CN104098858A - Polymer matrix composite material and preparation method thereof - Google Patents
Polymer matrix composite material and preparation method thereof Download PDFInfo
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- CN104098858A CN104098858A CN201310115602.7A CN201310115602A CN104098858A CN 104098858 A CN104098858 A CN 104098858A CN 201310115602 A CN201310115602 A CN 201310115602A CN 104098858 A CN104098858 A CN 104098858A
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Abstract
The invention discloses a polymer matrix composite material and a preparation method thereof. The polymer matrix composite material comprises a base material with the content larger than 50 vol% and modified ceramic powder with the content less than 50 vol% and not equal to 0 vol% based on the total volume of the base material and the modified ceramic powder, the base material is a polymer material, and the modified ceramic powder is dispersed in the base material and is prepared by processing the surface of ceramic powder with an organic small molecule with the content between 0.5-4 wt% based on the quality of the ceramic powder. The polymer matrix composite material has high collapse electric field, low dielectric loss tangent value and high energy density, so that the industrial utilization property of the polymer matrix composite material in energy-storage industries is substantially improved.
Description
Technical field
The present invention relates to a kind of polymer matrix composite, espespecially a kind of polymer matrix composite of the ceramic powder that contains upgrading.The present invention also relates to a kind of method of preparing this polymer matrix composite.
Background technology
Along with world energy sources shortage gradually, the sustainable problem of environment enjoys attention, and the development of new energy technology becomes the New Set that global economy is grown up gradually.
The key problem of new energy technology development is energy storage technology, yet for a long time, energy storage technology could not obtain enough attention always, causes energy storage technology slowly cannot meet the demand of new energy technology development.The basis of energy storage industry is energy storage material, it can be widely used in various fields, dielectric energy storage material such as a large important kind in energy storage material has been applied to the fields such as new forms of energy, intelligent grid, hybrid vehicle, medical electronics, electronic weaponry system, therefore energy storage material attracts research institution and the industrial community extensive concern of countries in the world, to developing high-performance and energy storage material cheaply.
According to the correlation theory of dielectric substance physics, the energy density of dielectric energy storage material (energy density) can be similar to and be expressed as: U=0.5 ε
0ε
re
b 2.Wherein, ε
0permittivity of vacuum, ε
rbe the relative permittivity of material, Eb (breakdown field) is the collapse electric field of material.Therefore, how to research and develop and possess the energy storage material of high relative dielectric constant and high collapse electric field and low-dielectric loss angle tangent value (Loss tangent) and then make this energy storage material there is the Research Emphasis that high-energy-density becomes academia and industrial community.
Traditional stupalith is as BaTiO
3deng having high relative dielectric constant and low-dielectric loss angle tangent value, but the collapse electric field of stupalith is very low, and its energy density is also lower; Polymer materials is as poly(vinylidene fluoride) (poly (vinylidene fluoride), PVDF) etc. there is high collapse electric field, but its shortcoming is to have low relative permittivity and high tangent of the dielectric loss angle value simultaneously, therefore polymer materials must could obtain high-energy-density under very high strength of electric field, and then has limited its application in energy storage industry.For the advantage in conjunction with stupalith and polymer materials, take polymkeric substance as base material, and in this base material, to be filled be the effective means that ceramic polymer matrix composite for obturator just becomes the energy storage material that obtains high-energy-density.Accordingly, polymer matrix composite due to its good insulating, density is low, snappiness good, cost is low and the advantage such as easy processing, becomes just gradually a research emphasis of energy storage material.
By add the stupalith of the high-k with certain volume ratio in polymeric substrate, in the scope of this certain volume ratio, raising along with the volume ratio of stupalith, the relative permittivity of matrix material just increases, but incident shortcoming is stupalith, in polymeric substrate, reunite, cause air to enter in the system of polymer matrix composite and non-uniform electric field intensity etc., and then cause the collapse electric field of polymer matrix composite and mechanical property declines and tangent of the dielectric loss angle value improves.Because energy density is limited by relative permittivity and collapse electric field simultaneously, the relative permittivity of therefore necessary active balance polymer matrix composite and collapse electric field and optimizing, as the volume ratio of the stupalith of obturator, just can obtain maximum energy-density.
Polymer matrix composite and the shortcoming of prior art are listed below: use barium titanate (BaTiO
3) and polyvinylidene difluoride (PVDF)-R 1216 [poly (vinylidenefluoride-co-hexafluoropropylene), P (VdF-HFP)] polymer matrix composite prepared, its shortcoming is to be limited to only have the low collapse electric field of 164 megavolt/rice (MV/m) and only have 3.2 joules of/cubic centimetre (J/cm
3) low energy densities; Use BaTiO
3the polymer matrix composite of preparing with epoxy resin, because its specific inductivity is lower, its energy density under the electric field of 200MV/m 2J/cm that only has an appointment
3; The polymer matrix composite that uses multi-walled carbon nano-tubes (multi-walled carbon nanotubes, MWCNTs) and polystyrene (Polystyrene, PS) to prepare, although its relative permittivity is high, energy density is also promoted to 4J/cm
3, but it is under the frequency of 1 kilohertz, and tangent of the dielectric loss angle value excessive (>0.1), is not suitable for being applied to industry.
In sum, the polymer matrix composite of prior art is due to ubiquity pottery and the compatible bad problem of polymeric substrate, although promote ceramic volumetric than the relative permittivity that can improve polymer matrix composite, but be difficult to keep height collapse electric field and the low-dielectric loss angle tangent of polymer matrix composite simultaneously, and then cause collapsing the rapid reduction of electric field and the increase of tangent of the dielectric loss angle value, the energy density of the polymer matrix composite therefore making also cannot effectively promote, and is difficult to practical application to industry.The collapse electric field of existing pottery-polymer matrix composite is often too low, for example, be less than 200MV/m, and under the frequency of a kilohertz (Hz), tangent of the dielectric loss angle value is greater than 0.05, and energy density seldom surpasses 4J/cm again
3.How to improve collapse electric field and the energy density of polymer matrix composite, and make this polymer matrix composite there is low-dielectric loss angle tangent value simultaneously, become the problem of needing solution in current energy storage material research badly.
Summary of the invention
Main purpose of the present invention is to provide a kind of polymer matrix composite and preparation method thereof, and it has high-energy-density, low-dielectric loss angle tangent value and high collapse electric field, the industry applications that is applied to energy storage industry so as to improving it simultaneously.
For reaching aforementioned object, the invention provides a kind of polymer matrix composite, it comprises:
One base material, this base material is polymer materials; And
One is scattered in the ceramic powder of the upgrading in this base material, the ceramic powder of this upgrading refers to that the surface of a ceramic powder is through organic molecule processing, and the quality of this ceramic powder of take is benchmark, the content of this organic molecule between 0.5 weight percent (wt%) between 4wt%; The cumulative volume of ceramic powder of this base material and this upgrading of wherein take is benchmark, and the content of this base material is greater than 50 volume percent (vol%), and the content of the ceramic powder of this upgrading is less than 50vol% and is not equal to 0vol%.
According to the present invention, the particle diameter of ceramic powder of the present invention can be selected arbitrarily so as to the ceramic powder of upgrading and base material are had preferably compatible and then the ceramic powder of upgrading is scattered in base material uniformly.Preferably, the particle diameter of ceramic powder such as but not limited to, between between 10 nanometers to 10 micron.
According to the present invention, polymer matrix composite of the present invention, utilize the ceramic powder of ceramic powder, base material and this upgrading of upgrading to there is the technical characterictic of the volume ratio of specified range and the certain content of organic molecule, the ceramic powder of upgrading and the compatibility of this base material are significantly increased, therefore the homogeneity of this polymer matrix composite is good, therefore polymer matrix composite of the present invention has advantages of high collapse electric field, low-dielectric loss angle tangent value and high-energy-density, therefore significantly improve the industry applications that it is applied to energy storage industry simultaneously.
Preferably, the molecular weight of this organic molecule is less than 1000Da.
According to the present invention, the molecular weight of this organic molecule is such as but not limited between between 25Da to 1000Da or between between 50Da to 900Da or between between 100Da to 800Da or between between 100Da to 700Da.
Preferably, this organic molecule contains a functional group, and this functional group is selected from following formed group: carbonyl and halogen.
According to the present invention, the functional group that the present invention contains carbonyl or halogen by this organic molecule, the ceramic powder of upgrading and the compatibility of base material are improved, and then the ceramic powder of upgrading is scattered in this base material more uniformly, therefore the homogeneity of polymer matrix composite of the present invention significantly increases.
Better, this organic molecule is carbonyl compound or the halogen organic compound that molecular weight is less than 1000Da.
Preferably, this organic molecule is selected from following formed group: ptfe phthalate, butyl phosphoric acid, 4,5-difluoro phthalic acid, 3,6-difluoro phthalic acid, 2-are amino-4,5-difluoro-benzoic acid with and combination.
Preferably, the cumulative volume of ceramic powder of this base material and this upgrading of take is benchmark, and the content of this base material is between between 70vol% to 95vol%, and the content of the ceramic powder of this upgrading is between between 5vol% to 30vol%.
Better, the cumulative volume of ceramic powder of this base material and this upgrading of take is benchmark, and the content of this base material is 90vol%, and the content of the ceramic powder of this upgrading is 10vol%.
According to the present invention, the technical characterictic that the content that the present invention is the ceramic powder of 90vol% and this upgrading by the content of this base material is 10vol%, make collapse electric field, energy density and the tangent of the dielectric loss angle value of polymer matrix composite all have lifting more significantly, therefore more significantly improve suitable its industry applications.
Preferably, wherein this base material is selected from following formed group: poly(vinylidene fluoride) [poly (vinylidene fluoride), PVDF], poly(vinylidene fluoride)-trifluoro-ethylene [poly (vinylidene fluoride-trifluoroethylene), P (VDF-TrFE)], poly(vinylidene fluoride)-trifluorochloroethylene [poly (vinylidene fluoride-hlorotrifluoroethylene), P (VDF-CTFE)] and poly(vinylidene fluoride)-R 1216 [poly (vinylidene fluoride-co-hexafluoropropylene), P (VDF-HFP)], polyethylene, polypropylene, polymethylmethacrylate, epoxy resin, polyimide with and combination.
Preferably, this ceramic powder under test frequency 1 kilohertz, its relative permittivity be greater than 10 and tangent of the dielectric loss angle value be less than 0.1.
According to the present invention, this ceramic powder is under 1 kilohertz in test frequency, and its relative permittivity is such as but not limited between between 10 to 20000 or between between 10 to 10000 or between 10 to 8000.
According to the present invention, this ceramic powder is under 1 kilohertz in test frequency, and its tangent of the dielectric loss angle value is such as but not limited between between 0.0001 to 0.01 or between 0.001 to 0.01.
Preferably, this ceramic powder is selected from following formed group: barium titanate, strontium-barium titanate and titanium dioxide.
Preferably, the collapse electric field of this polymer matrix composite is greater than 200MV/m, and under the frequency of 1 hertz (kHz), its tangent of the dielectric loss angle value is less than 0.04, and energy density is greater than 4.1J/cm
3.
Better, the collapse electric field of this polymer matrix composite is greater than 220MV/m, and under the frequency of 1kHz, tangent of the dielectric loss angle value is less than 0.03, and energy density is greater than 4.3J/cm
3.
Better again, the collapse electric field of this polymer matrix composite is greater than 260MV/m, and under the frequency of 1kHz, tangent of the dielectric loss angle value is less than 0.025, and energy density is greater than 4.34J/cm
3.Better, the collapse electric field of this polymer matrix composite is greater than 285MV/m, and energy density is greater than 5.1J/cm
3, and under the frequency of 1kHz, tangent of the dielectric loss angle value is less than 0.02.
Preferably, under the frequency of 1kHz, the relative permittivity of this polymer matrix composite is greater than 11, better, and relative permittivity is greater than 12, and better again, relative permittivity is greater than 17, better, and relative permittivity is greater than 25.
According to the present invention, the present invention measures the electric field of energy density of polymer matrix composite such as but not limited to approaching or equaling to collapse electric field.
The present invention more provides a kind of method of preparing aforesaid polymer matrix composite, and it comprises the following steps:
One ceramic powder is provided;
Use this ceramic powder of a solvent and an organic molecule, obtain a mixing solutions, the quality of ceramic powder of wherein take is benchmark, and the content of this organic molecule is between between 1wt% to 5wt%;
Powder and solvent in separated this mixing solutions, obtain the ceramic powder of a upgrading; And
The ceramic powder and the base material that mix this upgrading, to make this polymer matrix composite, the cumulative volume of ceramic powder of this base material and this upgrading of wherein take is benchmark, and the content of this base material is greater than 50vol%, and the content of the ceramic powder of this upgrading is less than 50vol% and is not equal to 0vol%.
According to the present invention, solvent of the present invention is such as but not limited to dehydrated alcohol, acetone, dimethyl formamide or its combination.
According to the present invention, the powder in this mixing solutions of separation of the present invention and solvent refer to powder and solvent in the separated mixing solutions of any isolation technique, such as but not limited to, centrifugal or filtration etc.
The method steps of preparing polymer matrix composite of the present invention is simple, and the polymer matrix composite making has advantages of again high collapse electric field, low-dielectric loss angle tangent value and high-energy-density simultaneously, therefore industry applications is high.
Preferably, the ceramic powder and the base material that mix this upgrading, to make the step of this polymer matrix composite, comprise ceramic powder and a base material that uses this upgrading of base material solvent, obtain the ceramic powder of a upgrading and the mixing solutions of base material, then the mode continuing with film, spin coating or hot pressing makes this polymer matrix composite.
According to the present invention, base material solvent of the present invention refers to the solvent of the base material that solubilized is selected, it can be adjusted voluntarily because of the base material of selected different polymer materialss, such as but not limited to, when this base material is fluorinated copolymer, for example, when poly(vinylidene fluoride), poly(vinylidene fluoride)-trifluoro-ethylene, poly(vinylidene fluoride)-trifluorochloroethylene or poly(vinylidene fluoride)-R 1216, this base material solvent can be acetone or dimethyl formamide.
Preferably, after the ceramic powder of this upgrading is mixed to the step that makes this polymer matrix composite with a base material, more comprise this polymer matrix composite of quench treatment, to obtain the polymer matrix composite after quench treatment, this polymer matrix composite of this quench treatment comprises that this polymer matrix composite is placed in to 150 ° of temperature ranges between C to 250 ° of C to be incubated, go through after a soaking time, then by the polymer matrix composite after this insulation be cooled to one between-80 ° of C to being less than 150 ° of temperature between C.
According to the present invention, the present invention, by the step of this this polymer matrix composite of quench treatment, can make the temperature of polymer matrix composite be incubated between 150 ° of C to 250 ° of C, so as to making this polymer matrix composite reach the state of melting; Relend by this polymer matrix composite is cooled to one between-80 ° of C to being less than 150 ° of temperature between C, make polymer matrix composite again crystallization to reach the preferably object of crystal property, and then more reduce polymer matrix composite tangent of the dielectric loss angle value, improve collapse electric field and improve energy density.Better, when this polymer matrix composite is cooled to lower temperature, more can significantly improve the performance of polymer matrix composite, i.e. the tangent of the dielectric loss angle value of better reduction polymer matrix composite, better raising collapse electric field and better raising energy density.
According to the present invention, of the present invention by this polymer matrix composite be cooled to one between-80 ° of C to be less than 150 ° of temperature between C instigate make in any way this polymer matrix composite be cooled to one between-80 ° of C to being less than 150 ° of temperature between C, its such as but not limited to: this polymer matrix composite is placed in to cold water, it is cooled between being about 130 ° of temperature between C to 140 ° of C or being cooled between being about 100 ° of temperature between C to 110 ° of C; This polymer matrix composite is placed in to frozen water, makes it be cooled between the temperature between 70 ° of C to 80 ° of C or be cooled between being about 10 ° of temperature between C to 20 ° of C; Or, this polymer matrix composite is placed in to low-temp reaction groove, it is cooled between-20 ° of C to the temperature between-80 ° of C.
According to the present invention, soaking time of the present invention can differently because of the temperature of insulation be adjusted arbitrarily, so as to making polymer matrix composite be issued to the state of melting in enough soaking times and enough temperature.Such as, but not limited to by this polymer matrix composite in the lower time of temperature of 200 ° of C, soaking time is 2 hours.
Below in conjunction with the drawings and specific embodiments, describe the present invention, but not as a limitation of the invention.
Accompanying drawing explanation
Fig. 1 is the schema of the preferred embodiment of the ceramic powder of preparation upgrading of the present invention.
Fig. 2 is the schema of the preferred embodiment of preparation polymer matrix composite of the present invention.
Fig. 3 is that embodiments of the invention 5 to embodiment 7 and comparative example 2 are to the measurement result figure of the collapse electric field of the polymer matrix composite of comparative example 4.
Fig. 4 is the measurement result figure of energy density of the polymer matrix composite of embodiments of the invention 5 to embodiment 7.
Fig. 5 is the measurement result figure of tangent of the dielectric loss angle value of the polymer matrix composite of embodiments of the invention 5 to embodiment 7.
Fig. 6 is the measurement result figure of relative permittivity of the polymer matrix composite of embodiments of the invention 5 to embodiment 7.
Embodiment
Below coordinate preferred embodiment graphic and of the present invention, further setting forth the present invention is to reach the technique means that predetermined goal of the invention is taked.
The experiment of following embodiment prepares described in flow process and source and the component proportions of each sample are described below;
Barium carbonate powder: the barium titanate crystal that is defined as cubic crystal structure after X-ray diffraction technology (X-ray diffraction, XRD) is analyzed; The particle diameter of this barium carbonate powder is 100 nanometers.
Dehydrated alcohol: purity: 98%.
Titanium dioxide powder: the structure that is defined as powder after X-ray diffraction technical Analysis is the titanium dioxide crystal of rutile structure (rutile, R type); The particle diameter of this titanium dioxide powder is 50 nanometers.
Barium-strontium titanate powder: be defined as pure phase strontium-barium titanate crystal after X-ray diffraction technical Analysis; The particle diameter of this barium-strontium titanate powder is 100 nanometers.
Ptfe phthalate (tetrafluorophthalic acid): purity: 97%.
Hysteresis Measuring System: model: TF analyzer2000, manufacturers: aixACCT (Germany), for measuring energy density and breaking down field strength, probe temperature: room temperature, the diameter of the sample electrode of use is 3 millimeters (mm).
Electric impedance analyzer: model: HP4294A, for measuring relative permittivity and tangent of the dielectric loss angle value, probe temperature: room temperature, the diameter of the sample electrode of use is 3 millimeters (mm).
Below enumerate several embodiment for the present invention that demonstrates, these embodiment not want to limit the scope of the invention by any way, but are used to indicate material of the present invention and the method how implemented.
Embodiment 1 prepares the barium carbonate powder of upgrading
The present embodiment makes the barium carbonate powder of upgrading with barium carbonate powder and ptfe phthalate, so as to making the surface of barium carbonate powder through ptfe phthalate modifying process, please refer to shown in Fig. 1, and its detailed preparation method is as described below:
First, complete ceramic powder, in the present embodiment, this ceramic powder is barium carbonate powder;
Disperse this ceramic powder in a solvent, continue and process 1 hour with ultrasonic vibrating, so as to ceramic powder is dispersed in solvent, obtain a ceramic powder suspension liquid, in the present embodiment, this solvent is the dehydrated alcohol of 100 milliliters;
Then, add organic molecule in this ceramic powder suspension liquid, in the present embodiment, this organic molecule is ptfe phthalate, the quality of the barium carbonate powder in this ceramic powder suspension liquid of wherein take is benchmark, and the addition of ptfe phthalate is 1wt%, continues and processes 30 minutes with ultrasonic vibrating, so as to making ptfe phthalate evenly mix with barium carbonate powder and be scattered in dehydrated alcohol, obtain a mixing solutions;
At the temperature of 80 ° of C, this mixing solutions of uniform stirring, goes through a mixing time, and in the present embodiment, this mixing time is 1 hour, but is not limited to this;
Finally, with powder and solvent in separated this mixing solutions of centrifugation technique, this powder obtaining is the ceramic powder of upgrading, in the present embodiment, and the barium carbonate powder that the ceramic powder of this upgrading is upgrading.The barium carbonate powder of the upgrading of the present embodiment is measured the content of ptfe phthalate with thermogravimetric analyzer, can learn that take the quality of barium carbonate powder is benchmark, should be that content of ptfe phthalate be 0.5wt%.
Embodiment 2 prepares the titanium dioxide powder of upgrading
The present embodiment makes the titanium dioxide powder of upgrading with titanium dioxide powder and ptfe phthalate, so as to making the surface of titanium dioxide powder through ptfe phthalate modifying process, its detailed preparation method roughly as described in Example 1, difference is that the selected ceramic powder of the present embodiment is titanium dioxide powder, and the quality of titanium dioxide powder in this ceramic powder suspension liquid of take is benchmark, and the addition of ptfe phthalate is 5wt%.The titanium dioxide powder of the upgrading of the present embodiment is measured the content of ptfe phthalate with thermogravimetric analyzer, can learn that take the quality of titanium dioxide powder is benchmark, and the content of this ptfe phthalate is between 3 to 4wt%.
Embodiment 3 prepares the barium-strontium titanate powder of upgrading
The present embodiment makes the barium-strontium titanate powder of upgrading with barium-strontium titanate powder and ptfe phthalate, so as to making the surface of barium-strontium titanate powder through ptfe phthalate modifying process, its detailed preparation method roughly as described in Example 1, difference is that the selected ceramic powder of the present embodiment is barium-strontium titanate powder, and the quality of barium-strontium titanate powder in this ceramic powder suspension liquid of take is benchmark, and the addition of ptfe phthalate is 1wt%.The Sr titanate powder of the upgrading of the present embodiment is measured the content of ptfe phthalate with thermogravimetric analyzer, can learn that take the quality of Sr titanate powder is benchmark, and the content of this ptfe phthalate is 0.5wt%.
Embodiment 4 prepares polymer matrix composite
The barium carbonate powder of the upgrading that the present embodiment mix embodiment 1 makes with as the poly(vinylidene fluoride) of base material, so as to preparing polymer matrix composite, please refer to shown in Fig. 2, its detailed preparation method is as described below:
The ceramic powder of complete upgrading, the ceramic powder of the upgrading that the present embodiment is selected is the barium carbonate powder of the upgrading of embodiment 1;
Disperse the ceramic powder of this upgrading in a base material solvent, continue and process 30 minutes with ultrasonic vibrating, obtain the ceramic powder suspension liquid of a upgrading, the selected base material solvent of the present embodiment is dimethyl formamide;
On the other hand, a complete base material, the selected base material of the present embodiment is poly(vinylidene fluoride);
Mix the ceramic powder suspension liquid of this base material and this upgrading and under normal temperature, stir 4 hours, obtain the ceramic powder of a upgrading and the mixing solutions of base material, wherein take the barium carbonate powder of this upgrading and the cumulative volume of this base material is benchmark, the content of this base material is 95vol%, and the content of the barium carbonate powder of this upgrading is 5vol%;
Continue the mixing solutions of the ceramic powder of this upgrading and base material is placed on a film machine, and lentamente by mixing solutions film to glass substrate of the ceramic powder of this upgrading and base material, then the temperature with 80 ° of C is dried the ceramic powder of this upgrading and the mixing solutions of base material, so as to removing the base material solvent in the ceramic powder of upgrading and the mixing solutions of base material, this base material solvent is dimethyl formamide, obtains polymer matrix composite;
This polymer matrix composite of quench treatment, it comprises this polymer matrix composite at the temperature of 200 ° of C, go through a soaking time, in the present embodiment, this soaking time is 2 hours, then this polymer matrix composite is placed in rapidly to frozen water and is cooled to a temperature that is less than 10 ° of C, dry after taking out, obtain the polymer matrix composite after quench treatment.
Embodiment 5 prepares polymer matrix composite
The barium carbonate powder of the upgrading that the present embodiment mix embodiment 1 makes with as the poly(vinylidene fluoride) of base material, so as to preparing polymer matrix composite, its detailed preparation method roughly as described in Example 4, difference is that it is benchmark that the present embodiment be take the barium carbonate powder of this upgrading and the cumulative volume of this base material, the content of this base material is 90vol%, and the content of the barium carbonate powder of this upgrading is 10vol%.
Embodiment 6 prepares polymer matrix composite
The barium carbonate powder of the upgrading that the present embodiment mix embodiment 1 makes with as the poly(vinylidene fluoride) of base material, so as to preparing polymer matrix composite, its detailed preparation method roughly as described in Example 4, difference is that it is benchmark that the present embodiment be take the barium carbonate powder of this upgrading and the cumulative volume of this base material, the content of this base material is 80vol%, and the content of the barium carbonate powder of this upgrading is 20vol%.
Embodiment 7 prepares polymer matrix composite
The barium carbonate powder of the upgrading that the present embodiment mix embodiment 1 makes with as the poly(vinylidene fluoride) of base material, so as to preparing polymer matrix composite, its detailed preparation method roughly as described in Example 4, difference is that it is benchmark that the present embodiment be take the barium carbonate powder of this upgrading and the cumulative volume of this base material, the content of this base material is 70vol%, and the content of the barium carbonate powder of this upgrading is 30vol%.
Comparative example 1 is prepared polymer matrix composite
The barium carbonate powder of the upgrading that this comparative example mix embodiment 1 makes with as the poly(vinylidene fluoride) of base material, so as to preparing polymer matrix composite, its detailed preparation method roughly as described in Example 4, difference is that it is benchmark that this comparative example be take the barium carbonate powder of this upgrading and the cumulative volume of this base material, the content of this base material is 40vol%, and the content of the barium carbonate powder of this upgrading is 60vol%.
Comparative example 2 is prepared polymer matrix composite
This comparative example is usingd barium carbonate powder and make polymer matrix composite as the poly(vinylidene fluoride) of base material, wherein organic molecule modifying process is not passed through on the surface of this barium carbonate powder, its detailed preparation method is as described below: first, complete barium carbonate powder, this barium carbonate powder is added in 30 milliliters of dimethyl formamides, continue and process 30 minutes with ultrasonic vibrating, form a ceramic powder suspension liquid;
A complete base material, this base material is poly(vinylidene fluoride), poly(vinylidene fluoride) is added to this ceramic powder suspension liquid, and under normal temperature, stir 4 hours, obtain the mixing solutions of a ceramic powder and base material, the cumulative volume of this barium carbonate powder and this base material of wherein take is benchmark, and the content of this base material is 90vol%, and the content of this barium carbonate powder is 10vol%;
Continue the mixing solutions of this ceramic powder and base material is placed on a film machine, and with low speed by mixing solutions film to glass substrate of this ceramic powder and base material, then with the dimethyl formamide in dry this ceramic powder of temperature of 80 ° of C and the mixing solutions of base material, obtain polymer matrix composite;
This polymer matrix composite is incubated to 2 hours at the temperature of 200 ° of C, is then placed in rapidly frozen water, after taking out, be dried and obtain the polymer matrix composite through quench treatment.
Comparative example 3 is prepared polymer matrix composite
This comparative example is usingd barium carbonate powder and make polymer matrix composite as the poly(vinylidene fluoride) of base material, wherein organic molecule modifying process is not passed through on the surface of this barium carbonate powder, its detailed preparation method is roughly as described in comparative example 2, difference is that it is benchmark that this comparative example be take the cumulative volume of this barium carbonate powder and this base material, the content of this base material is 80vol%, and the content of this barium carbonate powder is 20vol%.
Comparative example 4 is prepared polymer matrix composite
This comparative example is usingd barium carbonate powder and make polymer matrix composite as the poly(vinylidene fluoride) of base material, wherein organic molecule modifying process is not passed through on the surface of this barium carbonate powder, its detailed preparation method is roughly as described in comparative example 2, difference is that it is benchmark that this comparative example be take the cumulative volume of this barium carbonate powder and this base material, the content of this base material is 70vol%, and the content of this barium carbonate powder is 30vol%.
Comparative example 5 is prepared polymer matrix composite
This comparative example first makes the barium carbonate powder of upgrading with barium carbonate powder and ptfe phthalate, so as to making the surface of barium carbonate powder through ptfe phthalate modifying process, its detailed preparation method roughly as described in Example 1, difference is to take that the quality of the barium carbonate powder in this ceramic powder suspension liquid is benchmark, the addition of ptfe phthalate is 10wt%, then again the barium carbonate powder of this upgrading is mixed and makes polymer matrix composite with poly(vinylidene fluoride) as base material, its detailed preparation method roughly as described in Example 4, difference is that it is benchmark that this comparative example be take the barium carbonate powder of this upgrading and the cumulative volume of this base material, the content of this base material is 90vol%, the content of the barium carbonate powder of this upgrading is 10vol%.
Test case
This test case is measured collapse electric field, energy density, tangent of the dielectric loss angle value and the relative permittivity of each polymer matrix composite of embodiment 4 to embodiment 7 and comparative example 1 to 5, the test frequency of wherein measuring tangent of the dielectric loss angle value and relative permittivity is 1kHz, and the electric field of the energy density of each polymer matrix composite of measurement embodiment 4 to embodiment 7 is respectively 296MV/m, 285MV/m, 266MV/m and 226MV/m.
According to result, the collapse electric field of the polymer matrix composite of embodiment 4 be 296MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.018, relative permittivity be 11.6 and energy density be 4.7J/cm
3, the collapse electric field of the polymer matrix composite of embodiment 5 be 285MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.018, relative permittivity be 12.3 and energy density be 5.1J/cm
3, the collapse electric field of the polymer matrix composite of embodiment 6 be 266MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.025, relative permittivity be 17.5 and energy density be 4.3J/cm
3, the collapse electric field of the polymer matrix composite of embodiment 7 be 226MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.030, relative permittivity be 25.4 and energy density be 4.4J/cm
3, the collapse electric field of the polymer matrix composite of comparative example 1 be less than 100MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.052, relative permittivity be 39.7 and energy density be 1.4J/cm
3, the collapse electric field of the polymer matrix composite of comparative example 2 be 244MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.018, relative permittivity be 14.0 and energy density be 3.6J/cm
3, the collapse electric field of the polymer matrix composite of comparative example 3 be 226MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.021, relative permittivity be 19.9 and energy density be 4.1J/cm
3, the collapse electric field of the polymer matrix composite of comparative example 4 be 201MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.023, relative permittivity be 29.4 and energy density be 4.1J/cm
3, the collapse electric field of the polymer matrix composite of comparative example 5 is 280MV/m, in test frequency be that tangent of the dielectric loss angle value under 1kHz is 0.025, relative permittivity be 12.0 and energy density be 4.0J/cm
3, as shown in Figure 3, embodiment 5 to embodiment 7, energy density, tangent of the dielectric loss angle value and relative permittivity are to shown in Fig. 4 to 6 for the collapse electric field of embodiment 5 to embodiment 7 and comparative example 2 to 4.
According to Fig. 3 to Fig. 5, can learn, each polymer matrix composite compared to comparative example 1 to 5, each polymer matrix composite of embodiment 5 to embodiment 7 is compared with each polymer matrix composite of comparative example 2 to 4 respectively, there is the effect that collapse electric field obviously increases, meanwhile, the energy density of each polymer matrix composite of embodiment 4 to embodiment 7 is all greater than 4.1J/cm
3and tangent of the dielectric loss angle value is all less than 0.04 characteristic, therefore can learn that polymer matrix composite of the present invention can possess the advantage of high collapse electric field, high-energy-density and low-dielectric loss angle tangent value really, and then applicable to electron stored energy element simultaneously.Further, the collapse electric field of the polymer matrix composite of embodiment 5 up to 285MV/m, energy density up to 5.1J/cm
3and tangent of the dielectric loss angle value is 0.02, in each performance, all have more significantly and promote, and the energy density of the embodiment 5 relatively energy density of example 2 improves 42%, therefore when the content that polymkeric substance machine matrix material of the present invention is the barium carbonate powder of 90vol% and this upgrading in the content of base material is 10vol%, be more suitable for electron stored energy element.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection domain of the claims in the present invention.
Claims (13)
1. a polymer matrix composite, is characterized in that, it comprises:
One base material, this base material is polymer materials; And
One is scattered in the ceramic powder of the upgrading in this base material, and process through organic molecule on the surface that the ceramic powder of this upgrading refers to a ceramic powder, and to take the quality of this ceramic powder be benchmark, and the content of this organic molecule is between between 0.5wt% to 4wt%;
The cumulative volume of ceramic powder of this base material and this upgrading of wherein take is benchmark, and the content of this base material is greater than 50vol%, and the content of the ceramic powder of this upgrading is less than 50vol% and is not equal to 0vol%.
2. polymer matrix composite according to claim 1, is characterized in that, the molecular weight of this organic molecule is less than 1000Da.
3. polymer matrix composite according to claim 2, is characterized in that, this organic molecule contains a functional group, and this functional group is selected from following formed group: carbonyl and halogen.
4. polymer matrix composite according to claim 3, it is characterized in that, this organic molecule is selected from following formed group: ptfe phthalate, butyl phosphoric acid, 4,5-difluoro phthalic acid, 3,6-difluoro phthalic acid, 2-are amino-4,5-difluoro-benzoic acid with and combination.
5. according to the polymer matrix composite described in any one in claim 1 to 4, it is characterized in that, the cumulative volume of ceramic powder of this base material and this upgrading of take is benchmark, the content of this base material is between between 70vol% to 95vol%, and the content of the ceramic powder of this upgrading is between between 5vol% to 30vol%.
6. polymer matrix composite according to claim 5, is characterized in that, the cumulative volume of ceramic powder of this base material and this upgrading of take is benchmark, and the content of this base material is 90vol%, and the content of the ceramic powder of this upgrading is 10vol%.
7. polymer matrix composite according to claim 1, it is characterized in that, this base material is selected from following formed group: poly(vinylidene fluoride), poly(vinylidene fluoride)-trifluoro-ethylene, poly(vinylidene fluoride)-trifluorochloroethylene and poly(vinylidene fluoride)-R 1216, polyethylene, polypropylene, polymethylmethacrylate, epoxy resin, polyimide with and combination.
8. polymer matrix composite according to claim 1, is characterized in that, this ceramic powder under test frequency 1 kilohertz, its relative permittivity be greater than 10 and tangent of the dielectric loss angle value be less than 0.1.
9. polymer matrix composite according to claim 8, is characterized in that, this ceramic powder is selected from following formed group: barium titanate, strontium-barium titanate and titanium dioxide.
10. polymer matrix composite according to claim 1, is characterized in that, its collapse electric field is greater than 200MV/m, and energy density is greater than 4.1J/cm
3, and under the frequency of 1 kilohertz, its tangent of the dielectric loss angle value is less than 0.04.
11. 1 kinds of methods of manufacturing the polymer matrix composite described in any one in claim 1 to 10, is characterized in that, it comprises the following steps:
One ceramic powder is provided;
Use this ceramic powder of a solvent and an organic molecule, obtain a mixing solutions, the quality of ceramic powder of wherein take is benchmark, and the content of this organic molecule is between between 1wt% to 5wt%;
Powder and solvent in separated this mixing solutions, obtain the ceramic powder of a upgrading; And
The ceramic powder and the base material that mix this upgrading, to make this polymer matrix composite, the cumulative volume of ceramic powder of this base material and this upgrading of wherein take is benchmark, and the content of this base material is greater than 50vol%, and the content of the ceramic powder of this upgrading is less than 50vol% and is not equal to 0vol%.
12. methods according to claim 11, it is characterized in that, the ceramic powder and the base material that mix this upgrading, to make the step of this polymer matrix composite, comprise ceramic powder and a base material that uses this upgrading of base material solvent, obtain the ceramic powder of a upgrading and the mixing solutions of base material, then the mode continuing with film, spin coating or hot pressing makes this polymer matrix composite.
13. according to the method described in claim 11 or 12, it is characterized in that, after the ceramic powder of this upgrading is mixed to the step that makes this polymer matrix composite with a base material, more comprise this polymer matrix composite of quench treatment, to obtain the polymer matrix composite after quench treatment, this polymer matrix composite of this quench treatment comprises that this polymer matrix composite is placed in to 150 ° of temperature ranges between C to 250 ° of C to be incubated, go through after a soaking time, again the polymer matrix composite after this insulation is cooled to one between-80 ° of C to being less than 150 ° of temperature between C.
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