CN116535854B - Binary blending high-temperature energy storage polymer dielectric film and preparation method thereof - Google Patents
Binary blending high-temperature energy storage polymer dielectric film and preparation method thereof Download PDFInfo
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- 238000001035 drying Methods 0.000 claims description 34
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
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- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical group CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention relates to the technical field of polymer dielectric films, and discloses a binary blended high-temperature energy storage polymer dielectric film and a preparation method thereof, wherein the polymer dielectric film has a single-layer structure, and raw materials of the polymer dielectric film comprise PEI and PSU; the PSU accounts for 5-20% of the blend of the PEI and the PSU in percentage by mass. According to the invention, the composite film is prepared by blending two polymers, and the high-temperature energy storage performance of the polymer composite film is improved by blending the two polymers according to a certain proportion; the polymer composite film is prepared by adopting a solution casting method, the preparation process is simple, no special processing process exists, the production cost is low, and the method can be used for continuous production of the film.
Description
Technical Field
The invention relates to the technical field of polymer dielectric films, in particular to a binary blending high-temperature energy storage polymer dielectric film and a preparation method thereof.
Background
The demands for storage, absorption and supply of electrical power by electronic devices are increasing with the development of energy storage technology and the power electronics industry. Currently, the devices mainly used for energy storage are mainly batteries and capacitors. Typically, batteries belong to long term energy storage devices and capacitors belong to short term energy storage devices. Batteries can provide a long-term stable energy supply, but their power density is low; while capacitors typically have high power density and low energy density and are therefore often used to generate pulsed voltages or currents.
The polymer dielectric has the advantages of flexibility, easy processing, light weight, high breakdown strength and the like. Polymers such as Polyimide (PI), polyetherimide (PEI), polysulfone (PSU), polycarbonate (PC) and the like have higher glass transition temperature (more than or equal to 150 ℃), extremely low dielectric loss and high volume resistivity, and are widely used for researching high-temperature dielectric materials and applying the materials to electrons. However, at higher temperatures (150 ℃), the leakage current of the material increases dramatically, the conductivity loss is severe, and the energy storage density decreases. Therefore, the current research mainly increases the barrier energy level at the electrode and the medium by constructing a multilayer structure, and improves the energy storage performance of the polymer dielectric material at high temperature. For example, chinese patent publication No. CN101882507B discloses a polymer-based dielectric composite material of a multilayer structure and a method for preparing the same, the composite material provided being composed of three films stacked together; the volume fraction of the polymer in the outer layer film is 90%, and the volume fraction of the inorganic ceramic particles is 10%; the volume fraction of the polymer in the intermediate layer film is 50-80%, and the volume fraction of the inorganic ceramic particles is 20-50%. This method requires multi-layer hot pressing or coating, is complicated in process, and has a difficult control of the thickness of the multi-layer film, thus being disadvantageous for industrial production.
Disclosure of Invention
In order to solve the technical problems, the invention provides the binary blending high-temperature energy storage polymer dielectric film and the preparation method thereof, the improvement of the high-temperature energy storage performance of the polymer composite film is realized through binary blending, the polymer composite film is prepared by utilizing a solution casting process, and the prepared polymer dielectric composite film has the advantages of light weight, good flexibility, high output and the like, and can be applied to the emerging fields of flexible electronics, intelligent wearing and the like.
The aim of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a binary blended high-temperature energy storage polymer dielectric film, wherein the polymer dielectric film has a single-layer structure, and raw materials of the polymer dielectric film comprise PEI and PSU; the PSU accounts for 5-20% of the blend of PEI and PSU by mass.
Polymer-based dielectric materials have found wide application due to their excellent properties of high breakdown strength, low dielectric loss, excellent processability, and unique flexibility. However, polymer-based dielectric materials alone tend to have a low dielectric constant and at higher temperatures (150 ℃) the leakage current of the material increases dramatically, the conduction loss is severe and the energy storage density is reduced. According to the invention, PEI and PSU are blended, so that a synergistic effect of 1+1 & gt2 can be generated, and the high-temperature energy storage density of the binary blend film is effectively improved under the limit of a certain proportion. And the preparation process is simple, no special processing process exists, the production cost is low, and the method can be used for continuous production of films.
Preferably, the raw materials of the polymer dielectric film further comprise modified nano barium titanate accounting for 10-30% of the mass of the blend of PEI and PSU; the modified nano barium titanate is nano barium titanate coated and modified by imidazole polymer.
The organic polymer system has the advantages of high breakdown field strength, good flexibility and easy processing, but low dielectric constant. Whereas ceramic materials have a high dielectric constant, lower breakdown field strengths limit further increases in their energy storage density. Therefore, the advantages of high dielectric constant of the ceramic material, high breakdown field strength of the polymer and the like can be organically combined by adding the barium titanate into the binary blend polymer system, so that good energy storage characteristics, especially better high-temperature energy storage effect, are obtained.
Preferably, the preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate, performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring under the protection of nitrogen; then allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide are added for reaction under the protection of nitrogen, and the nanometer barium titanate coated by imidazole polymer is obtained through centrifugal separation;
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, heating for reaction under the protection of nitrogen, and centrifugally separating to obtain epoxy group grafted nano barium titanate;
(3) And blending and grinding the epoxy group grafted nano barium titanate and cyanate resin to obtain the modified nano barium titanate.
The incompatibility between the polymer matrix and the ceramic material leads to poor composite effect, the larger dielectric constant difference between the two phases can generate a highly uneven electric field, the breakdown strength is reduced, the internal defect or agglomeration can be generated due to the incompatibility after the composite, the performance is quite unstable, the dielectric loss is increased, and the energy storage effect is poor. Therefore, the invention can improve the incompatibility of barium titanate in a polymer matrix by coating the surface of the imidazole polymer with the modified nano barium titanate. The 1- (3-aminopropyl) imidazole can be polymerized with allyl isothiocyanate, and induce double bonds in the allyl isothiocyanate to be polymerized, so that a more compact polymer layer can be formed on the surface of barium titanate particles. Then, epoxy groups are introduced through the reaction of glycidyl methacrylate on the polymer layer, and the epoxy groups can react with cyanate groups in the film preparation, drying and curing processes, so that barium titanate particles can be fixed in a cyanate molecular chain structure, and the compatibility and dispersion uniformity between a ceramic material and a polymer matrix can be further improved.
In addition, the movement of the local segment in the molecular chain of PEI polymers causes beta-relaxation, and this secondary relaxation phenomenon causes a sharp increase in dielectric loss, which is very disadvantageous for its application in high temperature energy storage, especially at high temperatures. The imidazole polymer layer, glycidyl methacrylate and cyanate resin in the modified barium titanate all form hydrogen bond with carbonyl in PEI to limit beta-relaxation of PEI matrix, so that the high-temperature energy storage performance of the composite material is improved. In addition, the cyanate resin has excellent dielectric properties, namely low dielectric constant and low dielectric loss, excellent mechanical properties, high heat resistance and good processability, and can be helpful to obtain a composite film with better performance.
Preferably, in the step (1), the nano barium titanate includes a mass ratio of 1 to 3:7 to 9 barium titanate particles having an average particle diameter of 300 to 500nm and 50 to 150 nm; stirring for 2-3 hours under the protection of nitrogen; the reaction is carried out for 12-14 h at 30-35 ℃ under the protection of nitrogen; the mass ratio of the nano barium titanate to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate is 1:1.5 to 2.5:3 to 4.
The high-content nano ceramic powder is easy to agglomerate in the polymer matrix, so that a large number of holes are formed in the composite material, and the breakdown field intensity of the composite material is obviously reduced. The invention can well improve agglomeration through modifying barium titanate particles, and can effectively avoid forming defects and holes by compounding barium titanate particles with different particle diameters, and the particles are mutually communicated, so that the composite material has higher dielectric constant and simultaneously effectively reduces dielectric loss.
Preferably, in the step (2), the heating reaction is carried out under the protection of nitrogen, and the stirring reaction is carried out for 40-48 hours at 80-85 ℃; the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g: 1-2 mg: 0.8-1.2 g:100mL.
Preferably, in the step (3), the mass ratio of the epoxy group grafted nano barium titanate to the cyanate ester resin is 1:0.2 to 0.5.
In a second aspect, the invention also provides a preparation method of the binary blended high-temperature energy storage polymer dielectric film, which comprises the following steps:
step 1: adding PEI and PSU into an organic solvent, mixing, and stirring at 50-70 ℃ for 5-7.5h to completely dissolve the PEI and PSU, thereby obtaining a mixed solution A;
step 2: the modified nano barium titanate is put into an oil bath with the temperature of 125-130 ℃ for prepolymerization and catalyst is added dropwise, after the prepolymerization is carried out for 10-20 min, the modified nano barium titanate is taken out from the oil bath and added with the mixed solution A for blending, thus obtaining a mixture B;
step 3: and (3) dripping the mixture B onto a clean glass slide, adjusting the height of a scraper to uniformly spread the whole glass slide, and drying and curing to obtain the polymer dielectric film.
A polymer composite film is prepared by adopting a solution casting method, which relates to a solution casting process, and the high-temperature energy storage performance of the composite film is optimized by controlling the proportion of binary blend. The pre-polymerization of the modified nano barium titanate can enable the barium titanate particles to form pre-fixation on the cyanate resin, so that the stability and the uniform dispersibility are improved. The finally prepared composite polymer dielectric film has the characteristics of high dielectric constant, low dielectric loss, good high-temperature energy storage property, good flexibility and light weight.
Preferably, the drying and curing are as follows: drying for 1-2 h at 65-75 ℃ in a drying oven, and then placing in a blast drying oven for drying for 4-6 h at 200-220 ℃.
Preferably, the thickness of the polymer dielectric film is 8 to 12 μm.
Preferably, the organic solvent is one or more of N-methyl pyrrolidone, dimethylacetamide and dimethylformamide; the catalyst is 2-methyl-4-ethylimidazole.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite film is prepared by blending two polymers, and the high-temperature energy storage performance of the polymer composite film is improved by blending the two polymers according to a certain proportion;
(2) The modified nano barium titanate is adopted, so that the problems of poor compatibility and uneven dispersion of an inorganic filler and a matrix are avoided, the advantages of high dielectric constant of a ceramic material, high breakdown field strength of a polymer and the like are organically combined, dielectric loss is reduced, and good high-temperature energy storage characteristic is obtained;
(3) The polymer composite film is prepared by adopting a solution casting method, the preparation process is simple, no special processing process exists, the production cost is low, and the method can be used for continuous production of the film.
Detailed Description
The technical scheme of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto:
general examples
1. The binary blended high-temperature energy storage polymer dielectric film comprises 80-95% of PEI and 5-20% of PSU by mass percent. The polymer dielectric film has a single-layer structure and a thickness of 8-12 mu m.
The preparation method of the polymer dielectric film comprises the following steps:
step 1: adding PEI and PSU into an organic solvent, mixing, and stirring at 50-70 ℃ for 5-7.5h to completely dissolve the PEI and PSU, thereby obtaining a mixed solution A; the organic solvent is one or more of N-methyl pyrrolidone, dimethylacetamide and dimethylformamide;
step 2: and (3) dripping the mixed solution A onto a clean glass slide, regulating the height of a scraper to uniformly spread the whole glass slide, drying the glass slide for 0.8 to 1.2 hours at the temperature of 65 to 75 ℃ in an oven, and then placing the glass slide in a blast drying oven to dry the glass slide for 4 to 6 hours at the temperature of 200 to 220 ℃ to obtain the polymer dielectric film.
2. The binary blended high-temperature energy storage polymer dielectric film comprises 5-20% of PEI, 10-30% of PSU and 10-30% of modified nano barium titanate. The polymer dielectric film has a single-layer structure and a thickness of 8-12 mu m.
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate, and then performing ultrasonic dispersion, wherein the nano barium titanate comprises the following components in percentage by mass of 1-3: 7 to 9 barium titanate particles having an average particle diameter of 300 to 500nm and 50 to 150 nm; adding 1- (3-aminopropyl) imidazole, and stirring for 2-3 h under the protection of nitrogen; then allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide are added to react for 12 to 14 hours at the temperature of between 30 and 35 ℃ under the protection of nitrogen, and the nanometer barium titanate coated by imidazole polymer is obtained after centrifugal separation, washing and drying; the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:1.5 to 2.5: 3-4: 0.1 to 0.2:10.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 40-48 hours at 80-85 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g: 1-2 mg: 0.8-1.2 g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.2-0.5 to obtain the modified nano barium titanate.
The preparation method of the polymer dielectric film comprises the following steps:
step 1: adding PEI and PSU into an organic solvent, mixing, and stirring at 50-70 ℃ for 5-7.5h to completely dissolve the PEI and PSU, thereby obtaining a mixed solution A; the organic solvent is one or more of N-methyl pyrrolidone, dimethylacetamide and dimethylformamide;
step 2: the modified nano barium titanate is put into an oil bath with the temperature of 125-130 ℃ for prepolymerization and dropwise adding a catalyst, wherein the catalyst is 2-methyl-4-ethylimidazole, and after prepolymerization for 10-20 min, the catalyst is taken out from the oil bath and added with a mixed solution A for blending to obtain a mixture B;
step 3: and (3) dripping the mixture B onto a clean glass slide, regulating the height of a scraper to uniformly spread the whole glass slide, drying the glass slide for 1 to 2 hours at the temperature of 65 to 75 ℃ in an oven, and then placing the glass slide in a blast drying box to dry the glass slide for 4 to 6 hours at the temperature of 200 to 220 ℃ to obtain the polymer dielectric film.
Example 1
The preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.1g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 6h to completely dissolve to obtain a mixed solution A;
step 2: 1.5mL of the mixed solution A is dripped on a clean glass slide, the height of a scraper is adjusted to 200 mu m, the whole glass slide is uniformly paved, then the glass slide is dried for 1h at 70 ℃ in an oven, and the glass slide is placed in a blast drying box and dried for 4.5h at 200 ℃ to obtain the polymer dielectric film with the thickness of 10 mu m.
Example 2
The preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.2g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 7h to completely dissolve to obtain a mixed solution A;
step 2: 1.5mL of the mixed solution A is dripped on a clean glass slide, the height of a scraper is adjusted to 200 mu m, the whole glass slide is uniformly paved, then the glass slide is dried for 1h at 70 ℃ in an oven, and the glass slide is placed in a blast drying box and dried for 4.5h at 200 ℃ to obtain the polymer dielectric film with the thickness of 11 mu m.
Example 3
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate (comprising barium titanate particles with the average particle size of 400nm and barium titanate particles with the average particle size of 100nm in a mass ratio of 2:8), performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring for 2h under the protection of nitrogen; adding allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide, reacting for 14 hours at 30 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain imidazole polymer coated nano barium titanate; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:1.5:3.5:0.1:10.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 45 hours at 85 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; wherein the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g:1mg:1g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.35 to obtain the modified nano barium titanate.
The preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.2g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 7h to completely dissolve to obtain a mixed solution A;
step 2: 0.44g of modified nano barium titanate is put into an oil bath at 130 ℃ for prepolymerization, 0.01mL of 2-methyl-4-ethylimidazole is added dropwise, after prepolymerization for 15min, the mixture is taken out from the oil bath, and the mixed solution A is added for blending, so as to obtain a mixture B;
step 3: 1.5mL of the mixture B was dropped onto a clean glass slide, the height of the doctor blade was adjusted to 200 μm so as to uniformly spread over the entire glass slide, and then the glass slide was dried at 70℃for 1 hour in an oven, and then placed in a forced air drying oven and dried at 200℃for 4.5 hours to obtain a polymer dielectric film having a thickness of 12. Mu.m.
Example 4
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate (comprising barium titanate particles with average particle size of 500nm and 150nm in mass ratio of 1:9), performing ultrasonic dispersion, and stirring for 2h under nitrogen protection; adding allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide, reacting for 12 hours at 30 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain imidazole polymer coated nano barium titanate; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:2.5:3:0.1:10.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 48 hours at 80 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; wherein the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g:2mg:1.2g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.5 to obtain the modified nano barium titanate.
The preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.2g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 7h to completely dissolve to obtain a mixed solution A;
step 2: 0.6g of modified nano barium titanate is put into an oil bath at 130 ℃ for prepolymerization, 0.01mL of 2-methyl-4-ethylimidazole is added dropwise, after prepolymerization is carried out for 20min, the mixture is taken out from the oil bath, and the mixture is added into the mixed solution A for blending, thus obtaining a mixture B;
step 3: 1.5mL of the mixture B was dropped onto a clean glass slide, the height of the doctor blade was adjusted to 200 μm so as to uniformly spread over the entire glass slide, and then the glass slide was dried at 70℃for 1 hour in an oven, and then placed in a forced air drying oven and dried at 200℃for 4.5 hours to obtain a polymer dielectric film having a thickness of 12. Mu.m.
Example 5
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate (comprising barium titanate particles with the average particle size of 300nm and barium titanate particles with the average particle size of 100nm in a mass ratio of 3:7), performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring for 2h under the protection of nitrogen; adding allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide, reacting for 14 hours at 33 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain imidazole polymer coated nano barium titanate; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:1.5:4:0.2:10.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 40 hours at 85 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; wherein the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g:1mg:0.8g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.2 to obtain the modified nano barium titanate.
The preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.2g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 7h to completely dissolve to obtain a mixed solution A;
step 2: 0.3g of modified nano barium titanate is put into an oil bath at 130 ℃ for prepolymerization, 0.01mL of 2-methyl-4-ethylimidazole is added dropwise, after prepolymerization for 15min, the mixture is taken out from the oil bath, and the mixed solution A is added for blending, so as to obtain a mixture B;
step 3: 1.5mL of the mixture B was dropped onto a clean glass slide, the height of the doctor blade was adjusted to 200 μm so as to uniformly spread over the entire glass slide, and then the glass slide was dried at 70℃for 1 hour in an oven, and then placed in a forced air drying oven and dried at 200℃for 4.5 hours to obtain a polymer dielectric film having a thickness of 12. Mu.m.
Example 6
The difference from example 3 is that:
the preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.1g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 6h to completely dissolve to obtain a mixed solution A;
step 2: 0.44g of modified nano barium titanate is put into an oil bath at 130 ℃ for prepolymerization, 0.01mL of 2-methyl-4-ethylimidazole is added dropwise, after prepolymerization for 15min, the mixture is taken out from the oil bath, and the mixed solution A is added for blending, so as to obtain a mixture B;
step 3: 1.5mL of the mixture B was dropped onto a clean glass slide, the height of the doctor blade was adjusted to 200 μm so as to uniformly spread over the entire glass slide, and then the glass slide was dried at 70℃for 1 hour in an oven, and then placed in a forced air drying oven and dried at 200℃for 4.5 hours to obtain a polymer dielectric film having a thickness of 12. Mu.m.
Comparative example 1
The preparation method of the pure PEI film comprises the following steps:
step 1: adding 2g of PEI into 10mL of NMP, mixing, and stirring at 60 ℃ for 6 hours to completely dissolve the PEI to obtain solution A;
step 2: 1.5mL of the solution A is dripped on a clean glass slide, the height of a scraper is adjusted to 200 mu m, the scraper is uniformly paved on the whole glass slide, then the glass slide is dried for 1h at 70 ℃ in an oven, and the glass slide is placed in a blast drying box and dried for 4.5h at 200 ℃ to obtain a pure PEI film with the thickness of 10 mu m.
Comparative example 2
The preparation method of the pure PSU film comprises the following steps:
step 1: 2g of PSU is added into 10mL of NMP and mixed, and stirred for 6h at 60 ℃ to be completely dissolved, so as to obtain solution A;
step 2: 1.5mL of the solution A is dripped on a clean glass slide, the height of a scraper is adjusted to 200 mu m, the scraper is uniformly paved on the whole glass slide, then the glass slide is dried for 1h at 70 ℃ in an oven, and the glass slide is placed in a blast drying box and dried for 4.5h at 200 ℃ to obtain a pure PSU film with the thickness of 10 mu m.
Comparative example 3
The difference from example 3 is that: the modified nano barium titanate is nano barium titanate coated by only imidazole polymer.
The preparation method of the modified nano barium titanate comprises the following steps:
adding ethanol into nano barium titanate (comprising barium titanate particles with the average particle size of 400nm and barium titanate particles with the average particle size of 100nm in a mass ratio of 2:8), performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring for 2h under the protection of nitrogen; adding allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide, reacting for 14 hours at 30 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain imidazole polymer coated nano barium titanate, namely modified nano barium titanate; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:1.5:3.5:0.1:10.
comparative example 4
The difference from example 3 is that: the coating of imidazole polymer in the modified nano barium titanate is insufficient.
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate (comprising barium titanate particles with the average particle size of 400nm and barium titanate particles with the average particle size of 100nm in a mass ratio of 2:8), performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring for 2h under the protection of nitrogen; then allyl isothiocyanate is added to react for 14 hours at 30 ℃ under the protection of nitrogen, and the nanometer barium titanate coated by imidazole polymer is obtained after centrifugal separation, washing and drying; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate is 1:50:1.5:2.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 45 hours at 85 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; wherein the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g:1mg:1g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.35 to obtain the modified nano barium titanate.
Comparative example 5
The difference from example 3 is that: the modified nano barium titanate adopts barium titanate particles with single particle size.
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate (barium titanate particles with the average particle size of 100 nm), performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring for 2 hours under the protection of nitrogen; adding allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide, reacting for 14 hours at 30 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain imidazole polymer coated nano barium titanate; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:1.5:3.5:0.1:10.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 45 hours at 85 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; wherein the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g:1mg:1g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.35 to obtain the modified nano barium titanate.
Comparative example 6
The difference from example 4 is that: the grafting amount of cyanate resin in the modified nano barium titanate is excessive, and the adding amount of the modified nano barium titanate is excessive.
The preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate (comprising barium titanate particles with average particle size of 500nm and 150nm in mass ratio of 1:9), performing ultrasonic dispersion, and stirring for 2h under nitrogen protection; adding allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide, reacting for 12 hours at 30 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain imidazole polymer coated nano barium titanate; wherein the mass ratio of the nano barium titanate to the ethanol to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate to the dicumyl peroxide to the dimethyl sulfoxide is 1:50:2.5:3:0.1:10.
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, stirring and reacting for 48 hours at 80 ℃ under the protection of nitrogen, centrifugally separating, washing and drying to obtain epoxy group grafted nano barium titanate; wherein the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g:2mg:1.5g:100mL.
(3) The epoxy group grafted nano barium titanate and cyanate resin are prepared according to the following weight ratio of 1: blending and grinding in a mass ratio of 0.6 to obtain the modified nano barium titanate.
The preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding 2g of PEI and 0.2g of PSU into 10mL of NMP, mixing, and stirring at 65 ℃ for 7h to completely dissolve to obtain a mixed solution A;
step 2: 0.8g of modified nano barium titanate is put into an oil bath at 130 ℃ for prepolymerization, 0.01mL of 2-methyl-4-ethylimidazole is added dropwise, after prepolymerization is carried out for 20min, the mixture is taken out from the oil bath, and the mixture is added into the mixed solution A for blending, thus obtaining a mixture B;
step 3: 1.5mL of the mixture B was dropped onto a clean glass slide, the height of the doctor blade was adjusted to 200 μm so as to uniformly spread over the entire glass slide, and then the glass slide was dried at 70℃for 1 hour in an oven, and then placed in a forced air drying oven and dried at 200℃for 4.5 hours to obtain a polymer dielectric film having a thickness of 13. Mu.m.
Performance testing
Copper electrodes were vapor-deposited on the surfaces of the polymer films of the above examples and comparative examples, respectively, with a diameter of about 2mm and a thickness of 0.5. Mu.m. The ferroelectric properties are then measured and the energy storage properties are calculated. Dielectric properties, including dielectric constant, dielectric loss, and polarization curve and storage density were measured at a frequency of 10Hz, respectively, for the above examples and comparative examples, and the results of the related properties are shown in table 1 below.
TABLE 1
| Performance index | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Dielectric constant (10 KHz) | 3.1 | 3.4 | 3.0 | 2.9 |
| Dielectric loss (10 KHz) | 0.006 | 0.006 | 0.005 | 0.006 |
| Energy efficiency (E=500 MV/m,150 ℃ C.) | 78％ | 90％ | 19％ | 60％ |
| Energy storage Density (J/cm) 3 ，η>90％,150℃) | 2.42 | 3.17 | 1.58 | 1.66 |
TABLE 2
As can be seen from table 1, the data of examples 1-2 and comparative examples 1-2 show that the dielectric constant of the films is not significantly increased after a certain proportion of PSU is blended with PEI, compared to the pure PSU film and the pure PEI film, and the dielectric loss is hardly changed, indicating that the binary blend has little effect on the dielectric properties of the materials. But the energy efficiency of binary blending is obviously improved, mainly because binary polymer blending can generate a two-phase interface, which can block carriers and reduce the conductivity loss of the film at high temperature and high field strength. Thus, the binary blended polymer films have higher energy storage densities.
As can be seen from table 2, the data of examples 3 to 5 (compared with example 2) and example 6 (compared with example 1) show that the dielectric constant is significantly improved and the dielectric loss is maintained while the modified nano barium titanate is added, so that the problems of poor compatibility between the inorganic filler and the matrix and uneven dispersion are effectively solved and the higher energy density is obtained. Comparative example 4 shows that the compactness of the imidazole polymer layer coated on the surface of the nano barium titanate can influence the compatibility between the inorganic filler and the polymer matrix, so that the dielectric loss is increased and the energy storage density is reduced. Comparative examples 3 and 6 show that the modified barium titanate surface grafted cyanate ester resin also affects its compatibility in the polymer matrix, and the addition of cyanate ester resin can be advantageous in obtaining low dielectric loss and better high temperature energy storage characteristics. Comparative example 5 shows that the barium titanate particles with different particle diameters are compounded, so that defects and holes can be effectively avoided, the particles are mutually communicated, the composite material has a higher dielectric constant, and meanwhile, the dielectric loss is effectively reduced.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.
Claims (5)
1. The binary blending high-temperature energy storage polymer dielectric film is characterized in that the polymer dielectric film has a single-layer structure, and raw materials of the polymer dielectric film comprise PEI and PSU; the PSU accounts for 5-20% of the blend of the PEI and the PSU in percentage by mass; the raw materials of the polymer dielectric film also comprise modified nano barium titanate accounting for 10-30% of the mass of the blend of PEI and PSU;
the preparation method of the modified nano barium titanate comprises the following steps:
(1) Adding ethanol into nano barium titanate, performing ultrasonic dispersion, adding 1- (3-aminopropyl) imidazole, and stirring under the protection of nitrogen; then allyl isothiocyanate, dicumyl peroxide and dimethyl sulfoxide are added for reaction under the protection of nitrogen, and the nanometer barium titanate coated by imidazole polymer is obtained through centrifugal separation;
(2) Adding the nano barium titanate coated by the imidazole polymer, azodiisobutyronitrile and glycidyl methacrylate into N, N-dimethylformamide, mixing, heating for reaction under the protection of nitrogen, and centrifugally separating to obtain epoxy group grafted nano barium titanate;
(3) Blending and grinding the epoxy group grafted nano barium titanate and cyanate resin to obtain modified nano barium titanate;
in the step (1), the nano barium titanate comprises the following components in percentage by mass of 1-3: 7-9 barium titanate particles having an average particle diameter of 300-500 nm and 50-150 nm; stirring for 2-3 hours under the protection of nitrogen; the reaction is carried out for 12-14 h at 30-35 ℃ under the protection of nitrogen; the mass ratio of the nano barium titanate to the 1- (3-aminopropyl) imidazole to the allyl isothiocyanate is 1: 1.5-2.5: 3-4;
in the step (2), heating reaction is carried out under the protection of nitrogen, and stirring reaction is carried out for 40-48 h at 80-85 ℃; the mass volume ratio of the imidazole polymer coated nano barium titanate to the azodiisobutyronitrile to the glycidyl methacrylate to the N, N-dimethylformamide is 0.5g: 1-2 mg: 0.8-1.2 g:100mL;
in the step (3), the mass ratio of the epoxy group grafted nano barium titanate to the cyanate ester resin is 1: 0.2-0.5;
the preparation method of the binary blended high-temperature energy storage polymer dielectric film comprises the following steps:
step 1: adding PEI and PSU into an organic solvent, mixing, and stirring at 50-70 ℃ for 5-7.5h to completely dissolve the PEI and PSU, thereby obtaining a mixed solution A;
step 2: the modified nano barium titanate is placed in an oil bath at 125-130 ℃ for prepolymerization and catalyst is added dropwise, after the prepolymerization is carried out for 10-20 min, the modified nano barium titanate is taken out from the oil bath and added with the mixed solution A for blending, and a mixture B is obtained;
step 3: and (3) dripping the mixture B onto a clean glass slide, adjusting the height of a scraper to uniformly spread the whole glass slide, and drying and curing to obtain the polymer dielectric film.
2. A method of preparing a binary blended high temperature energy storage polymer dielectric film according to claim 1, comprising the steps of:
step 1: adding PEI and PSU into an organic solvent, mixing, and stirring at 50-70 ℃ for 5-7.5h to completely dissolve the PEI and PSU, thereby obtaining a mixed solution A;
step 2: the modified nano barium titanate is placed in an oil bath at 125-130 ℃ for prepolymerization and catalyst is added dropwise, after the prepolymerization is carried out for 10-20 min, the modified nano barium titanate is taken out from the oil bath and added with the mixed solution A for blending, and a mixture B is obtained;
step 3: and (3) dripping the mixture B onto a clean glass slide, adjusting the height of a scraper to uniformly spread the whole glass slide, and drying and curing to obtain the polymer dielectric film.
3. The method of claim 2, wherein the drying and curing is: and (3) drying for 1-2 hours at the temperature of 65-75 ℃ in an oven, and then placing in a forced air drying oven to dry for 4-6 hours at the temperature of 200-220 ℃.
4. The method of claim 2 or 3, wherein the polymer dielectric film has a thickness of 8 to 12 μm.
5. A process according to claim 2 or 3, wherein the organic solvent is one or more of N-methylpyrrolidone, dimethylacetamide and dimethylformamide; the catalyst is 2-methyl-4-ethylimidazole.
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