CN104098858B - Polymer matrix composite material and preparation method thereof - Google Patents
Polymer matrix composite material and preparation method thereof Download PDFInfo
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- CN104098858B CN104098858B CN201310115602.7A CN201310115602A CN104098858B CN 104098858 B CN104098858 B CN 104098858B CN 201310115602 A CN201310115602 A CN 201310115602A CN 104098858 B CN104098858 B CN 104098858B
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- 239000011160 polymer matrix composite Substances 0.000 title claims abstract description 49
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- 229920000642 polymer Polymers 0.000 claims description 86
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 53
- 230000015556 catabolic process Effects 0.000 claims description 38
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical class [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- XLOFNXVVMRAGLZ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2-trifluoroethene Chemical group FC(F)=C.FC=C(F)F XLOFNXVVMRAGLZ-UHFFFAOYSA-N 0.000 description 1
- COVXBJIKNGVTNV-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;1,1-difluoroethene Chemical group FC(F)=C.FC(F)=C(F)Cl COVXBJIKNGVTNV-UHFFFAOYSA-N 0.000 description 1
- DGOZIZVTANAGCA-UHFFFAOYSA-N 2-amino-4,5-difluorobenzoic acid Chemical compound NC1=CC(F)=C(F)C=C1C(O)=O DGOZIZVTANAGCA-UHFFFAOYSA-N 0.000 description 1
- VFLMWMTWWZGXGA-UHFFFAOYSA-N 3,6-difluorophthalic acid Chemical compound OC(=O)C1=C(F)C=CC(F)=C1C(O)=O VFLMWMTWWZGXGA-UHFFFAOYSA-N 0.000 description 1
- FFSBOABNRUJQFW-UHFFFAOYSA-N 4,5-difluorophthalic acid Chemical compound OC(=O)C1=CC(F)=C(F)C=C1C(O)=O FFSBOABNRUJQFW-UHFFFAOYSA-N 0.000 description 1
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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 invention relates to a polymer-based composite material, in particular to a polymer-based composite material containing modified ceramic powder. The invention also relates to a method for preparing the polymer matrix composite.
Background
With the gradual shortage of world energy, the problem of continuous operation of the environment is emphasized, and the development of new energy technology becomes a new index of global economic growth.
The core problem of the development of new energy technology is energy storage technology, however, the energy storage technology has not been paid enough attention for a long time, so that the energy storage technology cannot meet the requirement of the development of new energy technology at a later time. The basis of the energy storage industry is energy storage materials, which can be widely applied in many fields, for example, a large important type of dielectric energy storage materials in energy storage materials has been applied in the fields of new energy, smart power grids, hybrid electric vehicles, medical electronics, electronic weapon systems, etc., so that the energy storage materials attract extensive attention of research institutions and industrial industries of all countries in the world, and the energy storage materials with high performance and low cost can be developed.
According to the theory of dielectric physics, the energy density (energy density) of a dielectric energy storage material can be approximately expressed as: u =0.50 rEb 2. Wherein,0is a dielectric constant of a vacuum, and,ris the relative permittivity of the material and eb (breakthrough downfield) is the breakdown field of the material. Therefore, how to develop an energy storage material with high relative dielectric constant, high breakdown field and low dielectric Loss tangent (Loss tangent) and make the energy storage material have high energy density is the research and development focus of academia and industry.
Conventional ceramic materials such as BaTiO3The ceramic material has high relative dielectric constant and low dielectric loss tangent, but the breakdown electric field of the ceramic material is very low, and the energy density is also low;polymer materials such as polyvinylidene fluoride (PVDF) have a high breakdown field, but have the disadvantages of both low relative dielectric constant and high dielectric loss tangent, so the polymer materials must have high energy density at very high electric field strength, and thus the application of the polymer materials in the energy storage industry is limited. In order to combine the advantages of ceramic materials and polymer materials, a polymer-based composite material in which a polymer is used as a base material and the base material is filled with a ceramic material used as a filler becomes an effective means for obtaining an energy storage material with high energy density. Accordingly, polymer-based composite materials are becoming a research focus of energy storage materials due to their advantages of good insulation, low density, good flexibility, low cost, easy processing, etc.
By adding the ceramic material with high dielectric constant with a certain volume ratio into the polymer base material, the relative dielectric constant of the composite material is increased along with the increase of the volume ratio of the ceramic material in the range of the certain volume ratio, but the relative dielectric constant of the composite material is increased along with the increase of the volume ratio of the ceramic material, but the relative dielectric constant of the composite material has the following disadvantages that the ceramic material is agglomerated in the polymer base material, air enters a system of the polymer base composite material, the electric field intensity is nonuniform, and the like, and further the collapse electric field and the mechanical property of the polymer base composite material are reduced, and the dielectric. Since the energy density is limited by both the relative permittivity and the breakdown field, the relative permittivity and the breakdown field of the polymer-matrix composite material must be effectively balanced and the volume ratio of the ceramic material as the filler optimized to obtain the maximum energy density.
The polymer-based composites of the prior art and the disadvantages are listed below: using barium titanate (BaTiO)3) With polyvinylidene fluoride-hexafluoropropylene [ poly (vinylidenefluoride-co-hexafluoropropylene) ], P (VdF-HFP)]The polymer-based composite materials prepared have the disadvantages of being limited by a low breakdown field of only 164 megavolts per meter (MV/m) and only 3.2 joules per cubic centimeter (J/cm)3) Low energy density of (a); using BaTiO3And polymer-based composites prepared from epoxy resinsThe energy density of the composite material under an electric field of 200MV/m is only about 2J/cm due to the low dielectric constant3(ii) a Polymer-based composites prepared using multi-walled carbon nanotubes (MWCNTs) and Polystyrene (Polystyrene, PS) have an energy density of up to 4J/cm despite their high relative dielectric constant3But its dielectric loss tangent is too large at a frequency of 1kHz (>0.1) is not suitable for industrial applications.
In summary, the polymer matrix composite material in the prior art generally has the problem of poor compatibility between the ceramic and the polymer substrate, and although the increase of the volume ratio of the ceramic can increase the relative dielectric constant of the polymer matrix composite material, it is difficult to simultaneously maintain the high breakdown electric field and the low dielectric loss tangent of the polymer matrix composite material, which further leads to the rapid decrease of the breakdown electric field and the increase of the dielectric loss tangent value, so that the energy density of the prepared polymer matrix composite material cannot be effectively increased, and the practical application to the industry is difficult. The breakdown field of the existing ceramic-polymer matrix composite is often too low, for example less than 200MV/m, and the dielectric loss tangent is more than 0.05 at a frequency of one kilohertz (Hz), and the energy density rarely exceeds 4J/cm3. How to improve the breakdown electric field and the energy density of the polymer matrix composite material and enable the polymer matrix composite material to have a low dielectric loss tangent value becomes a problem which needs to be solved urgently in the research of the current energy storage material.
Disclosure of Invention
The main objective of the present invention is to provide a polymer-based composite material and a preparation method thereof, which simultaneously has high energy density, low dielectric loss tangent and high breakdown electric field, thereby improving the industrial applicability of the polymer-based composite material in the energy storage industry.
To achieve the above object, the present invention provides a polymer matrix composite, comprising:
a substrate, which is a polymer material; and
the modified ceramic powder is dispersed in the base material, the modified ceramic powder refers to ceramic powder, the surface of which is treated by organic micromolecules, and the content of the organic micromolecules is between 0.5 weight percent (wt%) and 4wt% based on the mass of the ceramic powder; wherein the base material is in an amount greater than 50 volume percent (vol%), and the modified ceramic powder is in an amount less than 50vol% and not greater than 0vol%, based on the total volume of the base material and the modified ceramic powder.
According to the invention, the grain diameter of the ceramic powder can be selected at will so that the modified ceramic powder has better compatibility with the base material and is uniformly dispersed in the base material. Preferably, the particle size of the ceramic powder is, for example, but not limited to, between 10 nm and 10 μm.
According to the invention, the technical characteristics that the modified ceramic powder, the substrate and the modified ceramic powder have the volume ratio in a specific range and the specific content of the organic micromolecules are utilized, so that the compatibility of the modified ceramic powder and the substrate is greatly improved, the uniformity of the polymer-based composite material is good, and the polymer-based composite material has the advantages of high breakdown electric field, low dielectric loss tangent value and high energy density, so that the industrial applicability of the polymer-based composite material in the energy storage industry is greatly improved.
Preferably, the small organic molecules have a molecular weight of less than 1000 Da.
According to the present invention, the molecular weight of the small organic molecule is, for example but not limited to, between 25Da and 1000Da, or between 50Da and 900Da, or between 100Da and 800Da, or between 100Da and 700 Da.
Preferably, the small organic molecule contains a functional group selected from the group consisting of: carbonyl and halogen.
According to the invention, the organic micromolecules contain carbonyl or halogen functional groups, so that the compatibility of the modified ceramic powder and the base material is improved, and the modified ceramic powder is more uniformly dispersed in the base material, and the uniformity of the polymer-based composite material is greatly improved.
More preferably, the small organic molecule is a carbonyl compound or a halogen organic compound with a molecular weight of less than 1000 Da.
Preferably, the small organic molecule is selected from the group consisting of: tetrafluorophthalic acid, butylphosphoric acid, 4, 5-difluorophthalic acid, 3, 6-difluorophthalic acid, 2-amino-4, 5-difluorobenzoic acid, and combinations thereof.
Preferably, the content of the base material is between 70vol% and 95vol%, and the content of the modified ceramic powder is between 5vol% and 30vol%, based on the total volume of the base material and the modified ceramic powder.
More preferably, the content of the base material is 90vol% and the content of the modified ceramic powder is 10vol% based on the total volume of the base material and the modified ceramic powder.
According to the present invention, the breakdown electric field, the energy density and the dielectric loss tangent of the polymer-based composite material are significantly improved by the technical characteristics that the content of the base material is 90vol% and the content of the modified ceramic powder is 10vol%, so that the industrial applicability of the polymer-based composite material is greatly improved.
Preferably, wherein the substrate is selected from the group consisting of: polyvinylidene fluoride [ poly (vinylidene fluoride), PVDF ], polyvinylidene fluoride-trifluoroethylene [ poly (vinylidene fluoride-trifluoroethylene), P (VDF-TrFE) ], polyvinylidene fluoride-chlorotrifluoroethylene [ poly (vinylidene fluoride-chlorotrifluoroethylene), P (VDF-CTFE) ], and polyvinylidene fluoride-hexafluoropropylene [ poly (vinylidene fluoride-co-hexafluoropropylene), P (VDF-HFP) ], polyethylene, polypropylene, polymethylmethacrylate, epoxy, polyimide, and combinations thereof.
Preferably, the ceramic powder has a relative dielectric constant greater than 10 and a dielectric loss tangent less than 0.1 at a test frequency of 1 kHz.
According to the present invention, the relative dielectric constant of the ceramic powder is, for example, but not limited to, between 10 and 20000, or between 10 and 10000, or between 10 and 8000 at a test frequency of 1 kHz.
According to the present invention, the ceramic powder has a dielectric loss tangent of, for example, but not limited to, 0.0001 to 0.01 or 0.001 to 0.01 at a test frequency of 1 kHz.
Preferably, the ceramic powder is selected from the group consisting of: barium titanate, barium strontium titanate, and titanium dioxide.
Preferably, the polymer matrix composite has a breakdown field of greater than 200MV/m, a dielectric loss tangent of less than 0.04 at a frequency of 1 Hertz (kHz), and an energy density of greater than 4.1J/cm3。
More preferably, the polymer-based composite material has a breakdown electric field of more than 220MV/m, a dielectric loss tangent of less than 0.03 at a frequency of 1kHz, and an energy density of more than 4.3J/cm3。
More preferably, the polymer-based composite material has a breakdown electric field of more than 260MV/m, a dielectric loss tangent of less than 0.025 at a frequency of 1kHz, and an energy density of more than 4.34J/cm3. More preferably, the polymer-based composite material has a breakdown electric field of more than 285MV/m and an energy density of more than 5.1J/cm3And a dielectric loss tangent of less than 0.02 at a frequency of 1 kHz.
Preferably, the relative dielectric constant of the polymer matrix composite material is greater than 11 at a frequency of 1kHz, more preferably, the relative dielectric constant is greater than 12, still more preferably, the relative dielectric constant is greater than 17, still more preferably, the relative dielectric constant is greater than 25.
In accordance with the present invention, the electric field for measuring the energy density of a polymer-based composite material according to the present invention is, for example, but not limited to, near or equal to the breakdown electric field.
The present invention further provides a method for preparing the polymer matrix composite, which comprises the following steps:
providing a ceramic powder;
mixing the ceramic powder and an organic micromolecule by using a solvent to obtain a mixed solution, wherein the content of the organic micromolecule is between 1wt% and 5wt% based on the mass of the ceramic powder;
separating the powder and the solvent in the mixed solution to obtain modified ceramic powder; and
mixing the modified ceramic powder with a base material to prepare the polymer matrix composite, wherein the content of the base material is more than 50vol% and the content of the modified ceramic powder is less than 50vol% and is not equal to 0vol% based on the total volume of the base material and the modified ceramic powder.
According to the present invention, the solvent of the present invention is, for example, but not limited to, absolute ethanol, acetone, dimethylformamide, or a combination thereof.
According to the present invention, the separation of the powder and the solvent in the mixed solution refers to the separation of the powder and the solvent in the mixed solution by any separation technique, such as, but not limited to, centrifugation or filtration.
The method for preparing the polymer-based composite material has simple steps, and the prepared polymer-based composite material has the advantages of high breakdown electric field, low dielectric loss tangent and high energy density, so the method has high industrial applicability.
Preferably, the step of mixing the modified ceramic powder with a substrate to obtain the polymer matrix composite comprises mixing the modified ceramic powder with a substrate by using a substrate solvent to obtain a mixed solution of the modified ceramic powder and the substrate, and then preparing the polymer matrix composite by a film coating, spin coating or hot pressing manner.
According to the present invention, the substrate solvent used in the present invention refers to a solvent that can dissolve the selected substrate, which can be self-adjusted depending on the substrate of the different polymer material selected, for example, but not limited to, acetone or dimethylformamide when the substrate is a fluorine-containing copolymer, for example, polyvinylidene fluoride-trifluoroethylene, polyvinylidene fluoride-chlorotrifluoroethylene or polyvinylidene fluoride-hexafluoropropylene.
Preferably, after the step of mixing the modified ceramic powder with a base material to prepare the polymer-based composite material, the step of quenching the polymer-based composite material to obtain the quenched polymer-based composite material comprises the steps of placing the polymer-based composite material in a temperature range of 150 ℃ to 250 ℃, preserving heat, and cooling the heat-preserved polymer-based composite material to a temperature of between-80 ℃ and less than 150 ℃ after a heat preservation time.
According to the invention, the step of quenching the polymer-based composite material can keep the temperature of the polymer-based composite material between 150 ℃ and 250 ℃ so as to enable the polymer-based composite material to reach a molten state; and then the polymer matrix composite is cooled to a temperature between-80 ℃ and less than 150 ℃, so that the polymer matrix composite is recrystallized to achieve the purpose of better crystallization performance, and further the dielectric loss tangent value of the polymer matrix composite is reduced, the breakdown electric field is improved and the energy density is improved. Preferably, the polymer matrix composite material is cooled to a lower temperature, so that the performance of the polymer matrix composite material can be greatly improved, namely the dielectric loss tangent value of the polymer matrix composite material is better reduced, the breakdown electric field is better improved, and the energy density is better improved.
According to the present invention, the cooling of the polymer matrix composite to a temperature between-80 ℃ and less than 150 ℃ is performed by any method, such as but not limited to: placing the polymer matrix composite in cold water to reduce the temperature to a temperature between about 130 ℃ and 140 ℃ or to a temperature between about 100 ℃ and 110 ℃; placing the polymer matrix composite in ice water and cooling to a temperature between 70 ℃ and 80 ℃ or to a temperature between about 10 ℃ and 20 ℃; or putting the polymer matrix composite material in a low-temperature reaction tank, and cooling to a temperature between-20 ℃ and-80 ℃.
According to the invention, the holding time can be adjusted at will according to the temperature of holding, so that the polymer-based composite material can reach a molten state under sufficient holding time and sufficient temperature. For example, but not limited to, the polymer matrix composite is incubated at a temperature of 200 ℃ for a period of 2 hours.
The invention is described in detail below with reference to the drawings and specific examples, but the invention is not limited thereto.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of preparing the modified ceramic powder of the present invention.
FIG. 2 is a flow chart of a preferred embodiment of the preparation of the polymer matrix composite of the present invention.
Fig. 3 is a graph showing the results of measuring the breakdown electric field of the polymer matrix composite materials of examples 5 to 7 and comparative examples 2 to 4 of the present invention.
Fig. 4 is a graph showing the results of measuring the energy density of the polymer matrix composites of examples 5 to 7 of the present invention.
Fig. 5 is a graph showing the results of measuring the dielectric loss tangent values of the polymer matrix composites of examples 5 to 7 of the present invention.
Fig. 6 is a graph showing the results of measuring the relative dielectric constant of the polymer matrix composite materials of examples 5 to 7 of the present invention.
Detailed Description
The technical means adopted by the invention to achieve the predetermined object of the invention are further described below with reference to the drawings and the preferred embodiments of the invention.
The sources and proportions of the components of the samples described and illustrated in the experimental preparation procedures of the following examples are set forth below;
barium titanate powder: the barium titanate crystal with a cubic crystal structure is determined after being analyzed by an X-ray diffraction (XRD) technology; the particle size of the barium titanate powder is 100 nanometers.
Anhydrous ethanol: purity: 98 percent.
Titanium dioxide powder: the titanium dioxide crystal with rutile structure (Rtype) is determined as powder after being analyzed by X-ray diffraction technology; the particle size of the titanium dioxide powder is 50 nanometers.
Barium strontium titanate powder: the barium strontium titanate crystal is determined to be a pure phase barium strontium titanate crystal after being analyzed by an X-ray diffraction technology; the grain diameter of the barium strontium titanate powder is 100 nanometers.
Tetrafluorophthalic acid (tetrafluorophtalic acid): purity: 97 percent.
Hysteresis loop test system: the model is as follows: TF analyzer2000, manufacturer: aixACCT (germany) for measuring energy density and breakdown field strength, test temperature: the sample electrode used was 3 millimeters (mm) in diameter at room temperature.
An impedance analyzer: the model is as follows: HP4294A, for measuring relative dielectric constant and dielectric loss tangent, test temperature: the sample electrode used was 3 millimeters (mm) in diameter at room temperature.
The following examples are presented to illustrate the present invention and are not intended to limit the scope of the invention in any way, but are intended to indicate how the materials and methods of the present invention may be practiced.
Example 1 preparation of modified barium titanate powder
In this embodiment, a modified barium titanate powder is prepared from barium titanate powder and tetrafluorophthalic acid, so as to modify the surface of the barium titanate powder with tetrafluorophthalic acid, as shown in fig. 1, the detailed preparation method is as follows:
firstly, ceramic powder is prepared, in the embodiment, the ceramic powder is barium titanate powder;
dispersing the ceramic powder in a solvent, and then treating the ceramic powder by ultrasonic oscillation for 1 hour to uniformly disperse the ceramic powder in the solvent to obtain a ceramic powder suspension, wherein the solvent is 100 ml of absolute ethyl alcohol in the embodiment;
then, adding small organic molecules into the ceramic powder suspension, in this embodiment, the small organic molecules are tetrafluorophthalic acid, wherein the amount of tetrafluorophthalic acid added is 1wt% based on the mass of barium titanate powder in the ceramic powder suspension, and then performing ultrasonic oscillation treatment for 30 minutes, so as to uniformly mix tetrafluorophthalic acid and barium titanate powder and disperse the mixture in absolute ethyl alcohol, thereby obtaining a mixed solution;
uniformly stirring the mixed solution at a temperature of 80 ℃ for a mixing time, which is 1 hour in the present embodiment, but is not limited thereto;
finally, the powder and the solvent in the mixed solution are separated by a centrifugal technology, and the obtained powder is modified ceramic powder, in this embodiment, the modified ceramic powder is modified barium titanate powder. The modified barium titanate powder of the present example was measured for the content of tetrafluorophthalic acid with a thermogravimetric analyzer, and it was found that the content of tetrafluorophthalic acid was 0.5wt% based on the mass of the barium titanate powder.
Example 2 preparation of modified titanium dioxide powder
The modified titania powder was prepared from titania powder and tetrafluorophthalic acid in this example, and the surface of the titania powder was subjected to tetrafluorophthalic acid modification treatment in a manner substantially as described in example 1, except that the ceramic powder used in this example was titania powder, and the amount of tetrafluorophthalic acid added was 5wt% based on the mass of titania powder in the ceramic powder suspension. The modified titanium dioxide powder of this example was measured for the content of tetrafluorophthalic acid by thermogravimetric analysis, and it was found that the content of tetrafluorophthalic acid was between 3 and 4wt% based on the mass of the titanium dioxide powder.
EXAMPLE 3 preparation of modified barium strontium titanate powder
The present embodiment uses barium strontium titanate powder and tetrafluorophthalic acid to prepare modified barium strontium titanate powder, so as to subject the surface of the barium strontium titanate powder to tetrafluorophthalic acid modification treatment, the detailed preparation method is substantially as described in embodiment 1, except that the ceramic powder selected in the present embodiment is barium strontium titanate powder, and the amount of tetrafluorophthalic acid added is 1wt% based on the mass of the barium strontium titanate powder in the ceramic powder suspension. The modified strontium titanate powder of the present example was measured for the content of tetrafluorophthalic acid by a thermogravimetric analyzer, and it was found that the content of tetrafluorophthalic acid was 0.5wt% based on the mass of the strontium titanate powder.
Example 4 preparation of Polymer-based composite
In this example, the modified barium titanate powder prepared in example 1 is mixed with polyvinylidene fluoride as a base material to prepare a polymer-based composite material, as shown in fig. 2, the detailed preparation method is as follows:
preparing modified ceramic powder, wherein the modified ceramic powder selected in the embodiment is the modified barium titanate powder of the embodiment 1;
dispersing the modified ceramic powder in a substrate solvent, and then performing ultrasonic oscillation treatment for 30 minutes to obtain a modified ceramic powder suspension, wherein the substrate solvent selected in the embodiment is dimethylformamide;
on the other hand, a substrate is prepared, and the substrate selected in the embodiment is polyvinylidene fluoride;
mixing the base material and the modified ceramic powder suspension, and stirring for 4 hours at normal temperature to obtain a modified ceramic powder and base material mixed solution, wherein the base material content is 95vol% and the modified barium titanate powder content is 5vol% based on the total volume of the modified barium titanate powder and the base material;
placing the modified mixed solution of the ceramic powder and the base material on a film coating machine, slowly coating the modified mixed solution of the ceramic powder and the base material on a glass substrate, and drying the modified mixed solution of the ceramic powder and the base material at the temperature of 80 ℃ so as to remove the base material solvent in the modified mixed solution of the ceramic powder and the base material, wherein the base material solvent is dimethylformamide, and thus obtaining the polymer matrix composite material;
quenching the polymer-based composite material, which includes maintaining the temperature of the polymer-based composite material at 200 ℃, wherein the temperature is maintained for 2 hours in this embodiment, then rapidly placing the polymer-based composite material in ice water to reduce the temperature to less than 10 ℃, taking out and drying to obtain the quenched polymer-based composite material.
Example 5 preparation of Polymer-based composite
This example was conducted in a manner similar to that described in example 4 except that the modified barium titanate powder obtained in example 1 was mixed with polyvinylidene fluoride as a base material to prepare a polymer-based composite material, and the content of the base material was 90vol% and the content of the modified barium titanate powder was 10vol%, based on the total volume of the modified barium titanate powder and the base material.
Example 6 preparation of Polymer-based composite
This example was conducted in a manner similar to that described in example 4 except that the modified barium titanate powder obtained in example 1 was mixed with polyvinylidene fluoride as a base material to prepare a polymer-based composite material, and the content of the base material was 80vol% and the content of the modified barium titanate powder was 20vol%, based on the total volume of the modified barium titanate powder and the base material.
Example 7 preparation of Polymer-based composite
This example was conducted in a manner similar to that described in example 4 except that the modified barium titanate powder obtained in example 1 was mixed with polyvinylidene fluoride as a base material to prepare a polymer-based composite material, and the content of the base material was 70vol% and the content of the modified barium titanate powder was 30vol%, based on the total volume of the modified barium titanate powder and the base material.
Comparative example 1 preparation of Polymer-based composite Material
This comparative example was prepared by mixing the modified barium titanate powder obtained in example 1 with polyvinylidene fluoride as a base material in a manner substantially as described in example 4, except that the content of the base material was 40vol% and the content of the modified barium titanate powder was 60vol%, based on the total volume of the modified barium titanate powder and the base material.
Comparative example 2 preparation of Polymer-based composite Material
In this comparative example, a polymer-based composite material was prepared from barium titanate powder whose surface was not subjected to a modification treatment with small organic molecules and polyvinylidene fluoride as a base material, and the detailed preparation method thereof was as follows: firstly, preparing barium titanate powder, adding the barium titanate powder into 30 ml of dimethylformamide, and then carrying out ultrasonic oscillation treatment for 30 minutes to form a ceramic powder suspension;
preparing a base material, wherein the base material is polyvinylidene fluoride, adding the polyvinylidene fluoride into the ceramic powder suspension, and stirring at normal temperature for 4 hours to obtain a mixed solution of the ceramic powder and the base material, wherein the content of the base material is 90vol% and the content of the barium titanate powder is 10vol% based on the total volume of the barium titanate powder and the base material;
placing the mixed solution of the ceramic powder and the base material on a film coating machine, coating the mixed solution of the ceramic powder and the base material on a glass substrate at a low speed, and drying the dimethylformamide in the mixed solution of the ceramic powder and the base material at the temperature of 80 ℃ to obtain a polymer-based composite material;
and (3) preserving the heat of the polymer-based composite material at the temperature of 200 ℃ for 2 hours, then quickly placing the polymer-based composite material in ice water, taking out the polymer-based composite material and drying the polymer-based composite material to obtain the polymer-based composite material subjected to quenching treatment.
Comparative example 3 preparation of Polymer-based composite Material
The polymer-based composite material was prepared from barium titanate powder and polyvinylidene fluoride as a base material, wherein the surface of the barium titanate powder was not subjected to a modification treatment with small organic molecules, and the detailed preparation thereof was substantially as described in comparative example 2, except that the content of the base material was 80vol% and the content of the barium titanate powder was 20vol%, based on the total volume of the barium titanate powder and the base material.
Comparative example 4 preparation of Polymer-based composite Material
The polymer-based composite material was prepared from barium titanate powder and polyvinylidene fluoride as a base material, wherein the surface of the barium titanate powder was not subjected to a modification treatment with small organic molecules, and the detailed preparation thereof was substantially as described in comparative example 2, except that the content of the base material was 70vol% and the content of the barium titanate powder was 30vol%, based on the total volume of the barium titanate powder and the base material.
Comparative example 5 preparation of Polymer-based composite Material
This comparative example was prepared by first preparing a modified barium titanate powder from a barium titanate powder and tetrafluorophthalic acid to subject the surface of the barium titanate powder to a tetrafluorophthalic acid modification treatment, and the detailed preparation was substantially as described in example 1, except that the amount of tetrafluorophthalic acid added was 10wt% based on the mass of the barium titanate powder in the ceramic powder suspension, and then the modified barium titanate powder was mixed with polyvinylidene fluoride as a base material to prepare a polymer-based composite material, and the detailed preparation was substantially as described in example 4, except that the content of the base material was 90vol% and the content of the modified barium titanate powder was 10vol% based on the total volume of the modified barium titanate powder and the base material.
Test example
This test example measured the collapse electric field, the energy density, the dielectric loss tangent value and the relative permittivity of each of the polymer-based composites of examples 4 to 7 and comparative examples 1 to 5, wherein the test frequency for measuring the dielectric loss tangent value and the relative permittivity was 1kHz, and the electric fields for measuring the energy densities of each of the polymer-based composites of examples 4 to 7 were 296MV/m, 285MV/m, 266MV/m and 226MV/m, respectively.
According to the results, the polymer base of example 4The composite material had a breakdown electric field of 296MV/m, a dielectric loss tangent at a test frequency of 1kHz of 0.018, a relative dielectric constant of 11.6 and an energy density of 4.7J/cm3The polymer-based composite material of example 5 had a breakdown electric field of 285MV/m, a dielectric loss tangent at a test frequency of 1kHz of 0.018, a relative dielectric constant of 12.3 and an energy density of 5.1J/cm3The polymer-based composite material of example 6 had a breakdown electric field of 266MV/m, a dielectric tangent at a test frequency of 1kHz of 0.025, a relative dielectric constant of 17.5 and an energy density of 4.3J/cm3The polymer-based composite material of example 7 had a breakdown field of 226MV/m, a dielectric loss tangent at a test frequency of 1kHz of 0.030, a relative dielectric constant of 25.4 and an energy density of 4.4J/cm3The polymer-based composite material of comparative example 1 had a breakdown electric field of less than 100MV/m, a dielectric tangent at a test frequency of 1kHz of 0.052, a relative dielectric constant of 39.7 and an energy density of 1.4J/cm3The polymer-based composite material of comparative example 2 had a breakdown field of 244MV/m, a dielectric loss tangent at a test frequency of 1kHz of 0.018, a relative dielectric constant of 14.0 and an energy density of 3.6J/cm3The polymer-based composite material of comparative example 3 had a breakdown field of 226MV/m, a dielectric tangent at a test frequency of 1kHz of 0.021, a relative dielectric constant of 19.9 and an energy density of 4.1J/cm3The polymer-based composite material of comparative example 4 had a breakdown field of 201MV/m, a dielectric tangent at a test frequency of 1kHz of 0.023, a relative dielectric constant of 29.4 and an energy density of 4.1J/cm3The polymer-based composite material of comparative example 5 had a breakdown field of 280MV/m, a dielectric tangent at a test frequency of 1kHz of 0.025, a relative dielectric constant of 12.0 and an energy density of 4.0J/cm3The breakdown fields of examples 5 to 7 and comparative examples 2 to 4 are shown in fig. 3, and examples 5 to 7, the energy density, the dielectric loss tangent and the relative dielectric constant are shown in fig. 4 to 6.
As can be seen from FIGS. 3 to 5, the polymers were compared with comparative examples 1 to 5The polymer-based composite materials of examples 5 to 7 have significantly increased breakdown field compared to the polymer-based composite materials of comparative examples 2 to 4, and the energy density of the polymer-based composite materials of examples 4 to 7 is greater than 4.1J/cm3And the dielectric loss tangent value is less than 0.04, so that the polymer-based composite material of the invention can be found to have the advantages of high breakdown electric field, high energy density and low dielectric loss tangent value, and can be further applied to electronic energy storage elements. Further, the polymer-based composite material of example 5 has a breakdown electric field as high as 285MV/m and an energy density as high as 5.1J/cm3The dielectric loss tangent value is 0.02, the performances are improved more remarkably, and the energy density of the embodiment 5 is improved by 42% compared with the energy density of the comparative example 2, so that the polymer-organic composite material of the invention is more suitable for electronic energy storage elements when the content of the base material is 90vol% and the content of the modified barium titanate powder is 10 vol%.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A polymer-matrix composite material, characterized in that it comprises:
a substrate, which is a polymer material; and
the modified ceramic powder is dispersed in the base material, the modified ceramic powder refers to the ceramic powder, the surface of which is treated by organic micromolecules, the organic micromolecules are tetrafluorophthalic acid, and the content of the organic micromolecules is between 0.5 and 4 weight percent based on the mass of the ceramic powder;
wherein the base material accounts for 80vol% to 95vol% of the total volume of the base material and the modified ceramic powder, the modified ceramic powder accounts for 5vol% to 20vol%, and the breakdown electric field of the polymer matrix composite material is greater than or equal to 266 MV/m.
2. The polymer-matrix composite of claim 1, wherein the small organic molecules have a molecular weight of less than 1000 Da.
3. The polymer-based composite material according to claim 1, wherein the base material is contained in an amount of 90vol% and the modified ceramic powder is contained in an amount of 10vol%, based on the total volume of the base material and the modified ceramic powder.
4. The polymer-matrix composite of claim 1, wherein the substrate is selected from the group consisting of: polyvinylidene fluoride, polyvinylidene fluoride-trifluoroethylene, polyvinylidene fluoride-chlorotrifluoroethylene, and polyvinylidene fluoride-hexafluoropropylene, polyethylene, polypropylene, polymethyl methacrylate, epoxy resins, polyimides, and combinations thereof.
5. The polymer-matrix composite of claim 1, wherein the ceramic powder has a relative dielectric constant greater than 10 and a dielectric loss tangent less than 0.1 at a test frequency of 1 kHz.
6. The polymer-matrix composite of claim 5, wherein the ceramic powder is selected from the group consisting of: barium titanate, barium strontium titanate, and titanium dioxide.
7. The polymer-matrix composite of claim 1, having an energy density greater than 4.1J/cm3And a dielectric loss tangent of less than 1kHz0.04。
8. A method for manufacturing a polymer matrix composite according to any one of claims 1 to 7, characterized in that it comprises the following steps:
providing a ceramic powder;
mixing the ceramic powder and an organic micromolecule by using a solvent to obtain a mixed solution;
separating the powder and the solvent in the mixed solution to obtain modified ceramic powder; and
mixing the modified ceramic powder with a base material to obtain the polymer matrix composite.
9. The method of claim 8, wherein the step of mixing the modified ceramic powder with a substrate to obtain the polymer matrix composite comprises mixing the modified ceramic powder with a substrate using a substrate solvent to obtain a mixed solution of the modified ceramic powder and the substrate, and then preparing the polymer matrix composite by coating, spin coating or hot pressing.
10. The method of claim 8 or 9, further comprising quenching the polymer-based composite material after the step of mixing the modified ceramic powder with a substrate to obtain the quenched polymer-based composite material, wherein the quenching step comprises holding the polymer-based composite material at a temperature ranging from 150 ℃ to 250 ℃ for a holding time, and then cooling the held polymer-based composite material to a temperature ranging from-80 ℃ to less than 150 ℃.
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