CN106543606A - 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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Abstract
The invention discloses a kind of high energy storage density polymer composite dielectrics and preparation method thereof；The composite dielectrics includes the fluorine-containing ferroelectric polymers matrix that mass fraction is 55～97.5% and 45～2.5% modified high-k Nano filling of dopamine.The preparation method is to be prepared by solution blending, casting film-forming and hot-forming technique.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, strengthen 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 features such as light weight, pliability are good, energy storage density is high, it is adaptable to prepare the advanced electronic and electrical equipment such as high energy storage density electric capacity, embedded capacitor, field-effect transistor.
Description
Technical field
The invention belongs to dielectric substance and energy storage material preparing technical field, and in particular to a kind of high energy storage density polymerization
Thing composite dielectrics and preparation method thereof.
Background technology
The dielectric substance of high energy storage density is brilliant in Mobile energy storage electric capacity, 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 electrolyte of high energy storage density of getting everything ready is to reduce electronic device volume, improve one of critical path of integrated level.
Theoretical according to electrolyte, the maximum energy storage density of dielectric substance can pass through formula：Umax=0.5 ε0εrEb 2Carry out
Calculate.Wherein ε0Refer to permittivity of vacuum, εrRefer to the dielectric constant of dielectric substance, EbRefer to puncturing for dielectric substance
Intensity.Therefore, only try to improve dielectric dielectric constant and breakdown strength, it is possible to which the energy storage for improving dielectric substance is close
Degree.At present, many for improving the research of polymeric matrix dielectric constant, which prepares two approach that mainly include：Addition has
The ceramic particle of high-k inserts conducting particles.The dielectric that introducing conducting particles can greatly improve composite is normal
Count, but the breakdown strength of composite drastically declines, and dielectric loss can be significantly increased so that this method is not suitable for preparing
The composite dielectric material of high energy storage density.The ceramic particle of addition high-k can not only improve the dielectric of composite
Constant, can also make composite keep high breakdown strength and low-dielectric loss.However, due to the pottery of most of high-ks
Porcelain particle is incompatible with polymeric matrix.When particularly ceramic particle is reduced in size to nanoscale, easily send out in the polymer
It is raw to reunite, cause that the breakdown strength of composite is greatly reduced, dielectric loss is significantly increased, limit composite energy storage density
Raising.Therefore, develop a kind of dielectric constant height and the high polymer composites of breakdown strength are used as high energy storage density material
Become extremely important.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of high energy storage density polymer composite dielectrics
And preparation method thereof.The Nano filling of high-k is modified using the dopamine with backbone, dopamine list
Unit forms a strata dopamine in Nano filling surface aggregate, and the long chain being grafted in poly-dopamine not only can be with matrix
Polymer chain mutually tangles, and can also prevent to contact with each other between Nano filling, and the interface such that it is able to improve composite is tied
With joint efforts, material internal defect is reduced, makes material possess higher dielectric constant, higher breakdown strength and relatively low dielectric are damaged
Consumption.
The purpose of the present invention is achieved through the following technical solutions：
The invention provides a kind of high energy storage density polymer composite dielectrics, including mass fraction is 55～97.5%
Fluorine-containing ferroelectric polymers matrix and 45～2.5% the modified high-k Nano filling of dopamine；The dopamine is to change
Property dopamine, the high-k Nano filling be Nano Ceramic Particles.The material based on fluoropolymer, with modified
The Nano Ceramic Particles of high-k are filler, are prepared by solution blending, casting film-forming and hot press forming technology.Institute
State Nano Ceramic Particles reaction of the modified Nano ceramic particle by the modified dopamine of backbone with high-k to be obtained.
The present invention can not be obtained using unmodified dopamine.
Preferably, described fluorine-containing ferroelectric polymers matrix is PVDF, P (VDF-HFP), P (VDF-TrFE) or P (VDF-
TrFE-CFE at least one in).
It is highly preferred that described fluorine-containing ferroelectric polymers matrix is P (VDF-HFP) or P (VDF-TrFE).Can ensure simultaneously
Composite possesses high dielectric constant, low dielectric loss.
Preferably, the modified high-k Nano filling of described dopamine is through the following steps that prepare：
Modified dopamine is dissolved in into formation solution a in isopropanol, high-k Nano filling is dispersed in into 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；Ethanol and water washing are used after centrifugation, the modified high-k Nano filling of the dopamine is obtained final product.
Preferably, the consumption of described modified dopamine for high-k Nano filling quality 0.5～35%.It is described
Modified dopamine consumption within the range when, the moderate one layer of fine and close organic layer of thickness can be formed on Nano filling surface.If modified
Dopamine consumption is too high, and the organic layer on Nano filling surface can be caused too thick；Consumption is too low, can cause the Nano filling surface can not
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 phenyls) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl.
More electedly, the modified dopamine is 2- amino -3- (3,4- dihydroxy phenyl) propanoic acid -1H, and 1H, 2H, 2H- are complete
Fluorine last of the ten Heavenly stems ester.
Preferably, the modified dopamine adopts 1-decanol or 1H, 1H, 2H, 2H- perfluor decanol and L-3,4- dihydroxy phenylpropyl alcohol
It is prepared by propylhomoserin reaction.The Nano filling of high-k is modified using the modified dopamine of backbone, can be in nanometer
Filler surface aggregate forms one layer of poly-dopamine with backbone.
Preferably, described high-k Nano filling is titanium dioxide, strontium titanates, barium strontium titanate, Barium metatitanate., zirconium titanium
At least one in lead plumbate, CaCu 3 Ti 4 O.
Preferably, described high-k Nano filling is nano-particle, nano wire or nanometer sheet.
From the point of view of the point for easily improving Nano filling dispersibility, the preferably modified high-k nanometer of the dopamine is filled out
Expect for 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H, the modified Nano filling of 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-k Nano filling be 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl be 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-k Nano filling be 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl be modified
Nanometer sheet or nano wire.
Present invention also offers a kind of preparation method of high energy storage density polymer composite dielectrics, methods described include as
Lower step：
A, the fluorine-containing ferroelectric polymers matrix is added into N, in N- diformamide solution at 65～75 DEG C stirring and dissolving,
Obtain solution A；
B, the high-k Nano filling that the dopamine is modified add N, in N- diformamide solution at room temperature
Stirring 25～30 minutes, obtains B solution；
C, mix the A and B solution at room temperature, after stirring 25～30 minutes, by solution cast film formation, and 85～95
DEG C drying 6～7 hours, obtains polymer composites；
D, by the polymer composites 60～65 DEG C vacuum drying 10～12 hours after, be placed in mould in 180
～185 DEG C, hot pressing 5～7 minutes under 10～15MPa, obtain final product high energy storage density polymer composite dielectrics.
Preferably, in step A, per 55～60mL N, in N- diformamide solution, add 2.75～4.875g fluorine-containing
Ferroelectric polymers matrix；In step B, per 5～100mL N, 0.125～2.25g in N- diformamide solution, is added to be modified
High-k Nano filling.
The present invention is that, in fluorine-containing ferroelectric polymers matrix, the modified high dielectric of dopamine of the addition with backbone is normal
Number Nano fillings, are prepared for a kind of high energy storage density polymer by solution blending, casting film-forming and the technique such as hot-forming multiple
Close electrolyte.
The present invention does filler using with the Nano Ceramic Particles of high-k, with higher fluorine-containing of intrinsic dielectric constant
Polymer does matrix, has the modified DOPA of backbone by one layer of the Nano Ceramic Particles Surface coating in high-k
Amine as compatilizer, to improve the dispersibility of Nano Ceramic Particles, and Nano Ceramic Particles and fluorine-containing ferroelectric polymers matrix
Between the compatibility, be remarkably improved polymeric matrix dielectric constant so as to reach, while keeping that composite is higher hits
The purpose of intensity and relatively low dielectric loss is worn, polymer-based high energy storage density material is prepared.
Compared with prior art, the present invention has following beneficial effect：The dopamine with backbone is selected to be modified
High-k Nano filling, relative to the activity polymerizating technology that surface initiation is typically in existing modification technology, in the present invention
The modified of high-k Nano filling can be completed by a step simple reaction；The dopamine with backbone being grafted
The dispersibility of high-k Nano filling can both have been improved, again can be well compatible with fluorine-containing ferroelectric polymers matrix, strengthen
Interface binding power between polymeric matrix and high-k Nano filling, reduces material internal defect, so as to reduce dielectric
Loss, enhancing breakdown strength.The present inventor chooses suitable polymeric matrix, high dielectric normal by constantly research
Content of modifying agent and each component of number Nano filling etc., by its synergism, obtains good invention effect.This
Bright prepared high energy storage density polymer composite dielectrics has the features such as light weight, pliability are good, energy storage density is high, is suitable for
In preparing the advanced electronic and electrical equipment such as high energy storage density electric capacity, embedded capacitor, field-effect transistor.
Description of the drawings
Detailed description non-limiting example made with reference to the following drawings by reading, the further feature of the present invention,
Objects and advantages will become more apparent upon：
Fig. 1 is that the preparation process that the present invention has the modified high-k Nano filling of the dopamine of backbone is illustrated
Figure；
The transmission electron microscope photo of modified titanium dioxide nanoplates of the Fig. 2 by adding in the embodiment of the present invention 1；
Fig. 3 is shone by the scanning and transmission electron microscopy of the modified barium carbonate nano wire added in the embodiment of the present invention 2
Piece；Wherein, it is electron microscope photo scanning to scheme a；Figure b is transmission electron microscope photo；
Pliability photos of the Fig. 4 for polymer composites prepared in the embodiment of the present invention 3；
Fig. 5 is shone for the transmission electron microscope of polymer composites ultrathin section prepared in the embodiment of the present invention 4
Piece；
Fig. 6 is shone for the transmission electron microscope of polymer composites ultrathin section prepared in the embodiment of the present invention 5
Piece；
Fig. 7 is the graph of a relation of the energy storage density with electric field of the polymer composites prepared by the embodiment of the present invention 2.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some changes and improvements can also be made.These belong to the present invention
Protection domain.
The experimental test sample of the present invention is under vulcanizing press (QLB-D types, Shanghai rubber machinery plant) by hot-forming.
Modified filler prepared by the present invention adopts field emission scanning electron microscope (Nova NanoSEM 450, the U.S.
FEI Co.) and projection electron microscope (2100 types of JEOL JEM, Jeol Ltd.) observed.
In composite prepared by the present invention filler dispersibility using retouch thoroughly ultramicroscope (2100 types of JEOL JEM,
Jeol Ltd.) observed.
The dielectric properties of the sample prepared by the present invention are using broadband dielectric spectroscopy instrument (40 types of Concept, Germany
Novocontrol companies) it is measured.
The energy storage density of the sample prepared by the present invention, by ferroelectricity analyser, (Premier II, U.S. Radiant are public
Department) determination 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 is by 97.5% mass point
2- amino -3- (3,4- dihydroxy phenyl) propanoic acid -1Hs of several PVDF as matrix and 2.5% mass fraction, 1H, 2H, 2H- are complete
The fluorine last of the ten Heavenly stems ester modified titanium dioxide nanoplate is constituted as filler.Wherein 2- amino -3- (3,4- dihydroxy phenyls) propanoic 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, the dopamine with backbone：1H, 1H, 2H, 2H- perfluor decanol and L-3,4- bloch reaction,
Obtain 2- amino -3- (3,4- dihydroxy phenyls) propanoic 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.
The titanium dioxide nanoplate filler that C, the dopamine of backbone are modified：By 2- amino -3- (3,4- dihydroxy benzenes
Base) propanoic 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) propanoic acid -1H, 1H, 2H,
The aqueous isopropanol of 2H- perfluoro decyls instills the hydrochloride buffer of three (methylol) aminomethane for being dispersed with titanium dioxide nanoplate
In liquid, 72-24 hours at 50-70 DEG C, are reacted.Ethanol and water washing are used after centrifugation, that is, obtains 2- amino -3- (3,4- dihydroxy benzenes
Base) propanoic acid -1H, the modified titanium dioxide nanoplate of 1H, 2H, 2H- perfluoro decyl.End 2- amino -3- (the 3,4- dihydroxy benzenes
Base) propanoic acid -1H, the consumption of 1H, 2H, 2H- perfluoro decyl is the 0.5～35% of titanium dioxide nanoplate quality, in the present embodiment
From 30%.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, methods described include as
Lower step：
Fluorine-containing ferroelectric polymers matrix described in 4.875g is added to 60mL N by step 1, 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) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl are modified
Nano titania be added to 5mL N, in N- diformamide solution, ultrasonic agitation 28 minutes, obtain B solution at room temperature；
Above-mentioned A and B solution are mixed, ultrasonic agitation 30 minutes by step 3 at room temperature, then by solution cast film formation, and
It is dried 7 hours in 85 DEG C of air dry oven, obtains polymer composites；
Step 4, the polymer composites that will be obtained in above-mentioned steps 3 are dried 12 little in 65 DEG C of vacuum drying oven
Shi Hou, is placed in mould 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 is by 85% mass fraction
P (VDF-HFP) as the modified titanium of 2- amino -3- (3,4- dihydroxy phenyls) decyl propionate of matrix and 15% mass fraction
Sour barium nano wire is constituted as filler.The modified barium titanate nano of wherein 2- amino -3- (3,4- dihydroxy phenyls) 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, the method synthesis 18017) reported；
B, the dopamine with backbone：1-decanol and L-3,4- bloch reaction, obtain 2- amino -3-
(3,4- dihydroxy phenyls) decyl propionate.The synthesis of this dopamine with backbone using document (Manolakis,
I.et al., Macromol.Rapid Commun.2014,35,71-76.) in method.
The barium titanate nano line filler that C, the dopamine of backbone are modified：By 2- amino -3- (3,4- dihydroxy phenyls)
Decyl propionate is dissolved in isopropanol, while barium titanate nano line to be dispersed in the hydrochloride buffer of three (methylol) aminomethane
In, then Barium metatitanate. will be dispersed with instilling dissolved with the aqueous isopropanol of 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate
In the hydrochloride buffer of three (methylol) aminomethane of nano wire, 72-24 hours at 50-70 DEG C, are reacted.Ethanol is used after centrifugation
And water washing, that is, obtain the modified barium titanate nano line of 2- amino -3- (3,4- dihydroxy phenyl) decyl propionate.The 2- ammonia
The consumption of base -3- (3,4- dihydroxy phenyl) decyl propionate for barium titanate nano line mass 0.5～35%, selects 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, methods described include as
Lower step：
Fluorine-containing ferroelectric polymers matrix described in 4.25g is added to 59mL N, in N- diformamide solution, in 65 by step 1
Stirring and dissolving at DEG C, obtains solution A；
Step 2, the barium titanate nano line that 0.75g 2- amino -3- (3,4- dihydroxy phenyl) decyl propionates are modified are added
To 35mL N, in N- diformamide solution, ultrasonic agitation 30 minutes, obtain B solution at room temperature；
Above-mentioned A and B solution are mixed, ultrasonic agitation 27 minutes by step 3 at room temperature, then by solution cast film formation, and
It is dried 6.5 hours in 90 DEG C of air dry oven, obtains polymer composites；
Step 4, the polymer composites that will be obtained in above-mentioned steps 3 are dried 11 little in 62 DEG C of vacuum drying oven
Shi Hou, is placed in mould 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 is by 75% mass fraction
, P (VDF-TrFE) it is modified as 2- amino -3- (3,4- dihydroxy phenyls) decyl propionate of matrix and 25% mass fraction
CaCu 3 Ti 4 O nano wire is constituted as filler.The modified copper titanate of wherein 2- amino -3- (3,4- dihydroxy phenyls) decyl propionate
The preparation process of calcium nano wire with embodiment 2, institute's difference is：High-k Nano filling used is CaCu 3 Ti 4 O
Nano wire.The synthesis of this CaCu 3 Ti 4 O nano wire adopts 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, methods described include as
Lower step：
Fluorine-containing ferroelectric polymers matrix described in 3.75g is added to 58mL N, in N- diformamide solution, in 68 by step 1
Stirring and dissolving at DEG C, obtains solution A；
Step 2, the CaCu 3 Ti 4 O nano wire that 1.25g 2- amino -3- (3,4- dihydroxy phenyl) decyl propionates are modified is added
Enter to 50mL N, in N- diformamide solution, ultrasonic agitation 25 minutes, obtain B solution at room temperature；
Above-mentioned A and B solution are mixed, ultrasonic agitation 25 minutes by step 3 at room temperature, then by solution cast film formation, and
It is dried 6 hours in 90 DEG C of air dry oven, obtains polymer composites；
Step 4, the polymer composites that will be obtained in above-mentioned steps 3 are dried 10 little in 60 DEG C of vacuum drying oven
Shi Hou, is placed in mould 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 is by 65% mass fraction
P (VDF-TrFE-CFE) as matrix and 35% mass fraction 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H, 1H,
The modified barium strontium titanate nano wire composition of 2H, 2H- perfluoro decyl.Wherein 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H,
With embodiment 1, institute's difference is the preparation process of the modified barium strontium titanate nano wire of 1H, 2H, 2H- perfluoro decyl：It is used
High-k Nano filling 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, methods described include as
Lower step：
Fluorine-containing ferroelectric polymers matrix described in 3.25g is added to 57mL N by step 1, 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) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl are modified
Barium strontium titanate nano wire be added to 85mL N, in N- diformamide solution, ultrasonic agitation 27 minutes, obtain B molten at room temperature
Liquid；
Above-mentioned A and B solution are mixed, ultrasonic agitation 26 minutes by step 3 at room temperature, then by solution cast film formation, and
It is dried 6 hours in 95 DEG C of air dry oven, obtains polymer composites；
Step 4, the polymer composites that will be obtained in above-mentioned steps 3 are dried 10 little in 62 DEG C of vacuum drying oven
Shi Hou, is placed in mould 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 is by 55% mass fraction
P (VDF-TrFE-CFE) as matrix and 45% mass fraction 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H, 1H,
The modified barium titanate nano particle composition of 2H, 2H- perfluoro decyl.Wherein 2- amino -3- (3,4- dihydroxy phenyls) propanoic acid -1H,
With embodiment 1, institute's difference is the preparation process of the modified barium titanate nano particle of 1H, 2H, 2H- perfluoro decyl：It is used
High-k Nano filling be barium titanate nano particle.
The present embodiment further relates to a kind of preparation method of high energy storage density polymer composite dielectrics, methods described include as
Lower step：
Fluorine-containing ferroelectric polymers matrix described in 2.75g is added to 55mL N by step 1, 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) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl are modified
Barium titanate nano particle be added to 100mL N, in N- diformamide solution, ultrasonic agitation 27 minutes, obtain B molten at room temperature
Liquid；
Above-mentioned A and B solution are mixed, ultrasonic agitation 26 minutes by step 3 at room temperature, then by solution cast film formation, and
It is dried 6 hours in 95 DEG C of air dry oven, obtains polymer composites；
Step 4, the polymer composites that will be obtained in above-mentioned steps 3 are dried 10 little in 62 DEG C of vacuum drying oven
Shi Hou, is placed in mould hot pressing 5 minutes under 182 DEG C, 12MPa, obtains high energy storage density polymer composite dielectrics.
Implementation result：The method of modifying of the high-k Nano filling used by the present invention is simple to operation, such as Fig. 1 institutes
Show, a step can be completed.Using high dielectric nano filler there is high draw ratio, such as adopt transmission electron microscope observable
There is typical two-dimensional sheet structure to the nano titanium oxide filler adopted by embodiment 1 (shown in Fig. 2).Using scanning and thoroughly
Penetrate ultramicroscope and (shown in Fig. 3) is observed to the barium titanate nano line being modified, it can be seen that be made in the embodiment of the present invention 2
There is the organic layer of one layer of 10nm or so on standby modified barium titanate nano line surface, it was demonstrated that the dopamine of backbone is successfully grafted
Nano filling surface is arrived；Polymer composites prepared by the present invention have good pliability, as shown in figure 4, implementing
Polymer composites prepared by example 3 be free to bend and do not rupture.Using transmission electron microscope observation embodiment 4
The composite ultrathin section prepared with embodiment 5 can find that Nano filling is uniformly dispersed in polymeric matrix, such as Fig. 5 and
Shown in Fig. 6；Tested by the energy storage capacity to the polymer composites prepared by the present invention, be illustrated in figure 7 enforcement
The energy storage density of the composite prepared by example 2 and the graph of a relation of electric field intensity.At room temperature to the sample prepared by the present invention
Breakdown strength up to 550kV/mm, the actual maximum energy storage density of material can reach 21.5J/cm3.The above results explanation,
Compared to 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 height and good pliability, it is adaptable to prepare portable high storage capacitor, 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 titanium dioxide nanoplate that dopamine is modified, the dopamine is unmodified dopamine, and its preparation method is：
By L-3,4- dihydroxyphenylalanines (dopamine) are dissolved in isopropanol, while titanium dioxide nanoplate is dispersed in
In the hydrochloride buffer of three (methylol) aminomethane, then will instill dissolved with L-3, the aqueous isopropanol of 4- dihydroxyphenylalanines
It is dispersed with the hydrochloride buffer of three (methylol) aminomethane of titanium dioxide nanoplate, 72-24 is reacted at 50-70 DEG C little
When.Ethanol and water washing are used after centrifugation, that is, obtains the modified titanium dioxide nanoplate of dopamine.The L-3,4- dihydroxies phenylpropyl alcohol ammonia
The consumption of acid for titanium dioxide nanoplate quality 0.5～35%, selects 30% in this comparative example.
Reunited one as the modified titanium dioxide nanoplate of dopamine is mutual using composite prepared by this comparative example
Rise, it is difficult to be effectively dispersed in polymeric matrix, it is impossible to obtain the sample for test.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make a variety of changes within the scope of the claims or change, this not shadow
Ring the flesh and blood of the present invention.In the case where not conflicting, the feature in embodiments herein and embodiment can any phase
Mutually combine.
Claims (10)
1. a kind of high energy storage density polymer composite dielectrics, it is characterised in that be 55～97.5% to contain including mass fraction
Fluorine ferroelectric polymers matrix and 45～2.5% the modified high-k Nano filling of dopamine；The dopamine is modified
Dopamine, the high-k Nano filling are Nano Ceramic Particles.
2. high energy storage density polymer composite dielectrics according to claim 1, it is characterised in that described fluorine-containing ferroelectricity
Polymeric matrix is PVDF, P (VDF-HFP), at least one in P (VDF-TrFE) or P (VDF-TrFE-CFE).
3. high energy storage density polymer composite dielectrics according to claim 2, it is characterised in that described 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, it is characterised in that described dopamine changes
Property high-k Nano filling through the following steps that prepare：
Modified dopamine is dissolved in into formation solution a in isopropanol, high-k Nano filling is dispersed in into three (methylols)
Solution b is formed in the hydrochloride buffer of aminomethane, then solution a is instilled in solution b, 72-24 is reacted at 50-70 DEG C little
When；Ethanol and water washing are used after centrifugation, the modified high-k Nano filling of the dopamine is obtained final product.
5. high energy storage density polymer composite dielectrics according to claim 4, it is characterised in that described modified DOPA
The consumption of amine for high-k Nano filling quality 0.5～35%.
6. the high energy storage density polymer composite dielectrics according to any one of claim 1,4 or 5, it is characterised in that
The modified dopamine has backbone, specially 2- amino -3- (3,4- dihydroxy phenyl) decyl propionates or 2- amino -3-
(3,4- dihydroxy phenyls) propanoic acid -1H, 1H, 2H, 2H- perfluoro decyl.
7. high energy storage density polymer composite dielectrics according to claim 6, it is characterised in that the modified dopamine
Prepared with L-3,4- bloch reactions using 1-decanol or 1H, 1H, 2H, 2H- perfluor decanol.
8. the high energy storage density polymer composite dielectrics according to any one of claim 1,4 or 5, it is characterised in that
Described Nano Ceramic Particles be titanium dioxide, strontium titanates, barium strontium titanate, Barium metatitanate., lead zirconate titanate, in CaCu 3 Ti 4 O at least
It is a kind of.
9. the high energy storage density polymer composite dielectrics according to any one of claim 1,4 or 5, it is characterised in that
Described high-k Nano filling is nano-particle, nano wire or nanometer sheet.
10. a kind of preparation method of the high energy storage density polymer composite dielectrics as any one of claim 1～9,
Characterized in that, methods described comprises the steps：
A, the fluorine-containing ferroelectric polymers matrix is added into N, in N- diformamide solution at 65～75 DEG C stirring and dissolving, obtain
Solution A；
B, the high-k Nano filling that the dopamine is modified add N, are stirred in N- diformamide solution at room temperature
25～30 minutes, obtain B solution；
C, mix the A and B solution at room temperature, it is after stirring 25～30 minutes, by solution cast film formation and dry at 85～95 DEG C
Dry 6～7 hours, obtain polymer composites；
D, by the polymer composites 60～65 DEG C vacuum drying 10～12 hours after, be placed in mould in 180～185
DEG C, hot pressing 5～7 minutes under 10～15MPa, obtain final product high energy storage density polymer composite dielectrics.
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