CN115058117A - Ultra-high temperature resistant polymer-based dielectric energy storage nano composite film and preparation method thereof - Google Patents
Ultra-high temperature resistant polymer-based dielectric energy storage nano composite film and preparation method thereof Download PDFInfo
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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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- 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
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention belongs to the technical field of dielectric composite materials, and particularly relates to an ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film and a preparation method thereof. According to the invention, titanium dioxide is nano-dispersed in Polyimide (PI) solution by using a solution blending method, and then the mixed solution is spin-coated on a substrate to obtain a composite film, so that the preparation method is simple and has strong controllability; the nano TiO prepared by the invention 2 PerPI film, high dielectric constant and wide using titanium dioxide nanoparticlesThe temperature range and the characteristics of the hollow structure improve the energy storage density and the dielectric constant of the PI film, and the dielectric property is stable under the high-temperature condition, so that the PI film is an ultra-high temperature resistant polymer-based dielectric energy storage nano composite film and can be applied to high-temperature energy storage devices.
Description
Technical Field
The invention belongs to the technical field of dielectric composite materials, and particularly relates to an ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film and a preparation method thereof.
Background
Dielectric capacitors have fast charge and discharge rates and high power densities, and have been widely used in the fields of advanced electronic systems and power systems. With the development of technology, hybrid vehicles (operating temperature over 200 ℃), aerospace, and underground oil and gas exploration (temperature up to 300 ℃) require a new generation of dielectric capacitors capable of operating stably at high temperatures. However, the polymer-based nanocomposite used in the conventional capacitor energy storage material is difficult to stably operate at high temperature (above 200 ℃).
Polyimide (PI) is a linear dielectric, and has been one of the most popular high temperature resistant polymers due to its high glass transition temperature (360 ℃), good thermal stability (500 ℃) and dielectric properties, and low dielectric loss. However, polyimide is a high-temperature polymer, and has a low dielectric constant, so that the breakdown strength is sharply reduced due to joule heat accumulation with the increase of temperature, and the energy storage density is also reduced.
Researches show that the PI-based nanocomposite material formed by introducing the high-dielectric nano filler into the PI matrix can improve the dielectric property and the energy storage property of the PI matrix at high temperature. Currently, commonly used PI-based nanonetworksThe preparation method of the composite material mainly comprises the following two methods: (1) preparing a polyimide composite material containing titanium dioxide nano fibers: the method prepares the titanium dioxide nano-fiber/polyimide nano-composite material by an in-situ polymerization method, wherein TiO accounts for 1 vol% at normal temperature 2 The dielectric constant of the/PI is 3.5 at 1kHz, and the dielectric loss is less than 0.005; the breakdown strength is 340MV/m at 150 ℃, and the energy storage density is 1.48J/cm 3 . The dielectric constant of the PI base is slightly increased under low load, and the dielectric constant difference between the nano filler and the PI base is large, so that the local electric field distortion is caused, the agglomeration is caused, and the breakdown strength is reduced. (2) Preparing a polyimide composite material containing titanium dioxide nano fibers: the method synthesizes lead titanate (PbTiO) by a molten salt method 3 ) Nano-fiber and preparing the lead titanate nano-fiber/polyimide nano-composite material by in-situ polymerization. 50 vol% PbTiO at normal temperature 3 The dielectric constant of the/PI is 46 at 1kHz, the dielectric loss tan delta is about 0.02, and the energy storage density is 16J/cm 3 (ii) a The breakdown strength is 300MV/m at 200 ℃ and the energy storage density is 14J/cm 3 . The PI base has the advantages that the dielectric constant is greatly improved, the dielectric loss is also large, the high load reduces the distance between fillers, the agglomeration is caused, the breakdown strength is reduced, and the PI base is not suitable for application of small devices and high-temperature energy storage equipment.
In summary, the polyimide composite material prepared by the prior method has the problems of large dielectric loss, easy agglomeration, small breakdown strength and the like, so that the polyimide composite material with high breakdown strength, high energy storage density and stable dielectric property at high temperature needs to be developed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the superhigh temperature resistant polymer-based dielectric energy storage nano composite film which is a nano titanium dioxide/polyimide composite film, has high dielectric constant and energy storage density at high temperature and has stable dielectric property.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides an ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film, which is a nano titanium dioxide/polyimide composite film.
Preferably, the mass percent of the nano titanium dioxide is 1-5%.
Too high a content of inorganic nanofillers may lead to aggregation and introduce more structural defects, thereby reducing the energy storage density.
Preferably, the polyimide can also be replaced by any one of polyether-ether-ketone, polyether-imide and polyphenylene sulfide.
Preferably, the titanium dioxide nanoparticles have a particle size of 200-500 nm and are hollow structures.
The hollow structure can increase the interfacial polarization and is beneficial to enhancing the breakdown strength of the composite film.
The invention also provides a preparation method of the ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film, which comprises the following steps:
s1, adding the polyimide powder into an amide solvent, and stirring and dissolving to obtain a polyimide solution;
s2, adding titanium dioxide nanoparticles into the polyimide solution, mixing and dispersing uniformly, adding polyimide powder into the mixed solution, and mixing and dispersing uniformly again to obtain a titanium dioxide/polyimide solution;
and S3, coating the titanium dioxide/polyimide solution on a substrate, and drying to obtain the titanium dioxide/polyimide composite film.
Preferably, the preparation method of the titanium dioxide nanoparticles comprises the following steps: two-dimensional Ti 3 C 2 T x And immersing the nano-sheet into a hydrogen peroxide solution for oxidation to obtain the titanium dioxide nano-particles.
Further, in the preparation method of the titanium dioxide nanoparticles, the hydrogen peroxide solution is a 30% hydrogen peroxide solution.
Preferably, in step 1, the amide solvent is N, N-Dimethylformamide (DMF).
Preferably, the mass ratio of the polyimide powder used in the step 1 to the step 2 is 1 (16-24); the mass ratio of the titanium dioxide nanoparticles to the total amount of the polyimide powder is (1:99) - (5: 95).
Preferably, the amount of the solvent is 6 to 8ml/g based on the total amount of the polyimide powder.
Preferably, in step 3, the substrate is a glass slide or conductive glass.
Preferably, in step 3, the coating is spin-coated on the substrate at a speed of 500 to 3500 rad/min.
The invention also provides application of the ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film, which can be applied to high temperature energy storage devices and applied to hybrid electric vehicle batteries, aerospace devices and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film, which is a nano titanium dioxide/polyimide composite film, titanium dioxide nano particles with high dielectric constant, wide temperature range and hollow structure are dispersed in a PI (polyimide) base material by a solution blending method, so that the energy storage density and dielectric constant of the PI film are improved, the dielectric property is stable under high temperature conditions, and the ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film is an ultrahigh temperature resistant polymer-based dielectric energy storage nano composite film and can be applied to high temperature energy storage devices.
Drawings
FIG. 1 is a scheme for preparing TiO 2 The process schematic diagram of the/PI nano composite film;
FIG. 2 is a scanning electron microscope picture of oxidized titanium dioxide nanoparticles;
FIG. 3 is a physical representation of a 1 wt% titanium dioxide nanoparticle/PI composite film;
FIG. 4 is a schematic representation of a composite film after deposition of an aluminum electrode;
FIG. 5 is a schematic representation of dielectric property and breakdown strength measurements;
FIG. 6 shows pure PI, 1, 2 and 5 wt% nano TiO 2 The dependence of the dielectric constant of the/PI composite film on the temperature;
FIG. 7 shows pure PI, 1, 2 and 5 wt% nano TiO 2 Dielectric of/PI composite filmThe dependence of losses on temperature;
FIG. 8 shows pure PI, 1, 2 and 5 wt% nano TiO 2 The Weber distribution diagram of the/PI composite film at normal temperature;
FIG. 9 shows pure PI, 1, 2 and 5 wt% nano TiO 2 The Weber distribution diagram of the/PI composite film at the ultra-high temperature of 300 ℃;
FIG. 10 shows pure PI, 1, 2 and 5 wt% nano TiO 2 And the energy storage density of the/PI composite film at normal temperature and ultrahigh temperature of 300 ℃.
Detailed Description
The following further describes embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 11 wt% Nano-TiO 2 Preparation of/PI composite film
In this example, two-dimensional Ti was used 3 C 2 The Tx nanosheet is prepared by a selective etching method in a laboratory of Zhongshan university. The specific preparation method is shown in figure 1 and comprises the following steps:
(1) 0.1g of two-dimensional Ti 3 C 2 T x Adding the nano-sheets into 10ml of deionized water, performing ultrasonic treatment (240W) for 10min to remove surface impurities, and adding the nano-sheets into 3ml of 30% H 2 O 2 Standing the solution for oxidizing for 30min, and oxidizing the oxidized two-dimensional Ti 3 C 2 T x The nano-sheets are put into a vacuum drying oven to be dried for 4 hours at the temperature of 150 ℃ to obtain TiO 2 Nanoparticles (shown in FIG. 2), TiO 2 The particle size of the nano particles is 200-500 nm, and the nano particles are of hollow structures.
(2) Adding 0.04g of PI powder into 8ml of N, N-dimethylformamide DMF solvent, and stirring for 30min at the rotating speed of 700rpm by using a magnetic stirrer until the PI powder is completely dissolved to obtain a PI/DMF mixed solution;
(3) 0.01g of TiO 2 Adding the nano particles into the mixed solution, stirring for 4h, and then performing ultrasonic treatment (240W) for 3 min; slowly adding 0.95g PI powder into the mixed solution, stirring for 4 hr, and ultrasonic treating (240W) for 3min to obtain TiO 2 Fully dispersing to obtain TiO 2 TiO in an amount of 1 wt% 2 a/PI/DMF dispersion solution;
(4) using conductive glass ITO as a substrate, spin-coating the dispersion liquid at the speed of 500rad/min and 3500rad/min for 5s, then spin-coating the dispersion liquid for 25s by the same method, and drying the dispersion liquid in a vacuum oven at 150 ℃ for 2h to obtain TiO 2 Nano TiO with content of 1 wt% 2 The structure of the/PI composite film (the actual film is shown in figure 3) is a single layer, and the thickness is 1.5 mu m.
Example 22 wt% Nano-TiO 2 Preparation of/PI composite film
The preparation method is the same as example 1, except that: TiO in step 3 2 The amount of nanoparticles was 0.02g and the amount of PI powder was 0.94g, giving TiO 2 2 wt% of nano TiO 2 The film structure of the/PI composite film (the film is the same as that in example 1) is a single layer and has a thickness of 2 μm.
EXAMPLE 35 wt% Nano-TiO 2 Preparation of/PI composite film
The preparation method is the same as example 1, except that: TiO in step 3 2 The amount of nanoparticles was 0.05g and the amount of PI powder was 0.91g, giving TiO 2 Nano TiO with content of 5 wt% 2 The film structure of the/PI composite film (the film is the same as that in example 1) is a single layer and has a thickness of 2.5 μm.
Example 4 Nano TiO 2 Performance characterization of the/PI composite films
The test objects were the nano TiO particles of examples 1 to 3 2 The aluminum back electrode is manufactured by adopting a sputtering process before testing.
The preparation method of the aluminum back electrode comprises the following steps: first, a magnetron sputtering vacuum coater (JCP-350M3, Beijing science and technology Co., Ltd., China) was used at a speed of 10nm/minSpeed of to nano TiO 2 Depositing aluminum electrodes on the/PI composite film, removing the mask plate after depositing for 30min to obtain a 300 nm-thick circular aluminum electrode array, wherein the diameter of each electrode and the distance between two units are respectively 1mm and 2mm, and a real object diagram of the composite film after depositing the aluminum electrodes is shown in FIG. 4.
Measurement of Nano TiO by precision impedance Analyzer (E4980A, Agilent) 2 Dielectric properties of the electrode of the/PI composite film with respect to temperature, which is controlled by the heating and cooling stages (HCP621VP, INSTEC), the dielectric properties and breakdown strength of the composite film are measured schematically as shown in fig. 5, voltages are applied to the conductive glass and aluminum electrodes on both sides of the film, and various dielectric data of the composite film are measured using an analyzer:
(1) pure PI, 1, 2 and 5 wt% of nano TiO 2 Dependence of the dielectric constant of the/PI composite film on temperature:
as shown in FIG. 6, different amounts of nano TiO 2 The dielectric constant of the/PI composite film is greatly improved compared with that of a pure PI film at different temperatures, and the dielectric constant of each composite film is only slightly reduced at 300 ℃, which shows that the nano TiO film 2 The dielectric property of the/PI composite film at high temperature is good.
(2) Pure PI, 1, 2 and 5 wt% Nano TiO 2 Dependence of the dielectric loss of the/PI composite film on temperature:
1 and 2 wt% Nano TiO as shown in FIG. 7 2 The dielectric loss of the/PI composite film is only slightly increased compared with that of a pure PI film at different temperatures, and 5 wt% of nano TiO 2 The loss of the/PI composite film increases sharply at 300 ℃ because the thermal motion of the molecules at high temperature increases rapidly, resulting in a sharp increase in conductivity loss.
(3) Pure PI, 1, 2 and 5 wt% nano TiO 2 The breakdown strength of the/PI composite film at normal temperature and 300 ℃ is as follows:
as shown in the weber distribution plots of fig. 8 and 9, with nano-TiO 2 Increased content of nano TiO 2 The breakdown strength of the/PI composite film is reduced, and the breakdown strength of the 1 wt% nano TiO2/PI composite film is only slightly lower than that of pure PI.
(4) Pure PI, 1, 2 and 5 wt% nano TiO 2 The energy storage density of the/PI composite film at normal temperature and 300 ℃ is as follows:
as shown in the bar chart of FIG. 10, the nano TiO with different contents at normal temperature 2 The energy storage density of the/PI composite film is higher than that of a pure PI film; 1 and 2 wt% of nano TiO at 300 DEG C 2 The energy storage density of the/PI composite film is greatly improved compared with that of a pure PI film, and 5 wt% of nano TiO 2 The high filler content of the/PI composite film leads to aggregation and introduces more structural defects, thereby reducing the energy storage density.
In summary, the filler is filled with a small content (1-2%) of TiO 2 Of nano TiO 2 Compared with a pure PI film, the dielectric constant and the energy storage density of the PI composite film are greatly improved at normal temperature and high temperature, and the dielectric loss is lower.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principles and spirit of the invention, and these embodiments are still within the scope of the invention.
Claims (10)
1. The ultrahigh temperature resistant polymer-based dielectric energy storage nanocomposite film is characterized in that the nanocomposite film is a nano titanium dioxide/polyimide composite film.
2. The ultra-high temperature resistant polymer-based dielectric energy storage nanocomposite film as claimed in claim 1, wherein the mass percentage of the nano titanium dioxide is 1-5%.
3. The ultra-high temperature resistant polymer-based dielectric energy storage nanocomposite film as claimed in claim 1, wherein the polyimide is further replaced by any one of polyetheretherketone, polyetherimide and polyphenylene sulfide.
4. The ultrahigh temperature-resistant polymer-based dielectric energy storage nanocomposite film according to claim 1, wherein the titanium dioxide nanoparticles have a particle size of 200-500 nm and are of a hollow structure.
5. The method for preparing the ultrahigh temperature resistant polymer-based dielectric energy storage nanocomposite film as claimed in any one of claims 1 to 4, comprising the following steps:
s1, adding the polyimide powder into an amide solvent, and stirring and dissolving to obtain a polyimide solution;
s2, adding titanium dioxide nanoparticles into the polyimide solution, mixing and dispersing uniformly, adding polyimide powder into the mixed solution, and mixing and dispersing uniformly again to obtain a titanium dioxide/polyimide solution;
and S3, coating the titanium dioxide/polyimide solution on a substrate, and drying to obtain the titanium dioxide/polyimide composite film.
6. The preparation method of the ultrahigh temperature-resistant polymer-based dielectric energy storage nanocomposite film as claimed in claim 5, wherein the preparation method of the titanium dioxide nanoparticles comprises the following steps: two-dimensional Ti 3 C 2 T x And immersing the nano-sheet into a hydrogen peroxide solution for oxidation to obtain the titanium dioxide nano-particles.
7. The preparation method of the ultrahigh temperature resistant polymer-based dielectric energy storage nanocomposite film according to claim 5, wherein the mass ratio of the polyimide powder used in the step 1 to the step 2 is 1 (18-24); the mass ratio of the titanium dioxide nanoparticles to the polyimide powder is (1-5) to (95-99).
8. The preparation method of the ultrahigh temperature resistant polymer-based dielectric energy storage nanocomposite film according to claim 5, wherein the amount of the amide solvent is 6-8 ml/g based on the total amount of the polyimide powder.
9. The method for preparing the ultrahigh temperature resistant polymer-based dielectric energy storage nanocomposite film according to claim 5, wherein in the step 3, the substrate is a glass slide or conductive glass.
10. The method for preparing the ultrahigh temperature resistant polymer-based dielectric energy storage nanocomposite film according to claim 5, wherein in the step 3, the coating is performed by spin coating on the substrate at a speed of 500-3500 rad/min.
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