CN105219021B - A kind of dielectric composite material - Google Patents
A kind of dielectric composite material Download PDFInfo
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- CN105219021B CN105219021B CN201510511446.5A CN201510511446A CN105219021B CN 105219021 B CN105219021 B CN 105219021B CN 201510511446 A CN201510511446 A CN 201510511446A CN 105219021 B CN105219021 B CN 105219021B
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Abstract
The invention discloses a kind of dielectric composite materials of multilayered structure, this multilayered structure specifically refers to be composed of with pure polymer layer inorganic/polymer composite layer, the number of plies of the dielectric composite material is no less than two layers, and the volume fraction of the polymeric layer is the 10%~45% of the dielectric composite material volume fraction.The preparation method of the present invention is simple, substantially improves single layer composite resistance and wears the problem of electric field ability reduces, the energy storage for being effectively improved composite material is horizontal.
Description
Technical field
The present invention relates to a kind of dielectric composite materials, have high energy storage density under high electric field more particularly to a kind of prepare
Composite material.
Background technology
In the industrial society that fossil energy crisis becomes increasingly conspicuous, the dielectric composite material of high energy storage density is increasingly by quotient
The concern of industry and science.Ceramic/polymer composite is considered as one of most potential dielectric composite material, because should
Material can be in combination with the feature that ceramic dielectric constant is big and polymer flexibility is good, according to dielectric material energy storage density (Ue)
Calculation formula：
Wherein, ε0, εrIt is respectively permittivity of vacuum, the electric field of composite material relative dielectric constant and application with E.From public affairs
Formula can obtain, improve the density of energy storage, then seeking to improve the high-k and high strike of composite material simultaneously
Wear electric field.Ceramic/polymer composite has been widely studied, and most of research concentrates on how improving Jie of composite material
Electric constant mutually modifies filling phase surface by exploring high performance filling with different methods, normal with the dielectric for improving compound
Number.However they all can all can not in face of a common problem due to the introducing of the very remote out-phase material of interfacial property difference
With the structure of the destruction polymer matrix of degree, and inevitable defect is introduced, it can be different to the anti-breakdown electric field of composite material
The reduction of degree.
The breakdown electric field for the energy-storage composite material reported at present is generally concentrated at this region 100-250kV/mm, that is,
It says, dielectric composite material is other than dielectric constant also has tremendous increase space, and there is also larger for the ability of anti-breakdown electric field
Room for promotion therefore how to realize that high-k and highly resistance breakdown electric field are the research of current dielectric composite material simultaneously
One difficult point.
Invention content
It is an object of the invention to the design innovation from structure, provide that a kind of preparation method is simple, has highly resistance breakdown potential
The composite material of field and high-k, to greatly improve its energy storage densities.
The technical scheme is that：
A kind of dielectric composite material is combined with polymeric layer by inorganic matter/polymer composite layer and forms multilayered structure,
The number of plies of the dielectric composite material is no less than two layers, and the volume fraction of the polymeric layer is the dielectric composite wood
Expect the 10%~45% of volume fraction.
Further, the dielectric composite material is replaced by inorganic matter/polymer composite layer with polymeric layer folded
Add to form multilayered structure, and no less than three layers, the outermost layer of dielectric composite material is inorganic matter/polymer composite layer.
Further, the number of plies of the dielectric composite material can be 3 layers, 4 layers, 5 layers or more layers.
Further, when the number of plies of the dielectric composite material is 3 layers, the volume fraction of the polymeric layer is
The 25%~35% of the dielectric composite material volume fraction.
Further, when the number of plies of the dielectric composite material is 5 layers, the volume fraction of the polymeric layer is
The dielectric composite material volume fraction is more preferably 25%~45%；Most preferably 25%~35%.
Further, the inorganic matter in the inorganic matter/polymer composite layer is selected from the ceramic powders of zero dimension, one
The ceramic powders of dimension, the conductive particles of zero dimension and one-dimensional conductor powder.
Further, the ceramic powders are barium titanate, lead magnesio-niobate lead zirconate titanate, barium strontium titanate, lead zirconate titanate
Or the one or several kinds in titanium dioxide,
Further, one kind in silver, gold, carbon black, carbon nanotube and graphene of the conductor powder or
It is several.
Further, the polymer in the inorganic matter/polymer composite layer is thermoplastic polymer, is selected from ring
One or more of oxygen resin, polystyrene, polypropylene, polyethylene, pvdf resin or polymethyl methacrylate.
Further, the inorganic matter/polymer composite layer is epoxy resin and lead magnesio-niobate lead zirconate titanate
Powder composite layer.Lead magnesio-niobate lead zirconate titanate powder is the 60vol% of Kynoar hexafluoropropene volume in composite layer.Polymerization
Nitride layer is epoxy resin.
Further, the lead magnesio-niobate lead zirconate-titanate ceramic powder is prepared by molten-salt growth method.
The layer structure of the dielectric composite material is the suspension method of spin coating or the cast successively by each layer
It is prepared by method.
The spin-coating method refers to first prepared polymer solution, and inorganic fill phase, the dispersion of mixed liquor ball milling are added thereto
After obtain A liquid, prepare pure polymer solution, be defined as B liquid.Using sol evenning machine, A liquid and B liquid are divided according to the number of plies of regulation
It does not coat on the glass substrate, the dielectric composite material of multilayered structure is obtained after dry.
In a preferred embodiment of this programme, the preparation method of the dielectric composite material is 8 mass %'s
Lead magnesio-niobate lead zirconate titanate powder and 2 mass % relative to epoxy resin 60vol% is added in epoxy resin solution thereto
The grain size of triethylamine, lead magnesio-niobate lead zirconate titanate powder is 100 nanometers~1 micron, and mixed liquor ball milling obtains A liquid in 24 hours, matches
The epoxy resin solution of 12 mass % is made, is B liquid.Using sol evenning machine, with 200 rpms of speed spin coating one on the cover slip
Layer A liquid, dries 10 points at room temperature, then successively distinguishes one layer of B liquid of spin coating and A liquid under conditions again.
In a preferred embodiment of this programme, the structure of the dielectric composite material is lead magnesio-niobate zirconium metatitanic acid
Lead/epoxy resin composite layer replaces the composite wood that superposition forms five-layer structure with pure Kynoar hexafluoropropene polymeric layer
Material, the maximum energy storage density measured under 344kV/mm electric fields are 4.02J/cm3
Beneficial effects of the present invention
It is an object of the invention to regulate and control the structure of composite material, provide that a kind of preparation method is simple, has highly resistance breakdown
The composite material of electric field and high-k, to greatly improve its energy storage densities.Specifically, the present invention is by devising one
The dielectric composite material of kind of multilayer, wherein composite material be by lead magnesio-niobate lead zirconate titanate/epoxy resin composite material with it is pure
Epoxy resin forms, and the multilayer materials film of good quality is prepared for by spin-coating method.Inventors discovered through research that this hair
In bright composite material, polymeric layer in the composite shared volume fraction the promotion of the performance of integral material is played it is non-
The effect of Chang Guanjian is higher than 45%, then leads to the decline of the energy storage density of integral material, together if volume fraction is less than 10%
When inventor find that middle layer is three layers, the most preferred volume fraction of volume fraction of polymer, which is 25-35%, can reach best
Energy storage density and anti-breakdown electric field (shown in Figure 2).During the experiment, inventor also surprisingly has found, system of the present invention
The anti-breakdown electric field of standby obtained composite material can be increased to 315kV/mm by the 162kV/mm of single layer composite, store up simultaneously
Can density by single layer composite 2.03J/cm3It is increased to 5.22J/cm3.And preparation process of the present invention is simple, and biography may be used
The spin coating proceeding of system creates condition for industrial practical application.
Description of the drawings
Fig. 1 is the microscopic appearance figure of layer composite material, and wherein Fig. 1 a and 1b are respectively three-decker and five layers of knot
Structure, it can be seen that apparent multilayered structure, interface is clearly demarcated, and zero defect, and intermediate straight polymer layer thickness is at gradient from figure
Variation.
Fig. 2 be different intermediate layer thickness three-decker composite materials and pure resin and single layer composite energy storage density and
Electric field ability comparison diagram is worn in resistance.Five samples that volume fraction is respectively 53%, 35%, 25%, 15% and 9% are three-layered nodes
Structure composite material, 100% and 0% is pure resin sample and single layer composite sample respectively.As can be seen that three-decker
The anti-breakdown electric field of composite material is significantly improved relative to single layer structure, and 315kV/mm is increased to from 184kV/mm, meanwhile, energy storage
Density is greatly improved relative to single layer structure composite material, and the maximum energy storage density of single layer structure composite material is 2.03J/cm3,
And the maximum energy storage density of the composite material of three-decker is increased to 5.22J/cm3。
Fig. 3 is the cross-section morphology figure of three-decker composite material prepared by casting.
Specific implementation mode
Following implementation is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1
The lead magnesio-niobate zirconium relative to epoxy resin 60vol% is added in the epoxy resin solution for preparing 8 mass % thereto
The grain size of the triethylamine of lead titanates powder and 2 mass %, lead magnesio-niobate lead zirconate titanate powder is 100 nanometers~1 micron, mixed liquor
Ball milling obtains A liquid for 24 hours, prepares the epoxy resin solution of 12 mass %, is B liquid.Using sol evenning machine, with 200 rpms
Speed one layer of A liquid of spin coating on the cover slip dries 10 points at room temperature, then successively one layer of B liquid of spin coating and A respectively under conditions again
Liquid.
Above-mentioned sample is 24 hours dry in 80 DEG C of air dry ovens, then under the conditions of 200 DEG C, 15MPa, hot pressing 10
Minute, it is cooled to room temperature, then carrying out electrode test, (specific electrode test method is to sputter 40nm thickness in sample upper and lower surface
Circular symmetrical gold electrode tests D-E loops with ferroelectricity instrument (Precision 10KV HVI-SC), calculates corresponding energy
Density), it is the 35% of entire sample that wherein the thickness of interbed is calculated by volume fraction, and anti-breakdown field strength is increased to 315kV/
Mm, maximum energy storage density are 5.22J/cm3。
Embodiment 2
It is prepared for gathering inclined fluorine with pure by lead magnesio-niobate lead zirconate titanate/epoxy resin composite layer according to the process of embodiment 1
Ethylene hexafluoropropene polymeric layer is alternately superimposed the composite material for forming five-layer structure, shown in shape appearance figure such as Fig. 1 (b).According to
The test method of embodiment 1, it is 4.02J/cm that its maximum energy storage density is measured under 344kV/mm electric fields3。
Embodiment 3
Using casting, three-decker composite material is prepared according to the process of embodiment 1.Its shape appearance figure is as shown in Figure 3.
Embodiment 4
The polymer solution of the Kynoar hexafluoropropene of 10 mass % is prepared, is B liquid, it is same according to embodiment 1
Mode obtains composite material, and corresponding microscopic appearance figure is Fig. 1 (b), and it is entire sample that wherein the thickness of interbed is calculated by volume fraction
The 25% of product, anti-breakdown field strength are increased to 280kV/mm, and maximum energy storage density is 5.12J/cm3。
Embodiment 5
The polymer solution of the Kynoar hexafluoropropene of 8 mass % is prepared, is B liquid, according to the same side of embodiment 1
Formula, obtains composite material, and it is the 15% of entire sample that wherein the thickness of interbed is calculated by volume fraction, and anti-breakdown field strength carries
Height arrives 260kV/mm, and maximum energy storage density is 4.32J/cm3。
Comparative example 1
It is added without lead magnesio-niobate lead zirconate titanate powder, embodiment 1 is carried out using only the epoxy resin solution of 8 mass %
Same electrode test, it is 2.12J/cm that its maximum energy storage density is measured under 365kV/mm electric fields3。
Comparative example 2
The lead magnesio-niobate lead zirconate titanate powder of the epoxy resin solution volume fraction 60% of opposite 8 mass % is added, prepares
The composite material of single layer, according to the test method of embodiment 1, its maximum energy storage density is measured under 162kV/mm electric fields is
2.56J/cm3。
Comparative example 3
The epoxy resin solution of 8 mass % is prepared, composite material is obtained according to 1 same mode of embodiment for B liquid,
It is the 9% of entire sample that the thickness of middle layer is calculated by volume fraction, and anti-breakdown field strength is 195kV/mm, maximum energy storage
Density is only 1.92J/cm3。
Comparative example 4
According to 1 same mode of embodiment, it is the 53% of entire sample that wherein the thickness of interbed is calculated by volume fraction, is obtained
To composite material, anti-breakdown field strength is 315kV/mm, and maximum energy storage density is only 3.21J/cm3.Overall performance is promoted
Not enough.
Claims (1)
1. a kind of dielectric composite material, which is characterized in that preparation method is：
The lead magnesio-niobate zirconium metatitanic acid relative to epoxy resin 60vol% is added in the epoxy resin solution for preparing 8 mass % thereto
The grain size of the triethylamine at lead powder end and 2 mass %, lead magnesio-niobate lead zirconate titanate powder is 100 nanometers~1 micron, mixed liquor ball milling
A liquid is obtained within 24 hours, the epoxy resin solution of 12 mass % is prepared, is B liquid；
It with 200 rpms of speed spin coating A liquid, dries 10 minutes at room temperature, then successively spin coating one respectively under the same conditions
It is the 35% of entire material that layer B liquid and A liquid, the wherein thickness of interbed are calculated by volume fraction；
After the completion of spin coating, 24 hours dry in 80 DEG C of air dry ovens, then under the conditions of 200 DEG C, 15MPa, hot pressing 10 divides
Clock is cooled to room temperature.
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| CN106218188B (en) * | 2016-07-27 | 2018-09-28 | 中国海洋大学 | The preparation method of high dielectric, low-loss composite material with laminated construction |
| CN109705502B (en) * | 2018-12-29 | 2020-05-22 | 中国科学技术大学 | Polymer-based composite material and preparation method thereof |
| CN114103336A (en) * | 2020-08-28 | 2022-03-01 | 浙江工业大学 | P (VDF-CTFE) composite film with sandwich structure and preparation method thereof |
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| CN104553199B (en) * | 2015-01-16 | 2017-10-13 | 哈尔滨理工大学 | The preparation method of three layers of dielectric polyvinylidene fluoride film |
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