CN111303576A - High-temperature-resistant composite film material based on submicron ceramic filler and preparation method thereof - Google Patents
High-temperature-resistant composite film material based on submicron ceramic filler and preparation method thereof Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 239000002245 particle Substances 0.000 claims abstract description 34
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 28
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical group [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 27
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical group Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004146 energy storage Methods 0.000 abstract description 39
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- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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Abstract
The invention discloses a submicron ceramic filler-based high-temperature-resistant composite film material and a preparation method thereof. The film capacitor is used in the field of electronic information, has a large amount of heat discharged, and needs to bear a certain temperature, such as 70 ℃, and can work for a long time. The invention relates to a high-temperature-resistant composite film material based on a submicron ceramic filler, which comprises a substrate polymer and a ceramic filler doped in the substrate polymer; the ceramic filler is barium titanate ceramic particles with the particle size of 60-900nm, and the ceramic particles are modified by a surfactant. The base polymer is PMMA. Compared with PVDF polymer, the invention has strong stability of energy storage performance in a high-temperature environment of 70 ℃, and still has higher energy storage density and energy storage efficiency. According to the invention, the 500nm barium titanate ceramic filler is added into the linear dielectric PMMA, so that the breakdown strength of the composite material is increased to the maximum extent, and the energy storage density and the energy storage efficiency are improved.
Description
Technical Field
The invention belongs to the technical field of electronic functional material preparation, and particularly relates to a preparation method of a high-temperature-resistant high-energy-storage-density high-efficiency composite film material based on a submicron ceramic filler.
Background
With the development of information technology, thin film capacitors are of great importance in the field of electronic devices and microelectronics, such as inverters, pulse power devices, and the like. With the rapid decrease of the size of the capacitor on the printed circuit board, the research on the novel thin and light high dielectric material becomes the leading topic in the information function material and the micro-electronics field.
Common capacitor materials comprise polymer materials and ceramic materials, the polymer has higher Young modulus and high dielectric field strength, the breakdown field strength of the polymer is close to 400MV/m, but the dielectric constant is lower, which affects the energy storage density, for example, the dielectric constant of common polymer composite material polypropylene (PP) is between 2 and 3, the dielectric constant of fluorine-containing polymer PVDF is between 8 and 10, and the dielectric constant of PMMA (polymethyl methacrylate) is between 3 and 4, on the other hand, the ceramic material has higher dielectric constant, high displacement and low remanent polarization, but the breakdown field strength is very low, as is common with the ceramic materials barium titanate, lead zirconate titanate (PZT), in order to compound the good electrical properties of the two materials, a new structural design of ceramic filler/polymer is developed, and ceramics with high dielectric constant are uniformly dispersed in a polymer matrix to form a composite system.
At present, a dielectric composite material system is obtainedHigher energy storage, e.g. polyvinylidene fluoride-barium titanate (PVDF/BaTiO)3) A composite material. But the energy storage efficiency is low, between about 50-60%. How to solve the problem is the focus at present. In addition, the film capacitor is used in the electronic information field, has a large amount of heat discharged, and needs to bear a certain temperature, such as 70 ℃, and can work for a long time.
Disclosure of Invention
The invention aims to provide a preparation method of a composite film material with high temperature resistance, high energy storage density and high efficiency based on a submicron ceramic filler.
The invention relates to a high-temperature-resistant composite film material based on a submicron ceramic filler, which comprises a substrate polymer and a ceramic filler doped in the substrate polymer; the ceramic filler is barium titanate ceramic particles with the particle size of 60-900 nm. The base polymer is PMMA.
The ceramic filler is subjected to surface modification treatment by adopting a coupling agent, so that the compatibility of the ceramic particles and a polymer is improved, and the coupling agent is dopamine hydrochloride, 3-aminopropyltriethoxysilane and (3-mercaptopropyl) trimethoxysilane.
The mass fraction of the ceramic filler in the composite film material is 0.1-30%.
The preparation method of the submicron ceramic filler-based high-temperature-resistant composite film material comprises the following steps:
and 3, dripping a coupling agent into the suspension obtained in the step 2, fully stirring and oscillating for 1-20 times to form stable mixed suspension.
Preferably, the material-liquid ratio of the PMMA polymer to the polar solution in the step 1 is 5-200 g/L.
Preferably, the polar solution described in step 1 is an analytically pure solvent of DMF, NMP or DMAC.
Preferably, the ceramic filler in step 2 is prepared by a solid phase method, a hydrothermal method or a sol-gel method.
Preferably, the mass of the coupling agent solution added in the step 3 is 0.1-20% of the mass of the ceramic filler added in the step 2.
Preferably, the barium titanate ceramic particles in step 1 are 500 nm.
Preferably, the coupling agent in step 3 is dopamine hydrochloride.
The invention has the beneficial effects that:
1. compared with PVDF polymer, PMMA polymer has lower dielectric loss and higher energy storage efficiency, and PMMA has better high temperature resistance compared with PVDF, so that the prepared composite film material has strong energy storage performance stability in a high-temperature environment of 70 ℃, and still has higher energy storage density and energy storage efficiency.
2. According to the invention, the 500nm barium titanate ceramic filler is added into the linear dielectric PMMA, so that the breakdown strength of the composite material is improved, and the energy storage density and the energy storage efficiency are also improved.
3. The surface of the 500nm barium titanate ceramic filler is subjected to surface modification treatment, so that a lipophilic group is attached to the surface of the ceramic filler, the interface compatibility between the filler and a polymer is improved, and the filler has better dispersibility in the polymer.
Under the synergistic effect of the advantages, the performance of the PMMA/DBT (500nm) composite material film obtains a remarkable effect, the invention adopts common polymethyl methacrylate as a matrix, adopts large-size ceramic particles with excellent dielectric property as a filler, the ceramic filler has high dielectric constant and low dielectric loss, and the ceramic particles in a composite material system and the composite matrix are coupled by using a coupling agent to prepare the composite material. Tests show that the composite film material has excellent performances of high temperature resistance, high energy storage density, high efficiency and the like.
Drawings
FIG. 1 is an SEM image of 500nm barium titanate particles;
FIG. 2 is an SEM image of a PMMA/DBT (500nm) composite thin film material prepared by the invention;
FIG. 3 is a Weibull plot of the breakdown strength of PMMA/DBT (500nm) composite film material prepared in accordance with the present invention and neat polymer PMMA;
FIGS. 4a and 4b are single-phase hysteresis loop diagrams of pure polymer PMMA and PMMA/DBT (500nm) composite film material prepared by the invention at room temperature of 25 ℃ respectively;
FIGS. 5a and 5b are single-phase hysteresis loop diagrams of pure polymer PMMA and PMMA/DBT (500nm) composite film material prepared by the invention at room temperature of 70 ℃ respectively;
FIGS. 6a and 6b are respectively a comparison graph of energy storage density and energy storage efficiency of pure polymer PMMA and PMMA/DBT (500nm) composite thin film material prepared by the invention at room temperature of 25 ℃.
FIGS. 7a and 7b are respectively a comparison graph of energy storage density and energy storage efficiency of pure polymer PMMA and PMMA/DBT (500nm) composite thin film material prepared by the invention at room temperature of 25 ℃.
FIGS. 8a and 8b are Weibull plots and comparative plots of breakdown strength and releasable energy of PMMA/DBT composite materials prepared from barium titanate ceramic particles with different particle sizes, respectively.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
A high-temperature resistant composite film material based on submicron ceramic filler comprises a base polymer and the ceramic filler doped in the base polymer; the ceramic filler adopts barium titanate ceramic particles with the particle size of 500 nm. The ceramic filler is subjected to surface modification, so that the compatibility of the ceramic filler and a polymer matrix is enhanced. The base polymer is PMMA. The mass fraction of the ceramic filler in the composite film material is 3 percent.
The surface modification treatment is carried out on the barium titanate ceramic particles with the particle size of 500nm, so that the compatibility of the ceramic filler and the polymer matrix is enhanced; dissolving PMMA (polymethyl methacrylate) serving as a base polymer by using a polar solvent, adding a certain amount of barium titanate ceramic particles into a PMMA solution to prepare a composite solution, casting a composite film material by a tape casting method, drying at 150-250 ℃ to obtain a composite material, and quenching at low temperature to obtain a PMMA/DBT (500nm) composite material film.
The SEM image of the composite film described in this example is shown in fig. 2; it can be seen that: the barium titanate and the polymer base are well fused, and the surface of the sample is smooth.
The breakdown field strength of the composite material film described in this example is shown in fig. 3, and the breakdown field strength of the composite material film containing 3 wt% of barium titanate reaches 700MV/m, which is increased by about 43% compared with the breakdown field strength of pure polymer PMMA, which indicates that the addition of 500nm barium titanate ceramic particles effectively increases the breakdown field strength of the dielectric material.
Under the environment of 25 ℃, the hysteresis loop of pure PMMA is shown in FIG. 4a, and the hysteresis loop of the composite material film in the example is shown in FIG. 4 b; comparing fig. 4a and 4b, it can be seen that the electric displacement and the residual polarization of the composite material film added with 500nm barium titanate are increased compared with the pure polymer PMMA, and the maximum breakdown voltage is also increased, thereby being helpful for increasing the energy storage.
Under the environment of 70 ℃, the hysteresis loop of pure PMMA is shown in FIG. 5a, and the hysteresis loop of the composite material film in the example is shown in FIG. 5 b; as can be seen from a comparison of fig. 4a, 4b, 5a and 5b, the polarization strength in the hysteresis loop of the composite film described in this example slightly increases with increasing temperature, but the effect is smaller. It can be seen that the composite film described in this example can stably operate in an environment of 70 ℃.
The energy storage value pair of pure PMMA and the composite material film described in the example is shown in FIGS. 6a and 6b under the environment of 25 ℃, and the energy storage of the composite material containing 3% barium titanate is up to 11.4J/cm3While the pure PMMA polymer has an energy storage of up to 3.6J/cm3. The composite material containing 3% barium titanate has an energy storage 3.1 times that of the pure PMMA polymer. The energy storage efficiency of the composite material containing 3% of barium titanate is still 83.5% under 650MV/m, and the high energy storage efficiency can be still maintained after the particles are added, which shows that the addition of the particles effectively improves the energy storage of the dielectric material and enhances the electrical property of the dielectric material.
In an environment of 70 ℃, the energy storage value pair of pure PMMA and the composite material film described in this example is shown in fig. 6a and 6b, and it can be seen from fig. 6a and 6b that the pure PMMA and PMMA/DBT (500nm) composite material film has the same rule at 25 ℃ and 70 ℃, the energy storage density increases with the increase of the electric field strength, the energy storage efficiency decreases with the increase of the electric field strength, and the energy storage efficiency of the PMMA/DBT (500nm) composite material film at 70 ℃ still has a higher level, for example, under an electric field of 200MV/m, the aging rate at 70 ℃ is still as high as 91.7%, and under a high temperature, the energy storage efficiency of 90% or more can be maintained, which indicates that the PMMA/DBT (500nm) composite material has stronger stability of energy storage performance at a high temperature.
Changing the grain size of the ceramic filler into 60nm, 100nm, 200nm and 300nm, respectively preparing composite materials as a control group of the application, and comparing breakdown field strength and energy storage density; according to fig. 8a, it can be seen that the breakdown field strength increases with the increase of the particle size of the added barium titanate, and when the particle size is 500nm, the breakdown field strength reaches up to 700Mv/m, which is significantly improved compared with 60nm, 100nm, 200nm and 300 nm; referring to FIG. 8b, it can be seen from the comparative graph of the releasable energy of the composite material prepared from barium titanate with different particle sizes, that the composite material prepared with a particle size of 500nm has a releasable energy density of 9.53J/cm at 650MV/m3Much higher than composite materials prepared with other particle sizes; it can be concluded that a size of 500nm is the optimum size for the measured data. It can be seen that the barium titanate ceramic material with the particle size of 500nm is selected as the fillerThe particle charging brings unexpected technical effects.
In conclusion, the PMMA/DBT (500nm) composite material has high energy storage density, high energy storage efficiency and stronger stability of energy storage performance at high temperature, and the preparation method has simple process, easy acquisition of the selected material, good performance and low price, so that the prepared composite material has good reliability and high toughness and can be produced in large batch.
Example 2
The preparation method of the submicron ceramic filler-based high-temperature-resistant composite film material (i.e. PMMA/DBT (500nm) composite material) comprises the following process steps:
(1) adding a certain amount of base polymer into the polar solution, and fully stirring for 6-12 hours at 40-80 ℃ until the base polymer is completely dissolved to form a clear and transparent polymer solution; the material-liquid ratio of the base polymer to the polar solution is 3-100 g/L. The base polymer is PMMA.
(2) And (2) adding a certain amount of surface-modified ceramic filler into the polymer solution obtained in the step (1), fully stirring, performing ultrasonic oscillation, and circulating for 2-5 times to form a stable suspension. The ceramic filler adopts barium titanate particles with the particle size of 500 nm; the material-liquid ratio of the ceramic filler to the polymer solution is 1-100 g/L.
(3) And (3) uniformly coating the suspension obtained in the step (2) on a glass sheet by adopting a tape casting method, then drying at the temperature of 60-120 ℃ for 30 min-4 h, removing the organic solvent, and taking the composite film off the glass sheet.
(4) And (4) putting the composite film obtained in the step (3) into an oven at 180-250 ℃ for melting for 60 min-4 h, and then immediately putting the composite film into a mixed solution at-196-0 ℃ for quenching for 30 min-1 h to obtain the final composite film.
Claims (10)
1. The composite film material based on submicron ceramic filler high temperature resistance comprises a base polymer and a ceramic filler doped in the base polymer; the method is characterized in that: the ceramic filler adopts barium titanate ceramic particles with the particle size of 60-900 nm; the base polymer is PMMA.
2. The submicron ceramic filler high temperature resistant composite film material in accordance with claim 1, characterized in that: the particle size of the barium titanate ceramic particles is 500 nm.
3. The submicron ceramic filler high temperature resistant composite film material in accordance with claim 1, characterized in that: the ceramic filler is subjected to surface modification treatment by adopting a coupling agent, so that the compatibility of the ceramic particles and a polymer is improved, and the coupling agent is dopamine hydrochloride, a 3-aminopropyltriethoxysilane solution and a (3-mercaptopropyl) trimethoxysilane solution.
4. The submicron ceramic filler high temperature resistant composite film material in accordance with claim 1, characterized in that: the mass fraction of the ceramic filler in the composite film material is 0.1-30%.
5. The method for preparing the submicron ceramic filler high temperature resistant composite film material according to claim 1, wherein: step 1, adding a polymer into a polar solution, and fully stirring until the polymer is completely dissolved to form a polymer solution; the polymer is polymethyl methacrylate;
step 2, adding the ceramic filler into the polymer solution, fully stirring and oscillating for 1-20 times to form stable suspension; the material-liquid ratio of the ceramic filler to the polymer solution is 1-100 g/L; the ceramic filler is nano-submicron barium titanate ceramic filler;
step 3, dripping a coupling agent into the suspension obtained in the step 2, fully stirring and oscillating for 1-20 times to form stable mixed suspension;
step 4, coating the mixed suspension obtained in the step 3 on a glass sheet, or casting a suspension film with the thickness of 1-100 um by adopting a casting machine; directly drying the mixture for 30-60min at the temperature of 60-120 ℃ to completely dry the polar solvent to obtain a composite film;
step 5, preserving the heat of the composite film obtained in the step 4 at 180-250 ℃ for 60-120 min, and then immediately putting the composite film into a low-temperature environment at 0 ℃ for quenching treatment for 30-60min to obtain a composite film material; the thickness of the obtained composite film material is 1-100 μm.
6. The method for preparing the submicron ceramic filler high temperature resistant composite film material according to claim 5, characterized in that: the material-liquid ratio of the PMMA polymer to the polar solution in the step 1 is 5-200 g/L.
7. The method for preparing the submicron ceramic filler high temperature resistant composite film material according to claim 5, characterized in that: the polar solution described in step 1 is an analytically pure solvent of DMF, NMP or DMAC.
8. The method for preparing the submicron ceramic filler high temperature resistant composite film material according to claim 5, characterized in that: the ceramic filler in the step 2 is prepared by a solid phase method, a hydrothermal method or a sol-gel method.
9. The method for preparing the submicron ceramic filler high temperature resistant composite film material according to claim 5, characterized in that: the mass of the coupling agent solution added in the step 3 is 0.1-20% of the mass of the ceramic filler added in the step 2.
10. The method for preparing the submicron ceramic filler high temperature resistant composite film material according to claim 5, characterized in that: the coupling agent in the step 3 is a 3-aminopropyltriethoxysilane solution with a concentration of 99% or a (3-mercaptopropyl) trimethoxysilane solution with a concentration of 97%.
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| US20170301466A1 (en) * | 2015-10-19 | 2017-10-19 | Powdermet, Inc. | High-Energy Density Nancomposite Capacitor |
| CN110330676A (en) * | 2019-06-20 | 2019-10-15 | 杭州电子科技大学 | A kind of preparation method of the high dielectric constant compound film material based on ceramic packing |
| CN110643129A (en) * | 2019-09-20 | 2020-01-03 | 西安理工大学 | Polymer-ceramic composite dielectric energy storage material and preparation method thereof |
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| CN105086297A (en) * | 2015-07-31 | 2015-11-25 | 西安交通大学 | Electric energy storage dielectric ceramic/polymer composite material and preparing method thereof |
| US20170301466A1 (en) * | 2015-10-19 | 2017-10-19 | Powdermet, Inc. | High-Energy Density Nancomposite Capacitor |
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