O solution, is finally placed in polytetrafluoro
It is tightened in the water heating kettle of ethylene liner, hydro-thermal reaction for 24 hours, is cooled to room temperature in 95 DEG C of environment, obtains barium titanate nano line.
2. dopamine is to BaTiO3The surface modification of nano wire
By BaTiO3It is scattered in Dopamine hydrochloride solution after nano wire cleaning, and pH to 8.5 is adjusted with weak ammonia liquor, then
60 DEG C of stirring 17h finally mix centrifugation with ethanol solution repeatedly with deionized water respectively, and 80 DEG C of vacuum drying for 24 hours, obtain surface
Dopamine after modification coats BaTiO3Nano wire.
3. dopamine BaTiO3Nano wire/PVDF based coextruded film preparation
Dopamine BaTiO is matched needed for weighing3Nano wire and PVDF base polymeric material, by two kinds of material dispersed/dissolveds
In nmp solvent, simultaneously ultrasound 2h is stirred for 24 hours, finely dispersed dopamine BaTiO is obtained3Nano wire/PVDF base composite solution.
After cleaning glass substrate, it is placed on clean miniature shock platform, then, by dopamine BaTiO3Nanometer
Line/PVDF base composite solution falls in glass substrate one end, gently streaks solution surface with the scraper of fixed thickness, guarantees that liquid film is thick
Degree is uniform；
Then, miniature shock platform is opened, amplitude is transferred to small as far as possible, vibration frequency is turned up, and mechanical shock 10min makes
BaTiO3Nano wire natural subsidence；
After 10min, glass substrate is transferred in 40 DEG C of vacuum drying ovens, dry 24 hours to drive away residual solvent and solidify
Film forming.
Gained film is removed from glass surface, takes two dopamine BaTiO prepared3Nano wire/PVDF base is compound
Film, the one side that two films are affixed on glass substrate is opposite to be bonded, and is put into mold hot-forming through 200 DEG C, is had
The amine-modified barium titanate nano line laminated film of the DOPA of sandwich structure.
The preparation of 2 strontium titanate nanoparticles composite three-layer dielectric energy-storage composite material of embodiment
By strontium titanate nanoparticles (can conventionally prepare, for details, reference can be made to prior art CN102139916A,
CN104003437A etc.) it is scattered in Dopamine hydrochloride solution, and pH to 8.5, then 60 DEG C of stirring 17h are adjusted with weak ammonia liquor,
Centrifugation is finally mixed with ethanol solution repeatedly with deionized water respectively, 80 DEG C of vacuum drying for 24 hours, obtain DOPA after surface modification
Amine coats strontium titanate nanoparticles.
Then, proportion dopamine strontium titanate nanoparticles and epoxy resin base polyalcohol material needed for weighing, by two kinds of materials
Material is dispersed/dissolved in nmp solvent, is stirred for 24 hours, and ultrasound 4h, is obtained finely dispersed dopamine strontium titanate nanoparticles/ring
Epoxy resin-based composite solution.
After cleaning glass substrate, it is placed on clean miniature shock platform, then, by dopamine strontium titanates nanometer
Grain/epoxy resin-matrix composite solution falls in glass substrate one end, gently streaks solution surface with the scraper of fixed thickness, guarantees liquid
Film thickness is uniform；
Then, miniature shock platform is opened, amplitude is transferred to small as far as possible, vibration frequency is turned up, and mechanical shock 15min makes
Strontium titanate nanoparticles natural subsidence；
Then, glass substrate is transferred in 45 DEG C of vacuum drying ovens, it is dry for 24 hours to drive away residual solvent and film-forming.
Gained film is removed from glass surface, takes two dopamine prepared strontium titanate nanoparticles/epoxy resin
Based coextruded film, the one side that two films are affixed on glass substrate is opposite to be bonded, and is put into mold hot-forming through 220 DEG C, is obtained
To the amine-modified strontium titanate nanoparticles laminated film of DOPA with sandwich structure.
The preparation of 3 barium strontium titanate nanometer sheet composite three-layer dielectric energy-storage composite material of embodiment
Barium strontium titanate nanometer sheet (can be prepared conventionally, for details, reference can be made to prior art CN103523824A etc.)
It is scattered in Dopamine hydrochloride solution, and pH to 8.5 is adjusted with weak ammonia liquor, then 60 DEG C of stirring 17h, finally use deionization respectively
Water mixes centrifugation with ethanol solution repeatedly, and for 24 hours, the dopamine cladding strontium titanates obtained after surface modification receives barium for 80 DEG C of vacuum drying
Nanometer sheet.
Then, proportion dopamine barium strontium titanate nanometer sheet and PI base polymeric material needed for weighing, by two kinds of materials dispersions/
It is dissolved in nmp solvent, stirs for 24 hours, and ultrasound 4h, it is compound to obtain finely dispersed dopamine barium strontium titanate nanometer sheet/PI base
Solution.
After cleaning glass substrate, it is placed on clean miniature shock platform, then, by dopamine barium strontium titanate nanometer
Piece/PI base composite solution falls in glass substrate one end, gently streaks solution surface with the scraper of fixed thickness, guarantees thickness of liquid film
Uniformly；
Then, miniature shock platform is opened, amplitude is transferred to small as far as possible, vibration frequency is turned up, and mechanical shock 15min makes
Barium strontium titanate nanometer sheet natural subsidence；
Then, glass substrate is transferred in 45 DEG C of vacuum drying ovens, it is dry for 24 hours to drive away residual solvent and film-forming.
Gained film is removed from glass surface, takes two dopamine barium strontium titanate nanometer sheet/PI bases prepared compound
Film, the one side that two films are affixed on glass substrate is opposite to be bonded, and is put into mold hot-forming through 220 DEG C, is had
The amine-modified barium strontium titanate nanometer sheet laminated film of the DOPA of sandwich structure.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of dielectric energy-storage composite material, which is characterized in that the dielectric energy-storage composite material is three-decker, comprising: on
Lower two layers of polymers layer and Inorganic Dielectric Material-polymer composite layer middle layer；
Wherein, dielectric energy-storage composite material is obtained by two panels double layer material is hot-forming, and every double layer material includes polymer
Layer and Inorganic Dielectric Material-polymer composite layer.
2. dielectric energy-storage composite material according to claim 1, which is characterized in that the Inorganic Dielectric Material is nanometer nothing
Machine dielectric material；
Preferably, the nano inorganic dielectric material includes: at least one of nano wire, nanometer sheet and nano particle；
Preferably, the inorganic nano dielectric material includes: barium titanate, strontium titanates, barium strontium titanate and nano titania material
At least one of material.
3. dielectric energy-storage composite material according to claim 1, which is characterized in that upper polymer layer includes: to gather inclined fluorine
Ethylene, epoxy resin, polyvinylidene fluoride copolymer, polypropylene, polyester, at least one of polyureas and polyimide layer；
And/or lower polymer layer includes: Kynoar, epoxy resin, polyvinylidene fluoride copolymer, polypropylene, polyester,
At least one of polyureas and polyimide layer；
Preferably, upper polymer layer is identical as the material of lower polymer layer.
4. a kind of preparation method of dielectric energy-storage composite material characterized by comprising Inorganic Dielectric Material and polymerization will be contained
The solution coating of object is on substrate, and under the conditions of vibration, so that Inorganic Dielectric Material settles, be then heating and curing molding；
Solidification gained film is removed from substrate, two pieces of films are bonded using the one side being in contact with substrate as binding face,
It is hot-forming, obtain the dielectric energy-storage composite material of interlayer structure.
5. the preparation method according to claim 4, which is characterized in that the preparation method further includes by Inorganic Dielectric Material
After being surface modified, the step that is redispersed in solution.
6. preparation method according to claim 5, which is characterized in that the step that the Inorganic Dielectric Material is surface modified
It suddenly include: that Inorganic Dielectric Material is subjected to surface coating decoration with dopamine.
7. the preparation method according to claim 4, which is characterized in that the Inorganic Dielectric Material is nano inorganic dielectric material
Material；
Preferably, the nano inorganic dielectric material includes: at least one of nano wire, nanometer sheet and nano particle；
Preferably, the inorganic nano dielectric material includes: barium titanate, strontium titanates, barium strontium titanate and nano titania material
At least one of material.
8. the preparation method according to claim 4, which is characterized in that the polymer includes: Kynoar, asphalt mixtures modified by epoxy resin
Rouge, polyvinylidene fluoride copolymer, polypropylene, polyester, at least one of polyureas and polyimides.
9. dielectric energy-storage composite material of any of claims 1-3 or the side as described in any one of claim 4-8
Application of the dielectric energy-storage composite material prepared by method in capacitor or the preparation of electrostatic accumulator.
10. including dielectric energy-storage composite material of any of claims 1-3 or by any one of claim 4-8 institute
State the device or device of dielectric energy-storage composite material prepared by method.
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| CN112708160A (en) * | 2020-12-28 | 2021-04-27 | 宁波大学 | Polymer-based composite material for capacitor and preparation method thereof |
| CN112708160B (en) * | 2020-12-28 | 2023-01-17 | 宁波大学 | Polymer-based composite material for capacitor and preparation method thereof |
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