CN118126322A - High-energy-storage polyetherimide dielectric material, preparation method and application thereof - Google Patents
High-energy-storage polyetherimide dielectric material, preparation method and application thereof Download PDFInfo
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- CN118126322A CN118126322A CN202410250272.0A CN202410250272A CN118126322A CN 118126322 A CN118126322 A CN 118126322A CN 202410250272 A CN202410250272 A CN 202410250272A CN 118126322 A CN118126322 A CN 118126322A
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- 239000004697 Polyetherimide Substances 0.000 title claims abstract description 143
- 229920001601 polyetherimide Polymers 0.000 title claims abstract description 143
- 238000004146 energy storage Methods 0.000 title claims abstract description 120
- 239000003989 dielectric material Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 24
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
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- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- -1 diamine phenyl ether compound Chemical class 0.000 claims abstract description 8
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- 239000004065 semiconductor Substances 0.000 claims abstract description 5
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 5
- 238000004100 electronic packaging Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- 230000015556 catabolic process Effects 0.000 claims description 14
- 230000010287 polarization Effects 0.000 claims description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000218378 Magnolia Species 0.000 description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a high energy storage polyetherimide dielectric material, a preparation method and application thereof, wherein the preparation method comprises the following steps: adding a diamine phenyl ether compound into a polar solvent to obtain a mixed solution, adding aromatic dianhydride into the mixed solution, and performing in-situ polymerization and vacuum treatment to obtain a polyether amic acid solution; preparing a film from the polyether-acid solution, carrying out a cyclization reaction by gradient heating to obtain a polyether-imide dielectric film, and drying to obtain a high-energy-storage polyether-imide dielectric material; the high energy storage polyetherimide dielectric material is applied to the fields of preparation of dielectric capacitors, semiconductors and electronic packaging; the method overcomes the defect that the prior art has smaller discharge energy density and charge-discharge efficiency at high temperature, and can not meet the application requirements of dielectric materials in high-temperature, high-electric-field and high-energy-storage-density environments.
Description
Technical Field
The invention belongs to the technical field of polymer dielectric materials used for high-voltage capacitors and preparation methods thereof, and particularly relates to a high-energy-storage polyetherimide dielectric material, a preparation method and application thereof.
Background
With the rapid development of electronic technology, power devices are developed towards high power, high integration and high charge and discharge efficiency; in the high-power electronic device, the temperature performance of the components is also required to be higher and higher. The dielectric capacitor is used as the most promising energy conversion and storage element at present, has high power density and low energy consumption, and has faster charge and discharge speed compared with other energy storage elements. Therefore, it can be used as many modern electronic devices, such as hybrid electric vehicles, biomedical devices, and electronic weapon systems.
In recent years, there has been an increasing demand for dielectric materials capable of operating efficiently at high temperatures of 150 ℃ in advanced electronic, electrified vehicle and aerospace power systems. However, dielectric polymers are limited by relatively low operating temperatures. For example, the dielectric polymer biaxially oriented polypropylene (BOPP) commonly used in industry has an operating temperature well below 105 ℃ under the action of an applied electric field, and although it has a very high resistance to electric field breakdown (600 kV/mm) at normal temperature, its low dielectric constant results in a lower polarization rate and an energy storage density of about 2J/cm 3. Because BOPP has poor thermal stability, when the temperature exceeds 85 ℃, the internal conductivity loss index is increased, and the discharge energy density and the charge-discharge efficiency are rapidly reduced, so that the thermal runaway phenomenon of the capacitor gradually occurs, and the application requirements of the environment with higher temperature and high electric field cannot be met.
The invention patent application with publication number of CN115141371A discloses a cross-linked polyetherimide dielectric material and a preparation method thereof, specifically 4,4 '-diaminodiphenyl ether and 4,4' -diphenyl ether dianhydride are taken as monomers, polyether amic acid is generated through polycondensation reaction, then a cross-linking agent of 2,4, 6-triaminopyrimidine is added for continuous reaction, and finally gradient heating is carried out for cyclization reaction, so that the cross-linked polyetherimide dielectric material is obtained. However, the discharge energy density and the charge-discharge efficiency are smaller at high temperature, for example, the maximum discharge energy density at 150 ℃ is 2.59J/cm 3, and the charge-discharge efficiency at 150 ℃ under 300kV/mm is 70.7-79.3%, so that the invention can not meet the application requirements of the dielectric material in the environment with high temperature and high energy storage density.
Disclosure of Invention
The invention aims to provide a high energy storage polyetherimide dielectric material, a preparation method and application thereof, which are used for overcoming the defect that the discharge energy density and the charge-discharge efficiency are smaller at high temperature in the prior art, and cannot meet the application requirements of the dielectric material in high-temperature, high-electric-field and high-energy-storage-density environments.
In order to achieve the above purpose, the present invention provides the following technical solutions:
Step 1, adding a diamine-based benzene ether compound into a polar solvent to obtain a mixed solution, adding aromatic dianhydride into the mixed solution, and performing in-situ polymerization reaction and vacuum treatment to obtain a polyether amic acid solution;
And 2, preparing a film from the polyether acid solution in the step 1, heating in a gradient way, performing a cyclization reaction to obtain a polyether imide dielectric film, and drying to obtain the high energy storage polyether imide dielectric material.
The polar solvent in the step 1 is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
In the in-situ polymerization reaction in the step 1, the aromatic dianhydride is added into the mixed solution for a plurality of times, and the stirring reaction is carried out for 1 to 1.5 hours for each time until the addition is completed, and then the stirring is continued for 40 to 60 minutes.
In the step 1, the diamine phenyl ether compound is prepared from the following components in percentage by mass: polar solvent: aromatic dianhydride= (1.13 to 1.17): (13.06-14.92): (3-3.03).
And (3) the film forming in the step (2) is wet film forming.
The film-making method of the wet film-making is one of a casting method, a spin coating method and a blade coating method.
The temperature rising rate of the gradient temperature rising in the step2 is 3-5 ℃/min, the temperature is sequentially raised to 100-110 ℃, 130-140 ℃, 190-200 ℃, 220-230 ℃, 250-260 ℃, 280-290 ℃ and 310-320 ℃, and the respective heat preservation is carried out for 0.5-1 h.
The high energy storage polyetherimide dielectric material is prepared by adopting the preparation method of any one of the high energy storage polyetherimide dielectric materials.
When the maximum breakdown field strength of the high energy storage polyetherimide dielectric material is 520kV/mm at 150 ℃, the maximum energy storage density is not less than 8J/cm 3, the polarization intensity is not less than 3.5 mu C/cm 2, and the charge and discharge efficiency is more than 86%.
A high energy storage polyetherimide dielectric material is applied to the fields of preparing dielectric capacitors, semiconductors and electronic packaging.
Compared with the prior art, the invention has the beneficial effects that:
Adding a small-molecular-weight diamine-based benzene ether compound into a polar solvent to obtain a mixed solution, adding aromatic dianhydride with larger molecular weight into the mixed solution to facilitate the full dissolution and reaction of reactants, and generating polyether amic acid solution through in-situ polymerization and vacuum treatment; in-situ polymerization takes a diamine-based benzene ether compound and aromatic dianhydride as monomers, and fills the monomers into a polar solvent as a disperse phase, so that in-situ polymerization is completed, bubbles in the solution are removed by vacuum treatment, good performance of a subsequently prepared high-energy-storage polyetherimide dielectric material is ensured, the ether bond in a polyetherimide acid solution molecular chain provides enough flexibility, good melt processing performance is realized, meanwhile, excellent mechanical and thermal properties of aromatic imide are reserved, and the ether bond is a polar group, so that dielectric performance of the polyetherimide can be improved; preparing a membrane from the polyether amic acid solution, and carrying out a cyclization reaction by gradient heating to obtain a dielectric film of the polyether imide acid solution; in the process, the temperature is gradually increased, so that the acidamide groups in the molecular chain of the polyether amic acid solution are subjected to cyclization reaction to generate a polyether imide structure; the purpose of gradient heating is to control the reaction rate, avoid thermal stress in the reaction process, and ensure the integrity and uniformity of the prepared high energy storage polyetherimide dielectric material; drying to obtain a high energy storage polyetherimide dielectric material; the residual moisture and other volatile substances in the polyetherimide dielectric film can be removed by drying, so that the obtained high-energy-storage polyetherimide dielectric material is more compact and stable. The raw materials used for preparing the high-energy-storage polyetherimide dielectric material are simple and easy to obtain, and the preparation process is simple and feasible and is suitable for large-scale industrial production.
Furthermore, the polar solvent adopted in the preparation method of the high energy storage polyetherimide dielectric material provided by the invention is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide with high boiling point, so that a plurality of organic and inorganic compounds can be dissolved, and the high energy storage polyetherimide dielectric material can be kept stable under the high temperature condition, and can be ensured to be capable of adapting to the application requirements in the high temperature environment.
Further, in-situ polymerization reaction in the preparation method of the high energy storage polyetherimide dielectric material provided by the invention, aromatic dianhydride is added into the mixed solution for a plurality of times, and stirring reaction is carried out for 1-1.5 h each time until the addition is completed, and stirring is continued for 40-60 min; the aromatic dianhydride is added for several times to avoid excessive reaction at one time, so that the polymerization reaction is out of control, and the reaction is stirred for 1 to 1.5 hours after the aromatic dianhydride is added each time, so that the molecular chain of the polyether amic acid solution has more opportunities to react with the aromatic dianhydride, the length of the molecular chain of the ether amic acid solution is gradually increased, the molecular weight of the polyetherimide is improved, and the polyetherimide with high molecular weight has better mechanical property, thermal stability and dielectric property.
Further, in the preparation method of the high energy storage polyetherimide dielectric material, gradient heating is carried out, the heating rate is 3-5 ℃/min, the temperature is sequentially increased to 100-110 ℃, 130-140 ℃, 190-200 ℃, 220-230 ℃, 250-260 ℃, 280-290 ℃ and 310-320 ℃, the thermal imidization is carried out, and under the condition, the thermal imidization is carried out, so that the polarization, breakdown field intensity and discharge energy density of the polyetherimide dielectric material can be improved, the energy storage density of the high energy storage polyetherimide dielectric material is improved, the integrity and uniformity of the polyether amic acid film are ensured, and the use requirements of high-temperature and high-electric field capacitor materials are greatly met.
The dielectric constant of the polyetherimide prepared by the invention is about 3.6 under the conditions of 30 ℃ and 10 3 kHz, the dielectric constant is improved by 1.125 times compared with that of the cross-linked polyetherimide dielectric material prepared by the prior art, the maximum breakdown field strength is 520kV/mm at 150 ℃, the maximum energy storage density is not less than 8J/cm 3, the polarization intensity is not less than 3.5 mu C/cm 2, the charge and discharge efficiency is more than 86%, and the maximum breakdown field strength is improved by 1.18 times and the maximum energy storage density is improved by more than 2.9 times compared with that of the cross-linked polyetherimide dielectric material prepared by the prior art; the charge-discharge efficiency of the polyetherimide dielectric material is 88.4% -93.0% under the conditions of 150 ℃ and 300kV/mm, and is improved by 1.17-1.25 times compared with that of the cross-linked polyetherimide dielectric material prepared by the prior art, so that the application requirements of the dielectric material in high-temperature, high-electric-field and high-energy-storage density environments are met; is a dielectric material promising for application in the modern electronic power fields such as dielectric capacitors, semiconductors, and electronic packages.
Drawings
FIG. 1 is an XRD pattern of a high energy storage polyetherimide dielectric material prepared in examples 1-3 of the present invention;
FIG. 2 is an infrared spectrum of the high energy storage polyetherimide dielectric material prepared in examples 1-3 of the present invention;
FIG. 3 is a graph showing the dielectric constant and the dielectric loss of the high energy storage polyetherimide dielectric material prepared in the examples 1-3 according to the present invention, wherein FIG. 3 (a) is a graph showing the dielectric constant of the high energy storage polyetherimide dielectric material prepared in the examples 1-3 according to the temperature, and FIG. 3 (b) is a graph showing the dielectric loss of the high energy storage polyetherimide dielectric material prepared in the examples 1-3 according to the temperature;
FIG. 4 is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of the invention prepared in examples 1-3 at 30deg.C, wherein FIG. 4 (a) is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of the invention prepared in example 1 at 30deg.C, FIG. 4 (b) is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of the invention prepared in example 2 at 30deg.C, and FIG. 4 (c) is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of the invention prepared in example 1 at 30deg.C;
FIG. 5 is a graph showing the change of the energy storage density and the charge-discharge efficiency with the electric field at 30℃for the high energy storage polyetherimide dielectric materials prepared in examples 1-3 of the present invention;
FIG. 6 is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of the invention prepared in examples 1-3 at 150deg.C, wherein FIG. 6 (a) is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of example 1 at 150deg.C, FIG. 6 (b) is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of example 2 at 150deg.C, and FIG. 6 (c) is a graph showing the hysteresis loop of the high energy storage polyetherimide dielectric material of example 3 at 150deg.C;
FIG. 7 is a graph showing the change of the energy storage density and the charge-discharge efficiency with the electric field at 150℃of the high energy storage polyetherimide dielectric material prepared in examples 1-3 of the present invention.
Detailed Description
Hereinafter, only certain exemplary embodiments are briefly described. As will be recognized by those of skill in the pertinent art, the described embodiments may be modified in various different ways without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature and not as restrictive.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; the device can be mechanically connected, electrically connected and communicated; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is less level than the second feature.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
General examples
Step 1, adding 13.06-14.92 g of N, N-dimethylacetamide DMAC into a three-neck flask, adding 1.13-1.17 g of 4,4' -diaminodiphenyl ether ODA produced by ALFA AESAR company, stirring by an electric stirrer until the mixture is fully dissolved to form a uniform mixed solution, keeping electric stirring, weighing 3-3.03 g of bisphenol A type diether dianhydride produced by Shanghai Michelia Biochemical technology Co Ltd, adding three times (the specific addition amount can be adjusted according to the quality of bisphenol A type diether dianhydride so as to ensure that the bisphenol A type diether dianhydride can be fully dissolved) into the mixed solution to fully dissolve the bisphenol A type diether dianhydride, stirring for 1-1.5 h each time, stirring for the next time for 1-1.5 h, continuously repeating the operation until the addition is completed, stirring for 40-60 min continuously to initiate polymerization, and adding the bisphenol A type diether dianhydride for three times to further lengthen the molecular chain of polyetherimide, thereby improving the molecular weight of the polyetherimide, and further enabling the polyetherimide to have better mechanical stability and dielectric property; placing the mixture into a vacuum drying box, vacuumizing for 12-14 hours, removing bubbles generated by stirring in the polyether polyamic acid solution, wherein the bubbles are difficult to remove by virtue of the polyether amic acid which is generated in a colloid form after electric stirring, and the bubbles are insufficient to remove, so that air holes are generated in the film during casting and the performance of the dielectric film is seriously affected;
Step 2, the polyether acid solution in the step 1 is scraped and coated by an automatic casting machine, the solution is scraped and coated on a clean glass plate by a scraper with the thickness of 12-18 mu m, the scraped and coated solution is put into an oven with the temperature of 80-100 ℃ for drying for 12-14 hours to remove the solvent, then the scraped and coated solution is put into a high-temperature precise oven for gradient heating, the heating rate is 3-5 ℃/min, the temperature is sequentially increased to 100-110 ℃, 130-140 ℃, 190-200 ℃, 220-230 ℃, 250-260 ℃, 280-290 ℃, 310-320 ℃ and each heat preservation time is 0.5-1 hour, the thermal imidization is completed, the polyether imide dielectric film with thermal imidization is obtained, the gradient heating can fully imidize, and meanwhile, water vapor generated in the imidization process can be rapidly removed by drying, so that the imidization efficiency and effect are enhanced, and the breakdown field intensity can be enhanced by complete imidization; taking out the polyetherimide dielectric film subjected to thermal imidization, putting the polyetherimide dielectric film into deionized water at 80-90 ℃, waiting for 0.5-2 h to fall off the glass by utilizing the difference of the thermal expansion coefficient (8.5X10-6/DEG C) of the glass and the thermal expansion coefficient (5.6X10-5/DEG C) of the polyetherimide, and then putting the polyetherimide dielectric film into an oven for processing for 6-8 h at 80-100 ℃ to remove the moisture in the polyetherimide dielectric film material, thus obtaining the high-energy storage polyetherimide dielectric material.
A high energy storage polyetherimide dielectric material is applied to the fields of preparing dielectric capacitors, semiconductors and electronic packaging.
Example 1
A preparation method of a high energy storage polyetherimide dielectric material comprises the following steps:
step 1, adding 13.06g of N, N-dimethylacetamide DMAC into a three-neck flask, adding 1.13g of 4,4' -diaminodiphenyl ether ODA produced by ALFA AESAR company, stirring by an electric stirrer until the mixture is fully dissolved to form a uniform mixed solution, keeping electric stirring, weighing 3g of bisphenol A type diether dianhydride produced by Shanghai Michelia Biochemical technology Co., ltd, adding the mixture into the mixed solution for three times to fully dissolve the bisphenol A type diether dianhydride, stirring each time for 1h, and continuously repeating the operation until the third reaction is finished and stirring for 40min to initiate polymerization to obtain a polyether amic acid solution; then placing the etheramic acid solution into a vacuum drying oven, and vacuumizing for 12 hours to remove bubbles generated by stirring in the polyetheramic acid solution;
And 2, carrying out blade coating on the polyether acid solution in the step 1 by using an automatic casting machine, carrying out blade coating on the solution on a clean glass plate by using a blade with the thickness of 12 mu m, putting the glass plate into an 80 ℃ oven for drying for 12 hours after blade coating to remove the solvent, then putting the glass plate into a high-temperature precise oven for gradient heating, wherein the heating rate is 3 ℃/min, sequentially heating to 100 ℃, 130 ℃, 190 ℃, 220 ℃, 250 ℃, 280 ℃ and 310 ℃ for 0.5 hour, completing thermal imidization, obtaining a thermal imidization polyether imide dielectric film, taking out the polyether imide dielectric film subjected to thermal imidization, putting the polyether imide dielectric film into 80 ℃ deionized water, and then putting the polyether imide dielectric film into the oven for 6 hours under the 80 ℃ after the film is peeled off from the glass, thus obtaining the high-energy-storage polyether imide dielectric material.
Example 2
The preparation method of the high energy storage polyetherimide dielectric material specifically comprises the following steps:
step 1, adding 13.99g of N, N-dimethylacetamide DMAC into a three-neck flask, adding 1.15g of 4,4' -diaminodiphenyl ether ODA produced by ALFA AESAR company, stirring by an electric stirrer until the mixture is fully dissolved to form a uniform mixed solution, keeping electric stirring, weighing 3.015g of bisphenol A type diether dianhydride produced by Shanghai Michelia Biochemical technology Co., ltd, adding the mixture into the mixed solution for three times to fully dissolve, stirring for 1.25 hours each time, adding the mixture again until the third reaction is finished, continuing stirring for 50 minutes to initiate polymerization, and vacuumizing in a vacuum drying oven for 13 hours to remove bubbles generated by stirring in a polyether polyamic acid solution;
Step 2, doctor-coating the prepared polyether amic acid solution after vacuumizing by using an automatic casting machine, doctor-coating the solution on a clean glass plate by using a doctor blade with the thickness of 15 mu m, putting the glass plate into a 90 ℃ oven for drying for 13 hours after doctor-coating to remove the solvent, then putting the glass plate into a high-temperature precise oven for gradient heating at the heating rate of 4 ℃/min, and sequentially heating to 105 ℃, 135 ℃, 195 ℃, 225 ℃, 255 ℃, 285 ℃, 315 ℃ and 0.75 hour after each heat preservation to finish thermal imidization to obtain a thermal imidization polyetherimide dielectric film; and taking out the polyetherimide dielectric film subjected to thermal imidization, putting the polyetherimide dielectric film into deionized water at 85 ℃, waiting for 1.25h, then falling off the film from glass, and putting the polyetherimide dielectric film into a baking oven at 90 ℃ for 7h to obtain the high-energy-storage polyetherimide dielectric material.
Example 3
A preparation method of a high energy storage polyetherimide dielectric material comprises the following steps:
Step 1, adding 14.92g of N, N-dimethylacetamide DMAC into a three-neck flask, adding 1.17g of 4,4' -diaminodiphenyl ether ODA produced by ALFA AESAR company, stirring by an electric stirrer until the mixture is fully dissolved to form a uniform mixed solution, keeping electric stirring, weighing 3-3.03 g of bisphenol A type diether dianhydride produced by Shanghai Michelia Biochemical technology Co., ltd, adding the mixture into the mixed solution for three times to fully dissolve, stirring for 1.5h each time, stirring for the next time for 1.5h, continuously repeating the operation until the third reaction is finished and stirring is continued for 60min to initiate polymerization, and vacuumizing in a vacuum drying box for 14h to remove bubbles generated by stirring in a polyether amide acid solution;
And 2, scraping the polyether acid solution obtained in the step 1 by using an automatic casting machine, scraping the solution on a clean glass plate by using a scraper with the thickness of 18 mu m, drying the glass plate in a 100 ℃ oven for 14h to remove the solvent after scraping, then placing the glass plate in a high-temperature precise oven for gradient heating, wherein the heating rate is 5 ℃/min, sequentially heating to 110 ℃, 140 ℃, 200 ℃, 230 ℃, 260 ℃, 290 ℃ and 320 ℃ for 1h, completing thermal imidization, obtaining a thermally imidized polyether imide dielectric film, taking out the thermally imidized polyether imide dielectric film, placing the thermally imidized polyether imide dielectric film into deionized water with the temperature of 90 ℃, waiting for 2h, removing the film from the glass, and then placing the glass plate in the 100 ℃ oven for processing for 8h to obtain the high-energy-storage polyether imide dielectric material.
Referring to fig. 1, the XRD patterns of the high energy storage polyetherimide dielectric materials prepared in examples 1-3 of the present invention were tested and analyzed by an X-ray diffractometer, and it can be seen through the analysis of the patterns that the high energy storage polyetherimide dielectric materials prepared in the present invention exhibit a broad amorphous peak at a diffraction angle 2θ=20°, corresponding to the amorphous characteristics generated by the regular arrangement of polyetherimide chains, which demonstrates the typical amorphous nature of polyetherimide.
Referring to FIG. 2, for the infrared spectra of the high energy storage polyetherimide dielectric materials prepared in examples 1-3 of the present invention, it can be seen that the high energy storage polyetherimide dielectric materials prepared in examples 1-3 observed C-N stretching peaks near wavenumbers of 750cm -1 and 1374cm -1, two absorption peaks occurring at 1778 and 1726cm -1, respectively, corresponding to asymmetric and symmetric stretching of the imidocarbon groups in the polyetherimide matrix, indicating that the polyetherimide dielectric materials were successfully prepared.
Referring to fig. 3, the high energy storage polyetherimide dielectric materials prepared in examples 1-3 are respectively cut into samples with the specification of 2cm x 2cm, gold electrodes with the diameter of 2-3 mm are plated on the upper and lower surfaces of the samples by using an ion sputtering instrument, the dielectric properties of the samples are tested by using a precise impedance analyzer, the dielectric constant of the polyetherimide prepared in examples 1-3 at 10 3 kHz is about 3.6, the dielectric constant is basically unchanged along with the change of temperature, the high energy storage polyetherimide dielectric materials have better temperature stability loss, the dielectric loss of the polyetherimide dielectric materials prepared in examples 1-3 is gradually increased along with the increase of temperature, the main reason for the increase is that the viscosity of the polymer is reduced along with the change of an electric field, but the dielectric loss is not completely synchronously changed, the whole dielectric loss is smaller than 0.004, the minimum dielectric loss can reach 0.0005, the polyetherimide dielectric material is stable within the temperature range of 30-200 ℃, the dielectric loss is basically unchanged along with the change of the temperature, the dielectric loss is lower than the dielectric loss of 0.004 under the temperature range, and the high energy storage polyetherimide dielectric materials have high temperature stability and meet the requirements of high dielectric field requirements of the application, and the invention are illustrated by the high dielectric stability.
Referring to fig. 4, after the high energy storage polyetherimide dielectric material samples prepared in the embodiments 1-3 of the present invention are tested by a ferroelectric analyzer, the discharge energy density and the charge-discharge efficiency are calculated by integrating the electric hysteresis loop, fig. 4 is an electric hysteresis loop diagram of the high energy storage polyetherimide dielectric material in the embodiments 1-3 of the present invention at 30 ℃, information such as polarization, charge-discharge efficiency, energy storage and the like can be obtained from the diagram, fig. 4 (a) is an electric hysteresis loop diagram of the high energy storage polyetherimide dielectric material in the embodiment 1 at 30 ℃, the polarization intensity at 440kV/mm is 3.82 μc/cm 2, the maximum breakdown field intensity is 580kV/mm, fig. 4 (b) is the high energy storage polyetherimide dielectric material in the embodiment 2, the polarization intensity at 440kV/mm is 4.17 μc/cm 2, the maximum breakdown field intensity is 560kV/mm, fig. 4 (C) is the high energy storage polyetherimide dielectric material in the embodiment 3, the polarization intensity at 440kV/mm is 440 μc/cm, and the high energy storage polyetherimide dielectric material has excellent high polarization performance at 2 mm.
Referring to FIG. 5, a graph showing the change of the energy storage density and the charge-discharge efficiency of the high energy storage polyetherimide dielectric material prepared in the examples 1-3 according to the present invention with the electric field at 30 ℃ is shown, wherein the maximum energy storage density of the high energy storage polyetherimide dielectric material prepared in the example 1 is 14.3J/cm 3, and the charge-discharge efficiency is 95.8%; the high energy storage polyetherimide dielectric material prepared in the embodiment 2 has the maximum energy storage density of 13.9J/cm 3, the charge-discharge efficiency of 95.0%, and the high energy storage polyetherimide dielectric material prepared in the embodiment 3 has the maximum energy storage density of 15.4J/cm 3 and the charge-discharge efficiency of 95.1%, so that the high energy storage polyetherimide dielectric material prepared in the invention has high energy storage density at room temperature and higher charge-discharge efficiency, and can meet the use requirements of room temperature and high electric field capacitor materials.
Referring to FIG. 6, in order to show the hysteresis loop diagrams of the high energy storage polyetherimide dielectric materials prepared in examples 1-3 of the present invention at 150 ℃, it can be seen from FIG. 6 (a) that the high energy storage polyetherimide dielectric material prepared in example 1 has a polarization intensity of 3.16 μC/cm 2 at 440kV/mm, a maximum breakdown field intensity of 520kV/mm, and from FIG. 6 (b) that the high energy storage polyetherimide dielectric material prepared in example 2 has a polarization intensity of 3.17 μC/cm 2 at 440kV/mm, a maximum breakdown field intensity of 500kV/mm; from FIG. 6 (C), it can be seen that the polarization intensity of the high energy storage polyetherimide dielectric material prepared in example 3 is 3.48 μC/cm 2 at 440kV/mm, and the maximum breakdown field intensity is 480kV/mm, so that the high energy storage polyetherimide dielectric material prepared in the invention has high breakdown field intensity at high temperature and high polarization intensity, and shows excellent energy storage performance.
Referring to FIG. 7, a graph showing the change of the energy storage density and the charge-discharge efficiency with the electric field at 150℃of the high energy storage polyetherimide dielectric materials prepared in examples 1-3 according to the present invention is shown, wherein the maximum energy storage density of the high energy storage polyetherimide dielectric materials prepared in example 1 is 8.9J/cm 3, and the charge-discharge efficiencies are 87.2% respectively; the high energy storage polyetherimide dielectric material prepared in example 2 has a maximum energy storage density of 8.4J/cm 3 and a charge-discharge efficiency of 86.1%; the high energy storage polyetherimide dielectric material prepared in example 3 has a maximum energy storage density of 8.0J/cm 3 and a charge-discharge efficiency of 86.2%; therefore, the high energy storage polyetherimide dielectric material prepared by the invention has high energy storage density at room temperature, higher charge and discharge efficiency and energy storage characteristic under a high electric field, and has wide application prospect in the fields of high-temperature and high-electric-field capacitors.
The table is a comparison of the performance test results of the dielectric materials of examples 1 to 3 and comparative examples 1 to 3 (comparative examples are disclosed in the invention patent publication No. CN115141371 a), and is specifically as follows:
As can be seen from the information in the table, compared with the comparative examples 1-3 in the prior art, the dielectric constant of the high energy storage polyetherimide dielectric material prepared in the examples 1-3 in the invention is obviously higher than that of the crosslinked polyetherimide dielectric material prepared in the comparative examples 1-3 in the prior art at 10 3 kHz; the high energy storage polyetherimide dielectric material prepared in the embodiments 1-3 of the invention has a maximum breakdown strength (kV/mm) at 30 ℃ which is obviously higher than that of the cross-linked polyetherimide dielectric material prepared in the comparative examples 1-3 of the prior art; the high energy storage polyetherimide dielectric material prepared in the embodiments 1-3 of the invention has the maximum discharge energy density (J/cm 3) at 30 ℃ and the corresponding charge-discharge efficiency (%) which is obviously higher than that of the cross-linked polyetherimide dielectric material prepared in the comparative examples 1-3 of the prior art; the high energy storage polyetherimide dielectric material prepared in the embodiments 1-3 of the invention has the maximum discharge energy density (J/cm 3) at 150 ℃ and the corresponding charge-discharge efficiency (%) which is obviously higher than that of the cross-linked polyetherimide dielectric material prepared in the comparative examples 1-3 of the prior art; the charge and discharge efficiency (%) of the high energy storage polyetherimide dielectric material prepared in the embodiment 1-3 of the invention at 150 ℃ and 300kV/mm is obviously higher than that of the cross-linked polyetherimide dielectric material prepared in the comparative example 1-3 of the prior art; therefore, the high energy storage polyetherimide dielectric material prepared by the invention has larger discharge energy density and charge-discharge efficiency at high temperature, and can meet the application requirements of the dielectric material in high-temperature, high-electric-field and high-energy-storage-density environments.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art. The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the high energy storage polyetherimide dielectric material is characterized by comprising the following steps of:
Step 1, adding a diamine-based benzene ether compound into a polar solvent to obtain a mixed solution, adding aromatic dianhydride into the mixed solution, and performing in-situ polymerization reaction and vacuum treatment to obtain a polyether amic acid solution;
And 2, preparing a film from the polyether acid solution in the step 1, heating in a gradient way, performing a cyclization reaction to obtain a polyether imide dielectric film, and drying to obtain the high energy storage polyether imide dielectric material.
2. The method for preparing a high energy storage polyetherimide dielectric material of claim 1, wherein the polar solvent in the step 1 is one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide.
3. The method for preparing a high energy storage polyetherimide dielectric material according to claim 1, wherein in the in-situ polymerization reaction in the step 1, the aromatic dianhydride is added into the mixed solution for several times, and each time the mixed solution is stirred for 1 to 1.5 hours, the stirring is continued for 40 to 60 minutes after the addition is completed.
4. The method for preparing a high energy storage polyetherimide dielectric material according to claim 1, wherein in the step 1, the diamine phenyl ether compound is prepared by the following mass ratio: polar solvent: aromatic dianhydride= (1.13 to 1.17): (13.06-14.92): (3-3.03).
5. The method for preparing a high energy storage polyetherimide dielectric material of claim 1, wherein the film preparation in the step 2 is a wet film preparation.
6. The method for preparing a high energy storage polyetherimide dielectric material of claim 5, wherein the wet film forming method is one of a casting method, a spin coating method and a doctor blade method.
7. The method according to claim 1, wherein the gradient heating rate in the step 2 is 3-5 ℃/min, and the temperature is sequentially raised to 100-110 ℃, 130-140 ℃, 190-200 ℃, 220-230 ℃, 250-260 ℃, 280-290 ℃ and 310-320 ℃, and the temperature is maintained for 0.5-1 h.
8. A high energy storage polyetherimide dielectric material, which is characterized in that the high energy storage polyetherimide dielectric material is prepared by the preparation method of the high energy storage polyetherimide dielectric material in any one of claims 1 to 7.
9. The high energy storage polyetherimide dielectric material of claim 8, wherein the high energy storage polyetherimide dielectric material has a maximum energy storage density of not less than 8J/cm 3, a polarization intensity of not less than 3.5 μc/cm 2, and a charge-discharge efficiency of 86% or more when the maximum breakdown field strength of the high energy storage polyetherimide dielectric material is 520kV/mm at 150 ℃.
10. Use of a high energy storage polyetherimide dielectric material as claimed in claim 8 in the manufacture of dielectric capacitors, semiconductors and electronic packaging.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118126322A true CN118126322A (en) | 2024-06-04 |
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