CN106543606B - High energy storage density polymer composite dielectrics and preparation method thereof - Google Patents
High energy storage density polymer composite dielectrics and preparation method thereof Download PDFInfo
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract
The invention discloses a kind of high energy storage density polymer composite dielectrics and preparation method thereof；The composite dielectrics includes the high dielectric constant nanofiller that mass fraction is modified for 55~97.5% fluorine-containing ferroelectric polymers matrix and 45~2.5% dopamine.The preparation method is that passing through solution blending, casting film-forming and hot-forming technique preparation.High dielectric constant nanoparticles are first carried out graft modification using the dopamine with backbone by the present invention, the dopamine with backbone can both improve the dispersibility of high dielectric constant nanoparticles, again can be well compatible with fluorine-containing ferroelectric polymers matrix, enhance the interface binding power between polymeric matrix and high dielectric constant nanoparticles filler.High energy storage density polymer composite dielectrics prepared by the present invention has the characteristics that light weight, flexibility are good, energy storage density is high, suitable for preparing the advanced electronic and electrical equipment such as high energy storage density capacitor, embedded capacitor, field effect transistor.
Description
Technical field
The invention belongs to dielectric substance and energy storage material preparation technical fields, and in particular to a kind of high energy storage density polymerization
Object composite dielectrics and preparation method thereof.
Background technique
The dielectric substance of high energy storage density is brilliant in Mobile energy storage capacitor, embedded capacitor, cable termination, field-effect
It is widely used in the electronic and electrical equipments such as body pipe.Currently, electronic device develops to directions such as integrated, miniaturizations, and makes
The standby dielectric with high energy storage density is to reduce one of electronic device volume, the critical path for improving integrated level.
According to dielectric theory, the maximum energy storage density of dielectric substance can pass through formula: Umax=0.5 ε0εrEb 2It carries out
It calculates.Wherein ε0Refer to permittivity of vacuum, εrRefer to the dielectric constant of dielectric substance, EbRefer to the breakdown of dielectric substance
Intensity.Therefore, only try to improve dielectric dielectric constant and breakdown strength, so that it may which the energy storage for improving dielectric substance is close
Degree.Currently, many for the research for improving polymeric matrix dielectric constant, preparation mainly includes two approach: addition has
The ceramic particle or filling conducting particles of high dielectric constant.The dielectric that introducing conducting particles can greatly improve composite material is normal
Number, but the breakdown strength of composite material sharply declines, and dielectric loss will increase dramatically, so that this method is not suitable for preparation
The composite dielectric material of high energy storage density.The dielectric of composite material not only can be improved in the ceramic particle of addition high dielectric constant
Constant can also make composite material keep high breakdown strength and low-dielectric loss.However, due to the pottery of most of high dielectric constants
Porcelain particle is incompatible with polymeric matrix.When especially ceramic particle is reduced in size to nanoscale, easily send out in the polymer
It is raw to reunite, it causes that the breakdown strength of composite material is greatly reduced, dielectric loss is significantly increased, limits composite material energy storage density
Raising.Therefore, the polymer composites that a kind of dielectric constant is high and breakdown strength is high are developed and are used as high energy storage density material
Become extremely important.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high energy storage density polymer composite dielectrics
And preparation method thereof.It is modified using nanofiller of the dopamine with backbone to high dielectric constant, dopamine list
Member forms a strata dopamine in nanofiller surface aggregate, and the long chain being grafted in poly-dopamine not only can be with matrix
Polymer chain is intertwine with each other, and can also prevent to contact with each other between nanofiller, so as to improve the interface knot of composite material
With joint efforts, material internal defect is reduced, material is made to have higher dielectric constant, higher breakdown strength and lower dielectric damage
Consumption.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of high energy storage density polymer composite dielectrics, are 55~97.5% including mass fraction
Fluorine-containing ferroelectric polymers matrix and 45~2.5% the modified high dielectric constant nanofiller of dopamine；The dopamine is to change
Property dopamine, the high dielectric constant nanofiller be Nano Ceramic Particles.The material is using fluoropolymer as matrix, with modification
The Nano Ceramic Particles of high dielectric constant are filler, are prepared by solution blending, casting film-forming and hot press forming technology.Institute
It states modified Nano ceramic particle and reacts obtained with the Nano Ceramic Particles of high dielectric constant by the modification dopamine of backbone.
The present invention cannot be obtained using unmodified dopamine.
Preferably, the fluorine-containing ferroelectric polymers matrix is PVDF, P (VDF-HFP), P (VDF-TrFE) or P (VDF-
At least one of TrFE-CFE).
It is highly preferred that the fluorine-containing ferroelectric polymers matrix is P (VDF-HFP) or P (VDF-TrFE).It can guarantee simultaneously
Composite material has high dielectric constant, low dielectric loss.
Preferably, the modified high dielectric constant nanofiller of the dopamine is through the following steps that preparation:
Modified dopamine is dissolved in formation solution a in isopropanol, high dielectric constant nanofiller is dispersed in three (hydroxyl first
Base) aminomethane hydrochloride buffer in formed solution b, then by solution a instill solution b in, react 72-24 at 50-70 DEG C
Hour；With the high dielectric constant nanofiller that ethyl alcohol and water washing are modified to get the dopamine after centrifugation.
Preferably, the dosage of the modification dopamine is the 0.5~35% of high dielectric constant nanofiller quality.It is described
When being modified dopamine dosage in the range, moderate one layer of thickness fine and close organic layer can be formed on nanofiller surface.If modified
Dopamine dosage is excessively high, and the organic layer that will lead to nanofiller surface is too thick；Dosage is too low, and will lead to nanofiller surface cannot
It is effectively covered by dopamine.
Preferably, the modified dopamine is with backbone, specially 2- amino -3- (3,4- dihydroxy phenyl) third
Sour last of the ten Heavenly stems ester or 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl.
More electedly, the modified dopamine is that 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- is complete
Fluorine last of the ten Heavenly stems ester.
Preferably, the modified dopamine uses 1- decyl alcohol or 1H, 1H, 2H, 2H- perfluor decyl alcohol and L-3,4- dihydroxyphenyl third
Propylhomoserin reaction preparation.The nanofiller of high dielectric constant is modified using the modification dopamine of backbone, it can be in nanometer
Filler surface polymerize to form one layer of poly-dopamine with backbone.
Preferably, the high dielectric constant nanofiller is titanium dioxide, strontium titanates, barium strontium titanate, barium titanate, zirconium titanium
At least one of lead plumbate, CaCu 3 Ti 4 O.
Preferably, the high dielectric constant nanofiller is nano particle, nano wire or nanometer sheet.
From the point of view of the easy point for improving nanofiller dispersibility, the modified high dielectric constant nanometer of the preferably described dopamine is filled out
Material is the modified nanofiller of 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl.
It is highly preferred that the fluorine-containing ferroelectric polymers matrix in the composite dielectrics is P (VDF-HFP), dopamine is modified
High dielectric constant nanofiller be that 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is modified
Nanometer sheet or nano wire.
It is highly preferred that the fluorine-containing ferroelectric polymers matrix in the composite dielectrics is P (VDF-TrFE), dopamine is modified
High dielectric constant nanofiller be that 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is modified
Nanometer sheet or nano wire.
The present invention also provides a kind of preparation methods of high energy storage density polymer composite dielectrics, and the method includes such as
Lower step:
A, the fluorine-containing ferroelectric polymers matrix is added N, in N- diformamide solution at 65~75 DEG C stirring and dissolving,
Obtain solution A；
B, the modified high dielectric constant nanofiller of the dopamine is added N, in N- diformamide solution at room temperature
Stirring 25~30 minutes, obtains B solution；
C, the A and B solution are mixed at room temperature, after stirring 25~30 minutes, by solution cast film formation, and 85~95
DEG C dry 6~7 hours, obtain polymer composites；
D, the polymer composites are placed in mold after 60~65 DEG C are dried in vacuo 10~12 hours in 180
~185 DEG C, under 10~15MPa hot pressing 5~7 minutes to get high energy storage density polymer composite dielectrics.
Preferably, in the step A, it is fluorine-containing that 2.75~4.875g is added in N- diformamide solution by every 55~60mL N
Ferroelectric polymers matrix；In the step B, it is modified that 0.125~2.25g is added in N- diformamide solution by every 5~100mL N
High dielectric constant nanofiller.
The present invention is that it is normal to add the high dielectric for having the dopamine of backbone modified in fluorine-containing ferroelectric polymers matrix
It is multiple to be prepared for a kind of high energy storage density polymer by solution blending, casting film-forming and the techniques such as hot-forming for number nanofillers
Close dielectric.
The present invention uses the Nano Ceramic Particles with high dielectric constant to do filler, higher fluorine-containing with intrinsic dielectric constant
Polymer does matrix, by coating one layer of modification DOPA with backbone on the Nano Ceramic Particles surface of high dielectric constant
Amine is as compatilizer, to improve the dispersibility and Nano Ceramic Particles and fluorine-containing ferroelectric polymers matrix of Nano Ceramic Particles
Between compatibility, be remarkably improved polymeric matrix dielectric constant to reach, while keeping composite material is higher to hit
The purpose for wearing intensity and lower dielectric loss, prepares polymer-based high energy storage density material.
Compared with prior art, the present invention is with following the utility model has the advantages that selection has the dopamine of backbone modified
High dielectric constant nanofiller, relative in existing modification technology be usually surface cause activity polymerizating technology, the present invention in
The modification of high dielectric constant nanofiller can be completed by a step simple reaction；The dopamine with backbone being grafted
Not only it can improve the dispersibility of high dielectric constant nanofiller, but also can be well compatible with fluorine-containing ferroelectric polymers matrix, enhance
Interface binding power between polymeric matrix and high dielectric constant nanofiller reduces material internal defect, to reduce dielectric
Loss, enhancing breakdown strength.It is normal to choose suitable polymeric matrix, high dielectric by constantly studying by the present inventor
The modifying agent of number nanofiller and the content of each component etc., are acted synergistically by it, obtain good invention effect.This hair
Bright prepared high energy storage density polymer composite dielectrics has the characteristics that light weight, flexibility are good, energy storage density is high, is applicable in
In preparing the advanced electronic and electrical equipment such as high energy storage density capacitor, embedded capacitor, field effect transistor.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the preparation process signal for the high dielectric constant nanofiller that the present invention has the dopamine of backbone modified
Figure；
Fig. 2 is the transmission electron microscope photo of the titanium dioxide nanoplate of added modification in the embodiment of the present invention 1；
Fig. 3 is that the scanning and transmission electron microscopy of added modified barium carbonate nano wire in the embodiment of the present invention 2 shines
Piece；Wherein, figure a is electron microscope photo scanning；Figure b is transmission electron microscope photo；
Fig. 4 is the flexibility photo of polymer composites prepared in the embodiment of the present invention 3；
Fig. 5 is that the transmission electron microscope of polymer composites ultra-thin section prepared in the embodiment of the present invention 4 shines
Piece；
Fig. 6 is that the transmission electron microscope of polymer composites ultra-thin section prepared in the embodiment of the present invention 5 shines
Piece；
Fig. 7 is the energy storage density of polymer composites and the relational graph of electric field prepared by the embodiment of the present invention 2.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, several changes and improvements can also be made.These belong to the present invention
Protection scope.
Experimental test sample of the invention is under vulcanizing press (QLB-D type, Shanghai rubber machinery plant) by hot-forming.
Modified filler prepared by the present invention uses field emission scanning electron microscope (Nova NanoSEM 450, the U.S.
FEI Co.) and projection electron microscope (2100 type of JEOL JEM, Jeol Ltd.) observed.
In composite material prepared by the present invention filler dispersibility using thoroughly retouch electron microscope (2100 type of JEOL JEM,
Jeol Ltd.) it is observed.
The dielectric properties of sample prepared by the present invention are using broadband dielectric spectroscopy instrument (40 type of Concept, Germany
Novocontrol company) it is measured.
The energy storage density of sample prepared by the present invention, by ferroelectricity analyzer, (Premier II, U.S. Radiant are public
Department) measurement sample dielectric displacement (D)-electric field (E) curve after calculated using formula U=∫ EdD.
Embodiment 1
The present embodiment is related to a kind of high energy storage density polymer composite dielectrics, and the composite material is by 97.5% mass point
Several PVDF is complete as 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- of matrix and 2.5% mass fraction
The fluorine last of the ten Heavenly stems ester modified titanium dioxide nanoplate is formed as filler.Wherein 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H,
The modified titanium dioxide nanoplate of 1H, 2H, 2H- perfluoro decyl is prepared by following steps:
A, titanium dioxide nanoplate: according to document (X.G.Han, et al., J.Am.Chem.Soc., 2009,131,
3152.) the method synthesis reported；
B, with the dopamine of backbone: 1H, 1H, 2H, 2H- perfluor decyl alcohol and L-3,4- bloch reaction,
Obtain 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl.This DOPA with backbone
The synthesis of amine is using in document (Manolakis, I.et al., Macromol.Rapid Commun.2014,35,71-76.)
Method.
C, the modified titanium dioxide nanoplate filler of the dopamine of backbone: by 2- amino -3- (3,4- dihydroxy benzenes
Base) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is dissolved in isopropanol, while titanium dioxide nanoplate is dispersed in three (hydroxyl first
Base) aminomethane hydrochloride buffer in, then will dissolved with 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H,
The aqueous isopropanol of 2H- perfluoro decyl instills the hydrochloride buffer for being dispersed with three (methylol) aminomethanes of titanium dioxide nanoplate
In liquid, reacted 72-24 hours at 50-70 DEG C.Ethyl alcohol and water washing are used after centrifugation to get 2- amino -3- (3,4- dihydroxy benzenes are arrived
Base) the modified titanium dioxide nanoplate of propionic acid -1H, 1H, 2H, 2H- perfluoro decyl.End 2- amino -3- (the 3,4- dihydroxy benzenes
Base) dosage of propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is the 0.5~35% of titanium dioxide nanoplate quality, in the present embodiment
Select 30%.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, and the method includes such as
Lower step:
Step 1, fluorine-containing ferroelectric polymers matrix described in 4.875g is added to 60mL N, in N- diformamide solution, in
Stirring and dissolving at 70 DEG C, obtains solution A；
Step 2,0.125g2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is modified
Nano titania be added to 5mL N, in N- diformamide solution, be stirred by ultrasonic 28 minutes at room temperature, obtain B solution；
Step 3, above-mentioned A and B solution are mixed at room temperature, is stirred by ultrasonic 30 minutes, then by solution cast film formation, and
It is 7 hours dry in 85 DEG C of air dry oven, obtain polymer composites；
Step 4, by polymer composites obtained in above-mentioned steps 3, dry 12 is small in 65 DEG C of vacuum oven
Shi Hou is placed in mold hot pressing 7 minutes under 185 DEG C, 15MPa, obtains high energy storage density polymer composite dielectrics.
Embodiment 2
The present embodiment is related to a kind of high energy storage density polymer composite dielectrics, and the composite material is by 85% mass fraction
P (VDF-HFP) titanium modified as 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate of matrix and 15% mass fraction
Sour barium nano wire is formed as filler.The wherein modified barium titanate nano of 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate
Line is prepared by following steps.
A, barium titanate nano line: according to document (G.Y.Wang, et al., ACS Applied Materials&
Interfaces2015,7,18017) the method synthesis reported；
B, with the dopamine of backbone: 1- decyl alcohol and L-3,4- bloch reaction obtain 2- amino -3-
(3,4- dihydroxy phenyl) decyl propionate.The synthesis of this dopamine with backbone using document (Manolakis,
I.et al., Macromol.Rapid Commun.2014,35,71-76.) in method.
C, the modified barium titanate nano line filler of the dopamine of backbone: by 2- amino -3- (3,4- dihydroxy phenyl)
Decyl propionate is dissolved in isopropanol, while barium titanate nano line being dispersed in the hydrochloride buffer of three (methylol) aminomethanes
In, then will dissolved with the aqueous isopropanol of 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate instill in be dispersed with barium titanate
In the hydrochloride buffer of three (methylol) aminomethanes of nano wire, reacted 72-24 hours at 50-70 DEG C.Ethyl alcohol is used after centrifugation
With water washing to get the barium titanate nano line modified to 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate.The 2- ammonia
The dosage of base -3- (3,4- dihydroxy phenyl) decyl propionate is the 0.5~35% of barium titanate nano line mass, is selected in the present embodiment
With 25%.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, and the method includes such as
Lower step:
Step 1, fluorine-containing ferroelectric polymers matrix described in 4.25g is added to 59mL N, in N- diformamide solution, in 65
Stirring and dissolving at DEG C, obtains solution A；
Step 2, the modified barium titanate nano line of 0.75g 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate is added
To 35mL N, in N- diformamide solution, it is stirred by ultrasonic 30 minutes at room temperature, obtains B solution；
Step 3, above-mentioned A and B solution are mixed at room temperature, is stirred by ultrasonic 27 minutes, then by solution cast film formation, and
It is 6.5 hours dry in 90 DEG C of air dry oven, obtain polymer composites；
Step 4, by polymer composites obtained in above-mentioned steps 3, dry 11 is small in 62 DEG C of vacuum oven
Shi Hou is placed in mold hot pressing 6 minutes under 184 DEG C, 11MPa, obtains high energy storage density polymer composite dielectrics.
Embodiment 3
The present embodiment is related to a kind of high energy storage density polymer composite dielectrics, and the composite material is by 75% mass fraction
, P (VDF-TrFE) is modified as 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate of matrix and 25% mass fraction
CaCu 3 Ti 4 O nano wire is formed as filler.The wherein modified copper titanate of 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate
The preparation step of calcium nano wire with embodiment 2, the difference is that: high dielectric constant nanofiller used is CaCu 3 Ti 4 O
Nano wire.The synthesis of this CaCu 3 Ti 4 O nano wire uses improved document (H.X.Tang, et al., NanoEnergy
2015,17,302-307.) in method.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, and the method includes such as
Lower step:
Step 1, fluorine-containing ferroelectric polymers matrix described in 3.75g is added to 58mL N, in N- diformamide solution, in 68
Stirring and dissolving at DEG C, obtains solution A；
Step 2, the modified CaCu 3 Ti 4 O nano wire of 1.25g 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate is added
Enter to 50mL N, in N- diformamide solution, is stirred by ultrasonic 25 minutes at room temperature, obtains B solution；
Step 3, above-mentioned A and B solution are mixed at room temperature, is stirred by ultrasonic 25 minutes, then by solution cast film formation, and
It is 6 hours dry in 90 DEG C of air dry oven, obtain polymer composites；
Step 4, by polymer composites obtained in above-mentioned steps 3, dry 10 is small in 60 DEG C of vacuum oven
Shi Hou is placed in mold hot pressing 5 minutes under 180 DEG C, 10MPa, obtains high energy storage density polymer composite dielectrics.
Embodiment 4
The present embodiment is related to a kind of high energy storage density polymer composite dielectrics, and the composite material is by 65% mass fraction
2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H as matrix and 35% mass fraction of P (VDF-TrFE-CFE),
The modified barium strontium titanate nano wire composition of 2H, 2H- perfluoro decyl.Wherein 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H,
The preparation step of the modified barium strontium titanate nano wire of 1H, 2H, 2H- perfluoro decyl with embodiment 1, institute the difference is that: it is used
High dielectric constant nanofiller be barium strontium titanate nano wire.The synthesis of this barium strontium titanate nano wire using document (S.Wang,
Et al., J.Phys.Chem.C 2015,119,25307-25318.) in method.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, and the method includes such as
Lower step:
Step 1, fluorine-containing ferroelectric polymers matrix described in 3.25g is added to 57mL N, in N- diformamide solution, in
Stirring and dissolving at 60-70 DEG C, obtains solution A；
Step 2,1.75g 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is modified
Barium strontium titanate nano wire be added to 85mL N, in N- diformamide solution, be stirred by ultrasonic 27 minutes at room temperature, it is molten to obtain B
Liquid；
Step 3, above-mentioned A and B solution are mixed at room temperature, is stirred by ultrasonic 26 minutes, then by solution cast film formation, and
It is 6 hours dry in 95 DEG C of air dry oven, obtain polymer composites；
Step 4, by polymer composites obtained in above-mentioned steps 3, dry 10 is small in 62 DEG C of vacuum oven
Shi Hou is placed in mold hot pressing 5 minutes under 182 DEG C, 12MPa, obtains high energy storage density polymer composite dielectrics.
Embodiment 5
The present embodiment is related to a kind of high energy storage density polymer composite dielectrics, and the composite material is by 55% mass fraction
2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H as matrix and 45% mass fraction of P (VDF-TrFE-CFE),
The modified barium titanate nano particle composition of 2H, 2H- perfluoro decyl.Wherein 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H,
The preparation step of the modified barium titanate nano particle of 1H, 2H, 2H- perfluoro decyl with embodiment 1, institute the difference is that: it is used
High dielectric constant nanofiller be barium titanate nano particle.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, and the method includes such as
Lower step:
Step 1, fluorine-containing ferroelectric polymers matrix described in 2.75g is added to 55mL N, in N- diformamide solution, in
Stirring and dissolving at 60-70 DEG C, obtains solution A；
Step 2,2.25g 2- amino -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl is modified
Barium titanate nano particle be added to 100mL N, in N- diformamide solution, be stirred by ultrasonic 27 minutes at room temperature, it is molten to obtain B
Liquid；
Step 3, above-mentioned A and B solution are mixed at room temperature, is stirred by ultrasonic 26 minutes, then by solution cast film formation, and
It is 6 hours dry in 95 DEG C of air dry oven, obtain polymer composites；
Step 4, by polymer composites obtained in above-mentioned steps 3, dry 10 is small in 62 DEG C of vacuum oven
Shi Hou is placed in mold hot pressing 5 minutes under 182 DEG C, 12MPa, obtains high energy storage density polymer composite dielectrics.
Implementation result: the method for modifying of high dielectric constant nanofiller used in the present invention is simple to operation, such as Fig. 1 institute
Show, a step can be completed.The high dielectric nano filler used has high draw ratio, such as uses transmission electron microscope observable
There is typical two-dimensional sheet structure to nano-titanium dioxide filler used by embodiment 1 (shown in Fig. 2).Using scanning and thoroughly
It penetrates electron microscope to observe (shown in Fig. 3) modified barium titanate nano line, it can be seen that made in the embodiment of the present invention 2
There is the organic layer of one layer of 10nm or so on the barium titanate nano line surface of standby modification, it was demonstrated that the dopamine of backbone is successfully grafted
Nanofiller surface is arrived；Polymer composites prepared by the present invention have good flexibility, as shown in figure 4, implementing
Polymer composites prepared by example 3 be free to bending and it is not broken.Using transmission electron microscope observation embodiment 4
The composite material ultra-thin section prepared with embodiment 5 can find that nanofiller is uniformly dispersed in a polymer matrix, such as Fig. 5 and
Shown in Fig. 6；It is tested by the energy storage capacity to polymer composites prepared by the present invention, is illustrated in figure 7 implementation
The energy storage density of composite material prepared by example 2 and the relational graph of electric field strength.At room temperature to sample prepared by the present invention
Breakdown strength up to 550kV/mm, the practical maximum energy storage density of material can achieve 21.5J/cm3.The above results explanation,
Compared to the prior art, the high energy storage density polymer composite dielectrics prepared by the present invention has breakdown strength height, energy storage close
The features such as degree is high and flexibility is good is suitable for the mobile high storage capacitor of preparation, embedded capacitor, field effect transistor etc.
Advanced electronic and electrical equipment.
Comparative example 1
This comparative example is related to a kind of high energy storage density polymer composite dielectrics, the high energy storage density polymer compound electric
Composition of medium and preparation method thereof is substantially the same manner as Example 1, the difference is that only: this comparative example is using nanoparticle
For the modified titanium dioxide nanoplate of dopamine, the dopamine is unmodified dopamine, preparation method are as follows:
By L-3,4- dihydroxyphenylalanine (dopamine) is dissolved in isopropanol, while titanium dioxide nanoplate being dispersed in
In the hydrochloride buffer of three (methylol) aminomethanes, then it will be instilled dissolved with L-3, the aqueous isopropanol of 4- dihydroxyphenylalanine
It is dispersed in the hydrochloride buffer of three (methylol) aminomethanes of titanium dioxide nanoplate, it is small that 72-24 is reacted at 50-70 DEG C
When.With ethyl alcohol and water washing to get the titanium dioxide nanoplate modified to dopamine after centrifugation.Third ammonia of L-3,4- dihydroxyphenyl
The dosage of acid is the 0.5~35% of titanium dioxide nanoplate quality, selects 30% in this comparative example.
The composite material prepared using this comparative example is reunited mutually due to the modified titanium dioxide nanoplate of dopamine one
It rises, it is difficult to be effectively dispersed in polymeric matrix, the sample for test can not be obtained.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or modify within the scope of the claims, this not shadow
Ring substantive content of the invention.In the absence of conflict, the feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (9)
1. a kind of high energy storage density polymer composite dielectrics, which is characterized in that including mass fraction be 55~97.5% to contain
Fluorine ferroelectric polymers matrix and 45~2.5% the modified high dielectric constant nanofiller of dopamine；The dopamine is to be modified
Dopamine, the high dielectric constant nanofiller are Nano Ceramic Particles；
The modified dopamine has backbone, specially 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate or 2- ammonia
Base -3- (3,4- dihydroxy phenyl) propionic acid -1H, 1H, 2H, 2H- perfluoro decyl.
2. high energy storage density polymer composite dielectrics according to claim 1, which is characterized in that the fluorine-containing ferroelectricity
Polymeric matrix is at least one of PVDF, P (VDF-HFP), P (VDF-TrFE) or P (VDF-TrFE-CFE).
3. high energy storage density polymer composite dielectrics according to claim 2, which is characterized in that the fluorine-containing ferroelectricity
Polymeric matrix is P (VDF-HFP) or P (VDF-TrFE).
4. high energy storage density polymer composite dielectrics according to claim 1, which is characterized in that the dopamine changes
Property high dielectric constant nanofiller through the following steps that preparation:
Modified dopamine is dissolved in formation solution a in isopropanol, high dielectric constant nanofiller is dispersed in trihydroxy methyl ammonia
Solution b is formed in the hydrochloride buffer of methylmethane, and then solution a is instilled in solution b, is reacted 72-24 hours at 50-70 DEG C；
With the high dielectric constant nanofiller that ethyl alcohol and water washing are modified to get the dopamine after centrifugation.
5. high energy storage density polymer composite dielectrics according to claim 4, which is characterized in that the modification DOPA
The dosage of amine is the 0.5~35% of high dielectric constant nanofiller quality.
6. high energy storage density polymer composite dielectrics according to claim 1, which is characterized in that the modified dopamine
Using 1- decyl alcohol or 1H, 1H, 2H, prepared by 2H- perfluor decyl alcohol and L-3,4- bloch reaction.
7. according to claim 1, high energy storage density polymer composite dielectrics described in any one of 4 or 5, which is characterized in that
The Nano Ceramic Particles be titanium dioxide, strontium titanates, barium strontium titanate, barium titanate, lead zirconate titanate, in CaCu 3 Ti 4 O at least
It is a kind of.
8. according to claim 1, high energy storage density polymer composite dielectrics described in any one of 4 or 5, which is characterized in that
The high dielectric constant nanofiller is nano particle, nano wire or nanometer sheet.
9. a kind of preparation method of such as high energy storage density polymer composite dielectrics according to any one of claims 1 to 8,
It is characterized in that, described method includes following steps:
A, the fluorine-containing ferroelectric polymers matrix is added N, in N- diformamide solution at 65~75 DEG C stirring and dissolving, obtain
Solution A；
B, N is added in the modified high dielectric constant nanofiller of the dopamine, is stirred at room temperature in N- diformamide solution
25~30 minutes, obtain B solution；
C, the A and B solution are mixed at room temperature, after stirring 25~30 minutes, by solution cast film formation, and it is dry at 85~95 DEG C
Dry 6~7 hours, obtain polymer composites；
D, the polymer composites are placed in mold after 60~65 DEG C are dried in vacuo 10~12 hours in 180~185
DEG C, under 10~15MPa hot pressing 5~7 minutes to get high energy storage density polymer composite dielectrics.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107342437B (en) * | 2017-08-04 | 2019-08-13 | 北京化工大学 | A kind of solid polymer electrolyte and preparation method thereof mixed with modified Nano filling |
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| CN112646213B (en) * | 2020-11-26 | 2022-09-27 | 中国科学院深圳先进技术研究院 | Preparation method of charge storage polymer-based composite material |
| CN112457611B (en) * | 2020-11-27 | 2022-10-18 | 陕西科技大学 | Polyvinylidene fluoride-based barium strontium titanate nanocomposite and preparation method thereof |
| CN112694699A (en) * | 2020-12-22 | 2021-04-23 | 深圳市信维通信股份有限公司 | Application and preparation method of fluorine-containing polymer |
| CN114927345A (en) * | 2022-05-19 | 2022-08-19 | 江苏科技大学 | PVDF composite energy storage material and preparation method thereof |
| CN115418028A (en) * | 2022-10-09 | 2022-12-02 | 上海第二工业大学 | Preparation method of modified barium titanate nanowire and high-dielectric composite material thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN103709565A (en) * | 2013-12-26 | 2014-04-09 | 清华大学 | Composite fiber and polymer based flexible composite film and preparation method thereof |
| CN103951915A (en) * | 2014-04-29 | 2014-07-30 | 上海交通大学 | Lightweight flexible polymer-based high-energy-density material and preparation method thereof |
| CN103951917A (en) * | 2014-04-29 | 2014-07-30 | 上海交通大学 | Flexible high-dielectric polymer composite material and preparation method thereof |
| CN105070868A (en) * | 2015-08-26 | 2015-11-18 | 厦门大学 | Dopamine-modifying ceramic composite separator and application thereof |
| CN105440583A (en) * | 2015-12-04 | 2016-03-30 | 武汉理工大学 | Dopamine compound modified or coated nano particle modified polymer composite material and preparation method thereof |
-
2016
- 2016-11-04 CN CN201610972805.1A patent/CN106543606B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN103709565A (en) * | 2013-12-26 | 2014-04-09 | 清华大学 | Composite fiber and polymer based flexible composite film and preparation method thereof |
| CN103951915A (en) * | 2014-04-29 | 2014-07-30 | 上海交通大学 | Lightweight flexible polymer-based high-energy-density material and preparation method thereof |
| CN103951917A (en) * | 2014-04-29 | 2014-07-30 | 上海交通大学 | Flexible high-dielectric polymer composite material and preparation method thereof |
| CN105070868A (en) * | 2015-08-26 | 2015-11-18 | 厦门大学 | Dopamine-modifying ceramic composite separator and application thereof |
| CN105440583A (en) * | 2015-12-04 | 2016-03-30 | 武汉理工大学 | Dopamine compound modified or coated nano particle modified polymer composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Enhanced dielectric and ferroelectric properties induced by dopamine-modified BaTiO3 nanofibers in flexible poly(vinylidene fluoride-trifluoroethylene) nanocomposites;Yu Song，等;《Journal of Materials Chemistry》;20120221;第22卷(第16期);第8064页左栏第38行-右栏第14行 * |
| Enhancement of dielectric properties and energy storage density in poly(vinylidene fluoride-co-hexafluoropropylene) ceramics;Hang Luo，等;《RSC Advances》;20150728;第5卷(第84期);第68516页左栏第26行-右栏第32行 * |
| Fabrication, characterization, properties and theoretical analysis of ceramic/PVDF composite flexible films with high dielectric constant and low dielectric loss;Bingcheng Luo，等;《Journal of Materials Chemistry A》;20131126;第2卷(第2期);第511页右栏第14行-倒数第1行 * |
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