CN116791277B - High-temperature-resistant composite dielectric and preparation method and application thereof - Google Patents
High-temperature-resistant composite dielectric and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HQOWCDPFDSRYRO-CDKVKFQUSA-N CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 Chemical compound CCCCCCc1ccc(cc1)C1(c2cc3-c4sc5cc(\C=C6/C(=O)c7ccccc7C6=C(C#N)C#N)sc5c4C(c3cc2-c2sc3cc(C=C4C(=O)c5ccccc5C4=C(C#N)C#N)sc3c12)(c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1)c1ccc(CCCCCC)cc1 HQOWCDPFDSRYRO-CDKVKFQUSA-N 0.000 claims abstract description 165
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 52
- 230000002195 synergetic effect Effects 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000009987 spinning Methods 0.000 claims description 72
- 238000010438 heat treatment Methods 0.000 claims description 66
- 238000001035 drying Methods 0.000 claims description 57
- 239000003517 fume Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 238000010041 electrostatic spinning Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 13
- 238000007731 hot pressing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 abstract description 82
- 229920001601 polyetherimide Polymers 0.000 abstract description 81
- 239000004695 Polyether sulfone Substances 0.000 abstract description 46
- 238000004146 energy storage Methods 0.000 abstract description 32
- 230000015556 catabolic process Effects 0.000 abstract description 17
- 239000003990 capacitor Substances 0.000 abstract description 10
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000009413 insulation Methods 0.000 abstract description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000003989 dielectric material Substances 0.000 description 18
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- 239000003792 electrolyte Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 12
- 239000000428 dust Substances 0.000 description 6
- 238000007667 floating Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
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- 238000011049 filling Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 229920006162 poly(etherimide sulfone) Polymers 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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Classifications
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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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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- Textile Engineering (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a high-temperature-resistant composite dielectric medium, a preparation method and application thereof, and belongs to the technical field of dielectric capacitors. The invention fills the ITIC into the polyetherimide matrix with high breakdown and high energy storage efficiency to prepare the composite medium, wherein the synergistic effect of the ITIC with multiple concentrations solves the problem that the polyetherimide can cause charge injection and charge migration in the medium along with the injection of electrons into the electrode under high temperature and high field. The conduction loss and the heat loss of the polyetherimide are reduced, and the insulation performance and the energy storage efficiency of the polyetherimide are improved. On the basis, polyether sulfone is added, when PESU molecular chains are added into PEI, the distance between the molecular chains is increased, the steering loss generated by dipole steering is reduced, and the energy storage efficiency is improved; meanwhile, the increase of sulfonyl and molecular spacing in PESU brings a certain improvement to the dielectric constant; furthermore, the sulfonyl and hydrogen on PEI methyl can also form a hydrogen bond, so that the breakdown strength is improved to a certain extent.
Description
Technical Field
The invention relates to a high temperature resistant composite dielectric medium, a preparation method and application thereof, and belongs to the technical field of dielectric capacitors.
Background
The dielectric capacitor has the unique advantage of high power density, is widely applied to the fields of rapid charge and discharge of high-power pulse power supplies, hybrid electric vehicles, electromagnetic weapons and the like, and with the progress of technology and the continuous improvement of device power, the working environment temperature of the dielectric capacitor is continuously increased, so that higher requirements are put on the temperature resistance and the insulation performance of dielectric materials. However, biaxially oriented polypropylene of the current commercial energy storage dielectric material has low energy storage density at normal temperature (-2J/cm) 3 ) And the high temperature resistance is poor, the conductivity loss is greatly increased under the high temperature environment, and the working stability and the service life of the high temperature environment are greatly shortened. In addition, under the high temperature and high electric field, the charge injection at the electrode and the charge migration in the medium of the all-organic medium are increased, the conduction loss and the heat loss are gradually increased, and the insulating property and the energy storage efficiency of the polymer dielectric medium are seriously deteriorated. The highest working temperature of the traditional commercial BOPP film capacitor is only 105 ℃, and the energy storage density at normal temperature is only 2J/cm 3 . An operating environment exceeding BOPP withstand temperature may cause the performance of the thin film capacitor to deteriorate extremely or even fail, seriously affecting the normal operation of the device. Secondary cooling systems are commonly used commercially to ensure proper operation of thin film capacitors, but this limits the miniaturization and weight reduction of the devices, which hinders the development of related industries. For the current situation that high temperature resistance and high energy storage density film capacitors are urgently needed in industrial production, it is necessary to manufacture an all-organic insulating medium capable of solving the problems of poor temperature resistance and low energy storage efficiency of polymer dielectrics.
Disclosure of Invention
Aiming at the problems of poor temperature resistance and low energy storage efficiency of the existing all-organic insulating medium, the invention provides a high-temperature-resistant composite dielectric medium, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the invention aims to provide a high temperature resistant composite dielectric which is of a laminated structure, wherein each layer is formed by taking PEI and/or PESU as a matrix and doping ITIC, and the concentration of the dielectric doping ITIC is sequentially from top to bottom and then from bottom to top; the thickness of the dielectric is 10-13 μm.
Further defined, the dielectric comprises 5 ITIC concentrations of 0.25wt%, 0.2wt%, 0.15wt%, 0.1wt% and 0.05wt%, respectively.
Further defined, when the dielectric comprises 5 ITIC concentrations, the spinning sequence is 0.25wt% ITIC solution, 0.2wt% ITIC solution, 0.15wt% ITIC solution; 0.1wt% itic solution, 0.05wt% itic solution, 0.1wt% itic solution, 0.15wt% itic solution, 0.2wt% itic solution, 0.25wt% itic solution.
Further defined, the dielectric comprises 4 ITIC concentrations of 0.25wt%, 0.2wt%, 0.15wt% and 0.1wt%, respectively.
Further defined, when the dielectric comprises 4 ITIC concentrations, the spinning sequence is 0.25wt% ITIC solution, 0.2wt% ITIC solution, 0.15wt% ITIC solution, 0.1wt% ITIC solution, 0.15wt% ITIC solution, 0.2wt% ITIC solution, 0.25wt% ITIC solution.
Further defined, the dielectric comprises 3 ITIC concentrations of 0.25wt%, 0.2wt% and 0.15wt%, respectively.
Further defined, when the dielectric comprises 3 ITIC concentrations, the spinning sequence is 0.25wt% ITIC solution, 0.2wt% ITIC solution, 0.15wt% ITIC solution, 0.2wt% ITIC solution, 0.25wt% ITIC solution.
Further defined, the mass ratio of PEI to PESU is 9:1, 8:2, 7:3 or 6:4.
The second object of the present invention is to provide a method for preparing the above-mentioned high temperature resistant composite dielectric, which comprises the following steps:
(1) Preparing spinning precursor liquid; taking PEI and/or PESU as a matrix, doping ITIC with different mass to obtain spinning precursor solutions with different ITIC concentrations;
(2) Sequentially carrying out electrostatic spinning on the obtained spinning precursor solutions with different ITIC concentrations, and carrying out primary curing treatment on each spinning precursor solution after spinning is completed to obtain a multi-concentration ITIC synergistic PEI and/or PESU blending base wet film;
(3) And sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain the high-temperature-resistant composite dielectric.
Further defined, (1) is: the ITIC is uniformly dispersed in N-methyl pyrrolidone solution, and a certain amount of PEI particles and/or PESU particles are added to prepare spinning precursor solutions with different ITIC concentrations.
Further defined, the specific operation of (1) is:
firstly, filtering N-methyl pyrrolidone solution by using a molecular sieve, weighing ITIC (integrated circuit) mass corresponding to different concentrations, adding the ITIC mass into the filtered N-methyl pyrrolidone solution, performing ultrasonic dispersion treatment on the solution for 1h under the ultrasonic power of 50-70W by using a double-layer beaker, stirring at the rotation speed of 200r/min for 1.5h, and filtering the solution by using 800-mesh qualitative filter paper after stirring;
and then, drying PEI particles and/or PESU particles in a baking oven at 150 ℃ for 4 hours to completely remove water, adding the dried PEI particles into the solution doped with ITIC, heating and stirring for 12 hours at 60 ℃ under 200r/min, filtering by using 400-mesh qualitative filter paper after stirring, performing ultrasonic treatment on the filtered solution for 0.5 hour under the ultrasonic power of 50-70W by using a double-layer beaker, stirring for 1 hour under the condition of 300r/min after ultrasonic treatment, standing for 12 hours, and standing for 2 hours in a vacuum baking oven to remove bubbles.
Further defined, the specific operation of (2) is:
raising the relative humidity of air in the electrostatic spinning machine to 60%, and keeping for 4 hours to remove floating dust; then raising the temperature to 40 ℃ for 4 hours, and reducing the humidity to 10% of the relative humidity of the air; and finally, carrying out electrostatic spinning.
Further defined, the electrospinning parameters in (2) are: the advancing speed of the injector is 0.15mm/min, the speed of the receiver is 200r/min, the receiving distance is 15cm, the applied voltage of the needle head of the injector gradually rises to 7KV from 5KV along with the concentration reduction, the voltage of the receiving end is correspondingly-5 to-7 KV, the temperature is 20 ℃, the relative humidity is 10%, and the spinning time of each spinning precursor solution is 15min.
Further defined, the spinning needle is 23G type.
Further defined, the injector needles of the spinning precursor solutions of different ITIC concentrations in (2) are applied with different voltages.
Further defined, the 0.25wt% ITIC solution applied voltage is 5KV, the 0.2wt% ITIC solution applied voltage is 5.5KV, the 0.15wt% ITIC solution applied voltage is 6KV, the 0.1wt% ITIC solution applied voltage is 6.5KV, and the 0.05wt% ITIC concentration solution applied voltage is 7KV.
Further limiting, the primary solidification treatment process after spinning of each spinning precursor solution is finished is as follows: the spinning machine is heated to 40 ℃ for solidification for 10min and ventilation for 10min.
Further defined, the drying process in (3) is: firstly, drying for 1-2 h at the normal pressure and 60 ℃; drying at 80 deg.C under 0.04MPa for 4 hr, and standing in a fume hood for 10min; drying at 120 deg.C under 0.06MPa for 2 hr, and standing in a fume hood for 20min; drying at 150 deg.C under 0.08MPa for 2 hr, and standing in a fume hood for 30min; drying at 200 deg.C under 0.09MPa for 2 hr, and standing in a fume hood for 40min; finally, drying for 2 hours at 200 ℃ under 0.1MPa, and standing for 40 minutes in a fume hood.
Further defined, the step-wise heat treatment in (3) is: placing the dried wet film between heating iron plates of a vulcanizing press, quickly heating to 250 ℃, slowly reducing the temperature to 200 ℃, preserving the heat for 30min, and then performing step heat treatment, wherein the first stage is hot-pressed for 20min at 2.5Mpa and 200 ℃; in the second stage, 5Mpa, heating to 2 ℃ and hot-pressing for 20min; in the third stage, 7.5Mpa, heating to 2 ℃ and hot-pressing for 15min; fourth, heating to 2 deg.C under 10Mpa, and hot-pressing for 15min; in the fifth stage, 12.5Mpa, heating to 2 ℃ and hot-pressing for 10min; in the sixth stage, 15Mpa is heated to 2 ℃ and hot pressed for 10min.
Further defined, the quenching treatment process in (3) is as follows: cooling to 0-25 ℃ by a cold water treatment device after the stepped heat treatment is completed.
The invention further provides an application of the high-temperature-resistant composite dielectric, which is particularly applied to the field of rapid charge and discharge.
Further defined, particularly for use in high power pulsed power supplies, hybrid vehicles, and electromagnetic weapons.
The invention has the beneficial effects that:
(1) The invention fills the ITIC into the polyetherimide matrix with high breakdown and high energy storage efficiency to prepare the composite medium, wherein the synergistic effect of the ITIC with multiple concentrations solves the problem that the polyetherimide can cause charge injection and charge migration in the medium along with the injection of electrons into the electrode under high temperature and high field. The conduction loss and the heat loss of the polyetherimide are reduced, and the insulation performance and the energy storage efficiency of the polyetherimide are improved. In addition, polyether sulfone (PESU) is added on the basis, when the PESU molecular chain is added into PEI, the distance between the molecular chains is increased, the steering loss generated by dipole steering is reduced, and the energy storage efficiency is improved; meanwhile, the increase of sulfonyl and molecular spacing in PESU brings a certain improvement to the dielectric constant; furthermore, the sulfonyl and hydrogen on PEI methyl can also form a hydrogen bond, so that the breakdown strength is improved to a certain extent.
(2) The invention has the synergistic effect of the multi-concentration ITIC, realizes that the multi-concentration synergistic composite medium can enhance the energy storage density and the charge and discharge efficiency under the condition of improving certain breakdown strength by balancing the breakdown strength and dielectric property of the multi-concentration ITIC, ensures that the composite medium keeps extremely high energy storage performance, and solves the defects of high dielectric loss and low energy storage efficiency of the traditional all-organic composite medium under high temperature and high field. Meanwhile, the ITIC is filled into the PEI/PESU blended composite medium matrix with high breakdown and high energy storage efficiency, wherein the synergistic effect of the ITIC with multiple concentrations solves the problems that the composite medium is injected with electrons along with the injection of electrodes under high temperature and high field to cause the injection of charges and the increase of charge migration in the medium, reduces conduction loss and heat loss, and improves the insulation performance and the energy storage efficiency.
(3) The invention provides a new mode for greatly improving the energy density and the charge-discharge efficiency of the multi-concentration synergistic composite medium based on the polyetherimide polymer, and the energy storage density of the full organic medium prepared by taking the polyetherimide as the matrix is 3.13J/cm under the electric field of 420MV/m at the temperature of 200 DEG C 3 The energy storage efficiency is 86.6%, and the method can be used for manufacturing dielectric energy storage devices with excellent energy storage characteristics, and has wide application prospects in the field of dielectric capacitors. The invention is based on PEIThe method for improving the energy density and the charge-discharge efficiency of the composite medium of the PESU (polyethylene terephthalate) multi-concentration ITIC (integrated circuit) provides a new mode, and the maximum energy storage density of the all-organic medium prepared by the method and taking polyetherimide and polyethersulfone as matrixes is 3.60J/cm 3 The energy storage efficiency is 88%, the method can be used for manufacturing dielectric energy storage devices with excellent energy storage characteristics, and has wide application prospects in the field of dielectric capacitors.
Drawings
FIG. 1 is an XRD contrast pattern of the composite electrolytes obtained in examples 1 to 3 and comparative example 1;
fig. 2 is SEM photographs of the composite electrolytes obtained in examples 1 to 3 and comparative example 1;
FIG. 3 is a graph showing the variation of dielectric constant with frequency of the composite electrolytes obtained in examples 1 to 3 and comparative example 1;
FIG. 4 is a Weibull distribution diagram of breakdown field strength at high temperature of 200℃of the composite electrolytes obtained in examples 1 to 3 and comparative example 1;
fig. 5 is a graph showing the energy storage characteristics of the composite electrolytes obtained in examples 1 to 3 and comparative example 1;
FIG. 6 is an XRD contrast pattern of the composite electrolytes obtained in example 4 and comparative examples 1 to 6;
FIG. 7 is an SEM photograph of a cross-section of a composite dielectric obtained in example 4;
fig. 8 is an SEM photograph of cross-sections of the composite dielectrics obtained in comparative examples 1 and 2;
fig. 9 is an SEM photograph of cross sections of the composite dielectrics obtained in comparative example 3 and comparative example 4;
fig. 10 is an SEM photograph of cross sections of the composite dielectrics obtained in comparative examples 5 and 6;
FIG. 11 is a graph showing the variation of the dielectric constant with frequency of the composite dielectrics obtained in example 4 and comparative examples 1 to 6;
FIG. 12 is a Weibull plot of the breakdown field strengths of the composite dielectrics obtained in example 4 and comparative examples 1-6;
fig. 13 is a graph showing the comparison of the energy storage characteristics of the composite dielectrics obtained in example 4 and comparative examples 1 to 6.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The PEI particles used in the following examples and comparative examples have a molecular formula of C 37 H 28 N 2 O 8 The relative density was 1.27g/ml and the glass transition temperature was 217 ℃. The molecular formula of the PESU particles is C 18 H 12 SO 4 The relative density was 1.37g/ml and the glass transition temperature was 225 ℃.
Example 1
The embodiment takes polyetherimide as a matrix, and is obtained by 5 polyetherimide with different ITIC concentration contents alternately layer by layer and through hot pressing and quenching processes, wherein the mass fraction change values of ITIC are 0.05wt.%, and the volume contents of the ITIC layers are as follows:
PEI-0.25wt.％ITIC、PEI-0.2wt.％ITIC、PEI-0.15wt.％ITIC、PEI-0.1wt.％ITIC、PEI-0.05wt.％ITIC、PEI-0.1wt.％ITIC、PEI-0.15wt.％ITIC、PEI-0.2wt.％ITIC、PEI-0.25wt.％ITIC。
the process steps for preparing the high temperature resistant composite dielectric in this example are as follows:
(1) Preparing spinning precursor liquid;
firstly, filtering N-methyl pyrrolidone solution by using a molecular sieve, weighing ITIC (integrated circuit) mass corresponding to different concentrations, adding the ITIC mass into the filtered N-methyl pyrrolidone solution, performing ultrasonic dispersion treatment on the solution for 1h under the ultrasonic power of 60W by using a double-layer beaker, stirring at the rotation speed of 200r/min for 1.5h, and filtering the solution by using 800-mesh qualitative filter paper after stirring;
and then, drying PEI particles in an oven at 150 ℃ for 4 hours to completely remove water, adding the dried PEI particles into the solution doped with ITIC, heating and stirring for 12 hours at 60 ℃ under 200r/min, filtering by using 400-mesh qualitative filter paper after stirring, performing ultrasonic treatment on the filtered solution for 0.5 hour under the ultrasonic power of 60W by using a double-layer beaker, stirring for 1 hour under the condition of 300r/min after ultrasonic treatment, standing for 12 hours, and standing for 2 hours in a vacuum oven to remove bubbles. The mass fractions of ITICs of the obtained spinning precursor solutions were 0.25wt.% ITICs, 0.2wt.% ITICs, 0.15wt.% ITICs, 0.1wt.% ITICs, and 0.05wt.% ITICs, respectively.
(2) Carrying out electrostatic spinning;
and (3) respectively sucking the PEI-ITIC spinning precursor liquid with each volume fraction obtained in the step one into an injector, and sequentially carrying out low-speed electrostatic spinning according to the sequence of PEI-0.25wt.% ITIC, PEI-0.2wt.% ITIC, PEI-0.15wt.% ITIC, PEI-0.1wt.% ITIC, PEI-0.05wt.% ITIC, PEI-0.1wt.% ITIC, PEI-0.15wt.% ITIC, PEI-0.2wt.% ITIC and PEI-0.25wt.% ITIC to obtain the wet film.
The electrostatic spinning process comprises the following steps:
firstly, raising the relative humidity of air in an electrostatic spinning machine to 60%, and keeping for 4 hours to remove floating dust;
then, the temperature is raised to 40 ℃ and kept for 4 hours to reduce the humidity to 10% of the relative humidity of the air;
finally, electrostatic spinning is carried out, and the specific spinning process is as follows:
the propelling speed of the injector is 0.15mm/min, the receiver speed is 200r/min, the receiving distance is 15cm, the spinning needle adopts 23G model, the voltage applied by the injector needle gradually rises to 7KV along with the concentration reduction, the voltage of the receiving end is correspondingly-5 KV to-7 KV, the spinning environment temperature is 20 ℃, and the air relative humidity is 10%. The applied voltage of the 0.25wt% ITIC solution is 5KV, and the voltage of a receiving end is-5 KV; the applied voltage of the 0.2wt% ITIC solution is 5.5KV, and the receiving terminal voltage is-5.5 KV; the applied voltage of the 0.15wt% ITIC solution is 6KV, and the voltage of the receiving end is-6 KV; the applied voltage of the 0.1wt% ITIC solution is 6.5KV, and the receiving terminal voltage is-6.5 KV; the applied voltage of the 0.05wt% ITIC concentration solution is 7KV and the receiving terminal voltage is-7 KV. And (3) spinning each layer of solution for 12min, heating the spinning machine to 40 ℃ for solidification for 10min after finishing spinning one layer, and ventilating for 10min.
(3) Wet film post-treatment;
and sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain the high-temperature-resistant composite dielectric. The specific process is as follows:
firstly heating the film after spinning in a fume hood at 60 ℃ for 1h by using a heating table, then drying the film in a vacuum oven at 80 ℃ and 0.04MPa in vacuum for 4h, taking out the film, and standing the film in the fume hood for 10min; drying under vacuum state of 0.06MPa at 120deg.C for 2 hr, taking out, and standing in a fume hood for 20min; drying under vacuum state of 0.08MPa at 150deg.C for 2 hr, taking out, and standing in a fume hood for 30min; drying under vacuum state of 0.09MPa at 200deg.C for 2 hr, taking out, and standing in a fume hood for 40min; finally drying for 2 hours under the condition of 0.1MPa in an empty state and 200 ℃, taking out, and standing for 40 minutes at a ventilated drying place.
<2> heating the heated iron plate to 300 ℃ by using a flat vulcanizing machine, and keeping for 1h; after cooling to room temperature, the temperature is gradually raised to 300 ℃ after alcohol is sprayed, and after the temperature is maintained for 1h, the temperature is cooled to room temperature. The film was placed between heated iron plates and the temperature was rapidly raised to 250 c followed by a slow decrease in temperature to 200 c for 30min. Then carrying out step heat treatment, wherein the first stage is kept for 20min at 200 ℃ under 2.5 mpa; the second stage is to raise the pressure to 5Mpa and the temperature to 2 ℃ and keep for 20min; the third stage is to keep at 7.5Mpa and 2 ℃ for 15min; step four, boosting to 10Mpa, heating to 2 ℃ and keeping for 15min; step five, boosting to 12.5Mpa, and raising the temperature to 2 ℃ and keeping for 10min; and step six, boosting to 15Mpa, and raising the temperature to 2 ℃ and keeping for 10min.
And (3) directly cooling to 0-25 ℃ by a cold water treatment device after the step heat treatment is completed. A dense 5-concentration synergistic composite dielectric with a thickness of about 10 μm was obtained.
Example 2
The embodiment takes polyetherimide as a matrix, and is obtained by alternately carrying out hot pressing and quenching on the polyetherimide with 4 different ITIC concentration contents layer by layer, wherein the mass fraction change value of ITIC is 0.05wt%, and the specific volume contents of the filler and ITIC in each filling phase are as follows:
PEI-0.25wt.％ITIC、PEI-0.2wt.％ITIC、PEI-0.15wt.％ITIC、PEI-0.1wt.％ITIC、PEI-0.15wt.％ITIC、PEI-0.2wt.％ITIC、PEI-0.25wt.％ITIC。
the process steps for preparing the high temperature resistant composite dielectric in this example are as follows:
(1) Preparing spinning precursor liquid;
firstly, filtering N-methyl pyrrolidone solution by using a molecular sieve, weighing ITIC (integrated circuit) mass corresponding to different concentrations, adding the ITIC mass into the filtered N-methyl pyrrolidone solution, performing ultrasonic dispersion treatment on the solution for 1h under the ultrasonic power of 60W by using a double-layer beaker, stirring at the rotation speed of 200r/min for 1.5h, and filtering the solution by using 800-mesh qualitative filter paper after stirring;
and then, drying PEI particles in an oven at 150 ℃ for 4 hours to completely remove water, adding the dried PEI particles into the solution doped with ITIC, heating and stirring for 12 hours at 60 ℃ under 200r/min, filtering by using 400-mesh qualitative filter paper after stirring, performing ultrasonic treatment on the filtered solution for 0.5 hour under the ultrasonic power of 60W by using a double-layer beaker, stirring for 1 hour under the condition of 300r/min after ultrasonic treatment, standing for 12 hours, and standing for 2 hours in a vacuum oven to remove bubbles. The mass fractions of ITICs of the obtained spinning precursor solutions were 0.25wt.% ITICs, 0.2wt.% ITICs, 0.15wt.% ITICs, and 0.1wt.% ITICs, respectively.
(2) Carrying out electrostatic spinning;
and (3) respectively sucking the PEI-ITIC spinning precursor liquid with each volume fraction obtained in the step one into an injector, and sequentially carrying out low-speed electrostatic spinning according to the sequence of PEI-0.25wt.% ITIC, PEI-0.2wt.% ITIC, PEI-0.15wt.% ITIC, PEI-0.1wt.% ITIC, PEI-0.15wt.% ITIC, PEI-0.2wt.% ITIC and PEI-0.25wt.% ITIC to obtain the wet film.
The electrostatic spinning process comprises the following steps:
firstly, raising the relative humidity of air in an electrostatic spinning machine to 60%, and keeping for 4 hours to remove floating dust;
then, the temperature is raised to 40 ℃ and kept for 4 hours to reduce the humidity to 10% of the relative humidity of the air;
finally, electrostatic spinning is carried out, and the specific spinning process is as follows:
the propelling speed of the injector is 0.15mm/min, the receiver speed is 200r/min, the receiving distance is 15cm, the spinning needle adopts 23G model, the voltage applied by the injector needle gradually rises to 7KV along with the concentration reduction, the voltage of the receiving end is correspondingly-5 KV to-7 KV, the spinning environment temperature is 20 ℃, and the air relative humidity is 10%. The applied voltage of the 0.25wt% ITIC solution is 5KV, and the voltage of a receiving end is-5 KV; the applied voltage of the 0.2wt% ITIC solution is 5.5KV, and the receiving terminal voltage is-5.5 KV; the applied voltage of the 0.15wt% ITIC solution is 6KV, and the voltage of the receiving end is-6 KV; the applied voltage of the 0.1wt% ITIC solution is 6.5KV and the receiving terminal voltage is-6.5 KV. And (3) spinning each layer of solution for 17min, heating the spinning machine to 40 ℃ for solidification for 10min after finishing spinning one layer, and ventilating for 10min.
(3) Wet film post-treatment;
and sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain the high-temperature-resistant composite dielectric. The specific process is as follows:
firstly heating the film after spinning in a fume hood at 60 ℃ for 1h by using a heating table, then drying the film in a vacuum oven at 80 ℃ and 0.04MPa in vacuum for 4h, taking out the film, and standing the film in the fume hood for 10min; drying under vacuum state of 0.06MPa at 120deg.C for 2 hr, taking out, and standing in a fume hood for 20min; drying under vacuum state of 0.08MPa at 150deg.C for 2 hr, taking out, and standing in a fume hood for 30min; drying under vacuum state of 0.09MPa at 200deg.C for 2 hr, taking out, and standing in a fume hood for 40min; finally drying for 2 hours under the condition of 0.1MPa in an empty state and 200 ℃, taking out, and standing for 40 minutes at a ventilated drying place.
<2> heating the heated iron plate to 300 ℃ by using a flat vulcanizing machine, and keeping for 1h; after cooling to room temperature, the temperature is gradually raised to 300 ℃ after alcohol is sprayed, and after the temperature is maintained for 1h, the temperature is cooled to room temperature. The film was placed between heated iron plates and the temperature was quickly raised to 250 c, then slowly lowered to 205 c and held for 30min. Then carrying out step heat treatment, wherein the first stage is kept for 20min at 205 ℃ under 2.5 mpa; the second stage is to raise the pressure to 5Mpa and the temperature to 2 ℃ and keep for 20min; the third stage is to keep at 7.5Mpa and 2 ℃ for 15min; step four, boosting to 10Mpa, heating to 2 ℃ and keeping for 15min; step five, boosting to 12.5Mpa, and raising the temperature to 2 ℃ and keeping for 10min; and step six, boosting to 15Mpa, and raising the temperature to 2 ℃ and keeping for 10min.
And (3) directly cooling to 0-25 ℃ by a cold water treatment device after the step heat treatment is completed. A dense 4-concentration synergistic composite dielectric with a thickness of about 10 μm was obtained.
Example 3
The embodiment takes polyetherimide as a matrix, and is obtained by alternately carrying out hot pressing and quenching on the polyetherimide with 3 different ITIC concentration contents layer by layer, wherein the mass fraction change value of ITIC is 0.05wt%, and the specific volume contents of the filler and ITIC in each filling phase are as follows:
PEI-0.25wt.％ITIC、PEI-0.2wt.％ITIC、PEI-0.15wt.％ITIC、PEI-0.2wt.％ITIC、PEI-0.25wt.％ITIC。
the process steps for preparing the high temperature resistant composite dielectric in this example are as follows:
(1) Preparing spinning precursor liquid;
firstly, filtering N-methyl pyrrolidone solution by using a molecular sieve, weighing ITIC (integrated circuit) mass corresponding to different concentrations, adding the ITIC mass into the filtered N-methyl pyrrolidone solution, performing ultrasonic dispersion treatment on the solution for 1h under the ultrasonic power of 60W by using a double-layer beaker, stirring at the rotation speed of 200r/min for 1.5h, and filtering the solution by using 800-mesh qualitative filter paper after stirring;
and then, drying PEI particles in an oven at 150 ℃ for 4 hours to completely remove water, adding the dried PEI particles into the solution doped with ITIC, heating and stirring for 12 hours at 60 ℃ under 200r/min, filtering by using 400-mesh qualitative filter paper after stirring, performing ultrasonic treatment on the filtered solution for 0.5 hour under the ultrasonic power of 60W by using a double-layer beaker, stirring for 1 hour under the condition of 300r/min after ultrasonic treatment, standing for 12 hours, and standing for 2 hours in a vacuum oven to remove bubbles. The mass fractions of ITICs of the obtained spinning precursor solutions were 0.25wt.% ITICs, 0.2wt.% ITICs, and 0.15wt.% ITICs, respectively.
(2) Carrying out electrostatic spinning;
and (3) respectively sucking the PEI-ITIC spinning precursor liquid with each volume fraction obtained in the step one into an injector, and sequentially carrying out low-speed electrostatic spinning according to the sequence of PEI-0.25wt.% ITIC, PEI-0.2wt.% ITIC, PEI-0.15wt.% ITIC, PEI-0.2wt.% ITIC and PEI-0.25wt.% ITIC to obtain the wet film.
The electrostatic spinning process comprises the following steps:
firstly, raising the relative humidity of air in an electrostatic spinning machine to 60%, and keeping for 4 hours to remove floating dust;
then, the temperature is raised to 40 ℃ and kept for 4 hours to reduce the humidity to 10% of the relative humidity of the air;
finally, electrostatic spinning is carried out, and the specific spinning process is as follows:
the propelling speed of the injector is 0.15mm/min, the receiver speed is 200r/min, the receiving distance is 15cm, the spinning needle adopts 23G model, the voltage applied by the injector needle gradually rises to 7KV along with the concentration reduction, the voltage of the receiving end is correspondingly-5 KV to-7 KV, the spinning environment temperature is 20 ℃, and the air relative humidity is 10%. The applied voltage of the 0.25wt% ITIC solution is 5KV, and the voltage of a receiving end is-5 KV; the applied voltage of the 0.2wt% ITIC solution is 5.5KV, and the receiving terminal voltage is-5.5 KV; the applied voltage of the 0.15wt% ITIC solution is 6KV and the receiving terminal voltage is-6 KV. And (3) spinning each layer of solution for 24min, heating the spinning machine to 40 ℃ for solidification for 10min after finishing spinning one layer, and ventilating for 10min.
(3) Wet film post-treatment;
and sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain the high-temperature-resistant composite dielectric. The specific process is as follows:
firstly heating the film after spinning in a fume hood at 60 ℃ for 1h by using a heating table, then drying the film in a vacuum oven at 80 ℃ and 0.04MPa in vacuum for 4h, taking out the film, and standing the film in the fume hood for 10min; drying under vacuum state of 0.06MPa at 120deg.C for 2 hr, taking out, and standing in a fume hood for 20min; drying under vacuum state of 0.08MPa at 150deg.C for 2 hr, taking out, and standing in a fume hood for 30min; drying under vacuum state of 0.09MPa at 200deg.C for 2 hr, taking out, and standing in a fume hood for 40min; finally drying for 2 hours under the condition of 0.1MPa in an empty state and 200 ℃, taking out, and standing for 40 minutes at a ventilated drying place.
<2> heating the heated iron plate to 300 ℃ by using a flat vulcanizing machine, and keeping for 1h; after cooling to room temperature, the temperature is gradually raised to 300 ℃ after alcohol is sprayed, and after the temperature is maintained for 1h, the temperature is cooled to room temperature. The film was placed between heated iron plates and the temperature was rapidly raised to 250 c followed by a slow decrease in temperature to 210 c for 30 minutes. Then carrying out step heat treatment, wherein the first stage is kept for 20min at 210 ℃ under 2.5 mpa; the second stage is to raise the pressure to 5Mpa and the temperature to 2 ℃ and keep for 20min; the third stage is to keep at 7.5Mpa and 2 ℃ for 15min; step four, boosting to 10Mpa, heating to 2 ℃ and keeping for 15min; step five, boosting to 12.5Mpa, and raising the temperature to 2 ℃ and keeping for 10min; and step six, boosting to 15Mpa, and raising the temperature to 2 ℃ and keeping for 10min.
And (3) directly cooling to 0-25 ℃ by a cold water treatment device after the step heat treatment is completed. A dense 3-concentration synergistic composite dielectric with a thickness of about 10 μm was obtained.
Comparative example 1
The comparative example provides a preparation of a pure polyetherimide medium, comprising the following specific method steps:
(1) Preparing spinning precursor liquid;
firstly, filtering N-methyl pyrrolidone solution by using a molecular sieve;
and then, drying PEI particles in an oven at 150 ℃ for 4 hours to completely remove water, adding the dried PEI particles into N-methylpyrrolidone solution, heating and stirring for 12 hours at 60 ℃ and 200r/min, filtering by using 400-mesh qualitative filter paper after stirring, performing ultrasonic treatment on the filtered solution for 0.5 hour under the ultrasonic power of 60W by using a double-layer beaker, stirring for 1 hour under the condition of 300r/min after ultrasonic treatment, standing for 12 hours, and standing for 2 hours in a vacuum oven to remove bubbles. The spinning precursor liquid is obtained.
(2) Carrying out electrostatic spinning;
and (3) sucking the spinning precursor liquid obtained in the step (I) into an injector, and carrying out low-speed electrostatic spinning to obtain the wet film.
The electrostatic spinning process comprises the following steps:
firstly, raising the relative humidity of air in an electrostatic spinning machine to 60%, and keeping for 4 hours to remove floating dust;
then, the temperature is raised to 40 ℃ and kept for 4 hours to reduce the humidity to 10% of the relative humidity of the air;
finally, electrostatic spinning is carried out, and the specific spinning process is as follows:
the propelling speed of the injector is 0.15mm/min, the receiving speed is 200r/min, the receiving distance is 15cm, the spinning needle adopts 23G model, the voltage applied to the injector needle is 6.5KV, the voltage of the receiving end is-6.5 KV, the spinning environment temperature is 20 ℃, and the air relative humidity is 10%. Spinning for 120min, heating to 40deg.C for solidifying for 10min, and ventilating for 10min.
(3) Wet film post-treatment;
and sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain the high-temperature-resistant composite dielectric. The specific process is as follows:
firstly heating the film after spinning in a fume hood at 60 ℃ for 1h by using a heating table, then drying the film in a vacuum oven at 80 ℃ and 0.04MPa in vacuum for 4h, taking out the film, and standing the film in the fume hood for 10min; drying under vacuum state of 0.06MPa at 120deg.C for 2 hr, taking out, and standing in a fume hood for 20min; drying under vacuum state of 0.08MPa at 150deg.C for 2 hr, taking out, and standing in a fume hood for 30min; drying under vacuum state of 0.09MPa at 200deg.C for 2 hr, taking out, and standing in a fume hood for 40min; finally drying for 2 hours under the condition of 0.1MPa in an empty state and 200 ℃, taking out, and standing for 40 minutes at a ventilated drying place.
<2> heating the heated iron plate to 300 ℃ by using a flat vulcanizing machine, and keeping for 1h; after cooling to room temperature, the temperature is gradually raised to 300 ℃ after alcohol is sprayed, and after the temperature is maintained for 1h, the temperature is cooled to room temperature. The film was placed between heated iron plates and the temperature was quickly raised to 250 c, then slowly lowered to 205 c and held for 30min. Then carrying out step heat treatment, wherein the first stage is kept for 20min at 205 ℃ under 2.5 mpa; the second stage is to raise the pressure to 5Mpa and the temperature to 2 ℃ and keep for 20min; the third stage is to keep at 7.5Mpa and 2 ℃ for 15min; step four, boosting to 10Mpa, heating to 2 ℃ and keeping for 15min; step five, boosting to 12.5Mpa, and raising the temperature to 2 ℃ and keeping for 10min; and step six, boosting to 15Mpa, and raising the temperature to 2 ℃ and keeping for 10min.
And (3) directly cooling to 0-25 ℃ by a cold water treatment device after the step heat treatment is completed. A dense polyetherimide full composite dielectric was obtained having a thickness of about 10 μm.
Effect example 1
The four composite electrolytes obtained in examples 1 to 3 and comparative example 1 were characterized in terms of structure and performance, and the results were as follows:
(1) Fig. 1 shows XRD comparison patterns of the composite electrolytes obtained in examples 1 to 3 and comparative example 1, and it is understood from fig. 1 that the multi-concentration synergistic composite medium provided in examples 1 to 3 does not form a new crystalline phase as compared with PEI in comparative example 1, and the structure of the composite medium is not affected by doped multi-concentration ITIC.
(2) Fig. 2 is SEM pictures of the composite electrolytes obtained in examples 1 to 3 and comparative example 1, and as can be seen from fig. 2, the scanning electron microscope pictures of the four composite electrolytes are all of uniform texture, compact and defect-free structures, and have no phenomena such as phase separation, filling and stacking, and the like, thus demonstrating that ITIC can be well compatible with PEI.
(3) Fig. 3 is a graph showing the variation of the dielectric constants with frequency of the composite electrolytes obtained in examples 1 to 3 and comparative example 1, and it is understood from fig. 3 that the dielectric constants and dielectric losses of the four composite electrolytes provided in examples 1 to 3 and comparative example 1 all have good stability with the variation of frequency, and no large relaxation phenomenon occurs with the variation of frequency. Meanwhile, because ITIC is a polar small molecule, the dielectric constant of the composite medium is slightly improved after the ITIC is added.
(4) Fig. 4 shows weibull plots of breakdown field strengths of the composite electrolytes obtained in examples 1 to 3 and comparative example 1 at a high temperature of 200 ℃, and as can be seen from fig. 4, the breakdown field strengths of the 5 ITIC concentration synergistic composite media obtained in example 1 are higher than those of other insulating media, because the high electron affinity of ITIC attracts electrons to block electron migration in the media, so that the breakdown field strength is improved. Under high temperature and high field, the synergistic effect of various concentrations can reduce the ITIC as the intrinsic excitation electron of the molecular semiconductor, so that the reduction of the mobile charge in the medium further improves the breakdown strength.
(5) FIG. 5 is a graph showing the comparison of the energy storage characteristics of the composite electrolytes obtained in examples 1 to 3 and comparative example 1. As can be seen from FIG. 5, the energy storage density of the 5 ITIC concentrations of the composite media obtained in example 1 is higher than that of other composite media, and 3.13J/cm can be obtained at 200℃and under an electric field of 420MV/m 3 Storage density and 86% efficiency. This is due to the synergistic effect of the multiple concentrations, optimizing polarization and breakdown properties between the concentrations, while reducing the intrinsic excited electrons of ITIC as molecular semiconductors reduces conduction losses and improves efficiency.
Example 4
The embodiment takes PEI/PESU blending composite medium as a matrix, is obtained by alternately carrying out electrostatic spinning layer by layer on PEI/PESU blending composite medium with 5 ITIC concentration contents and carrying out hot pressing and quenching processes, wherein the mass ratio of PEI to PESU is 8:2, the volume fraction change value of ITIC is 0.05wt%, and the mass fractions of ITIC in specific layers are as follows:
PEI/PESU-0.25wt.％ITIC、PEI/PESU-0.2wt.％ITIC、PEI/PESU-0.15wt.％ITIC、PEI/PESU-0.1wt.％ITIC、PEI/PESU-0.05wt.％ITIC。
the process steps for preparing the high temperature resistant composite dielectric in this example are as follows:
(1) Preparing spinning precursor liquid;
firstly, filtering N-methyl pyrrolidone solution by using a molecular sieve, weighing ITIC (integrated circuit) mass corresponding to different concentrations, adding the ITIC mass into the filtered N-methyl pyrrolidone solution, performing ultrasonic dispersion treatment on the solution for 1h under the ultrasonic power of 60W by using a double-layer beaker, stirring at the rotation speed of 200r/min for 1.5h, and filtering the solution by using 800-mesh qualitative filter paper after stirring;
and then, drying PEI particles and PESU particles in an oven at 150 ℃ for 4 hours to completely remove water, adding the dried PEI particles and PESU particles (the mass ratio of PEI to PESU is 8:2) into the solution doped with ITIC, heating and stirring for 12 hours at 60 ℃ under 200r/min, filtering by using 400-mesh qualitative filter paper after stirring, performing ultrasonic treatment on the filtered solution for 0.5 hour under 60W ultrasonic power by using a double-layer beaker, stirring for 1 hour under 300r/min after ultrasonic treatment, standing for 12 hours, and standing for 2 hours in a vacuum oven to remove bubbles. The mass fractions of ITICs of the obtained spinning precursor solutions were 0.25wt.% ITICs, 0.2wt.% ITICs, 0.15wt.% ITICs, 0.1wt.% ITICs, and 0.05wt.% ITICs, respectively.
(2) Carrying out electrostatic spinning;
and (3) sucking the PEI/PESU-ITIC spinning precursor liquid with each volume fraction obtained in the step (I) into a syringe respectively, and sequentially carrying out low-speed electrospinning according to the sequence of PEI/PESU-0.25wt.% ITIC, PEI/PESU-0.2wt.% ITIC, PEI/PESU-0.15wt.% ITIC, PEI/PESU-0.1wt.% ITIC, PEI/PESU-0.05wt.% ITIC, PEI/PESU-0.1wt.% ITIC, PEI/PESU-0.15wt.% ITIC, PEI/PESU-0.2wt.% ITIC and PEI/PESU-0.25wt.% ITIC to obtain the wet film.
The electrostatic spinning process comprises the following steps:
firstly, raising the relative humidity of air in an electrostatic spinning machine to 60%, and keeping for 4 hours to remove floating dust;
then, the temperature is raised to 40 ℃ and kept for 4 hours to reduce the humidity to 10% of the relative humidity of the air;
finally, electrostatic spinning is carried out, and the specific spinning process is as follows:
the propelling speed of the injector is 0.15mm/min, the receiver speed is 200r/min, the receiving distance is 15cm, the spinning needle adopts 23G model, the voltage applied by the injector needle gradually rises to 7KV along with the concentration reduction, the voltage of the receiving end is correspondingly-5 KV to-7 KV, the spinning environment temperature is 20 ℃, and the air relative humidity is 10%. The applied voltage of the 0.25wt% ITIC solution is 5KV, and the voltage of a receiving end is-5 KV; the applied voltage of the 0.2wt% ITIC solution is 5.5KV, and the receiving terminal voltage is-5.5 KV; the applied voltage of the 0.15wt% ITIC solution is 6KV, and the voltage of the receiving end is-6 KV; the applied voltage of the 0.1wt% ITIC solution is 6.5KV, and the receiving terminal voltage is-6.5 KV; the applied voltage of the 0.05wt% ITIC concentration solution is 7KV and the receiving terminal voltage is-7 KV. And (3) spinning each layer of solution for 15min, heating the spinning machine to 40 ℃ for solidification for 10min after finishing spinning one layer, and ventilating for 10min.
(3) Wet film post-treatment;
and sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain the high-temperature-resistant composite dielectric. The specific process is as follows:
firstly heating the film after spinning in a fume hood at 60 ℃ for 1h by using a heating table, then drying the film in a vacuum oven at 80 ℃ and 0.04MPa in vacuum for 4h, taking out the film, and standing the film in the fume hood for 10min; drying under vacuum state of 0.06MPa at 120deg.C for 2 hr, taking out, and standing in a fume hood for 20min; drying under vacuum state of 0.08MPa at 150deg.C for 2 hr, taking out, and standing in a fume hood for 30min; drying under vacuum state of 0.09MPa at 200deg.C for 2 hr, taking out, and standing in a fume hood for 40min; finally drying for 2 hours under the condition of 0.1MPa in an empty state and 200 ℃, taking out, and standing for 40 minutes at a ventilated drying place.
<2> heating the heated iron plate to 300 ℃ by using a flat vulcanizing machine, and keeping for 1h; after cooling to room temperature, the temperature is gradually raised to 300 ℃ after alcohol is sprayed, and after the temperature is maintained for 1h, the temperature is cooled to room temperature. The film was placed between heated iron plates and the temperature was rapidly raised to 250 c followed by a slow decrease in temperature to 200 c for 30min. Then carrying out step heat treatment, wherein the first stage is kept for 20min at 200 ℃ under 2.5 mpa; the second stage is to raise the pressure to 5Mpa and the temperature to 2 ℃ and keep for 20min; the third stage is to keep at 7.5Mpa and 2 ℃ for 15min; step four, boosting to 10Mpa, heating to 2 ℃ and keeping for 15min; step five, boosting to 12.5Mpa, and raising the temperature to 2 ℃ and keeping for 10min; and step six, boosting to 15Mpa, and raising the temperature to 2 ℃ and keeping for 10min.
And (3) directly cooling to 0-25 ℃ by a cold water treatment device after the step heat treatment is completed. A dense 5-concentration synergistic composite dielectric (abbreviated as 20% pesu-9 layer) was obtained with a thickness of about 10 μm.
Comparative example 2
The comparative example provides a preparation of a pure polyethersulfone media, which differs from comparative example 1 in that: the polyether sulfone was used in place of the polyetherimide and the rest of the procedure and parameter settings were the same as in comparative example 1 to give a dense polyether sulfone composite dielectric with a thickness of about 10 μm.
Comparative example 3
The comparative example provides a preparation of a PEI and PESU blended composite medium, and the specific preparation is different from comparative example 1 in that: the use mass is 9:1 with PESU, the remainder of the procedure and parameter settings were the same as comparative example 1, resulting in a dense PEI/PESU (9:1) blend composite media with a thickness of about 10 μm.
Comparative example 4
The comparative example provides a preparation of a PEI and PESU blended composite medium, and the specific preparation is different from comparative example 1 in that: the use mass is 8:2 with PESU, the remainder of the procedure and parameter settings were the same as comparative example 1, resulting in a dense PEI/PESU (8:2) blend composite media with a thickness of about 10 μm.
Comparative example 5
The comparative example provides a preparation of a PEI and PESU blended composite medium, and the specific preparation is different from comparative example 1 in that: the use mass is 7:3 with PESU, the remainder of the procedure and parameter settings were the same as comparative example 1, resulting in a dense PEI/PESU (7:3) blend composite media with a thickness of about 10 μm.
Comparative example 6
The comparative example provides a preparation of a PEI and PESU blended composite medium, and the specific preparation is different from comparative example 1 in that: the use mass is 6:4 with PESU, the remainder of the procedure and parameter settings were the same as comparative example 1, resulting in a dense PEI/PESU (6:4) blend composite media with a thickness of about 10 μm.
Effect example 2
The four composite dielectrics obtained in example 4 and comparative examples 1 to 6 were characterized for structure and performance, and the results were as follows:
fig. 6 shows XRD contrast patterns of the composite electrolytes obtained in example 4 and comparative examples 1 to 6, and it is understood from fig. 6 that pure PESU has a higher peak value in the vicinity of a low angle relative to pure PEI. Thus, as the PESU content increases, the peak value of the PESU/PEI composite media increases gradually around an angle value of 20, demonstrating the successful introduction of PESU.
Fig. 7 to 10 are SEM photographs of cross sections of the composite dielectrics obtained in example 4 and comparative examples 1 to 6, respectively, and it is understood that the dielectrics of various doping ratios have a uniform texture, a dense and defect-free structure, and no phenomena such as significant phase separation and packing phase accumulation occur. The PEI, the PESU and the ITIC have good compatibility.
Fig. 11 is a graph showing the change in dielectric constant with frequency of the composite dielectrics obtained in example 4 and comparative examples 1 to 6, and it is clear from fig. 11 that the relative dielectric constant and dielectric loss of PESU are relatively high with respect to PEI. As the amount of PESU introduced into the PEI increases, both the dielectric constant and dielectric loss of the PEI/PESU increase. At PEI: pesu=6:4, the dielectric constant is greatest, since dipole steering polarization is more likely to occur due to increased molecular chain spacing. The dielectric losses were kept at a low value for the seven media provided in example 4 and comparative examples 1, 2, 3, 4, 5, 6.
Fig. 12 shows the weibull plots of the breakdown field strengths of the composite dielectrics obtained in example 4 and comparative examples 1 to 6, and it is clear from fig. 12 that the breakdown strength is the greatest at PEI: pesu=8:2 as the PESU content increases and then decreases. On the basis of PEI: PESU=8:2 composite medium, the breakdown strength is further improved by 480kv/mm after the synergistic effect of ITIC with 5 concentrations.
Fig. 13 is a graph comparing the energy storage characteristics of the composite dielectrics obtained in example 4 and comparative examples 1 to 6, and it can be seen from fig. 13 that the energy storage density of the 5 concentrations of the composite dielectric material in example 4 is higher than that of the other composite dielectric materials in a synergistic effect based on PEI: pesu=8:2 composite dielectric material. At a high temperature of 200 ℃ and an electric field strength of 440MV/m, 3.6J/cm can be obtained 3 Storage density and 88% efficiency.
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.
Claims (7)
1. A preparation method of a high temperature resistant composite dielectric medium is characterized in that the dielectric medium is of a laminated structure, each layer is formed by taking PEI and/or PESU as a matrix and doping ITIC, and the concentration of the dielectric medium doping ITIC is sequentially from top to bottom and then from bottom to top; the thickness of the dielectric is 10-13 mu m;
the preparation method of the high temperature resistant composite dielectric medium comprises the following steps:
(1) Preparing spinning precursor liquid; taking PEI and/or PESU as a matrix, doping ITIC with different mass to obtain spinning precursor solutions with different ITIC concentrations;
(2) Sequentially carrying out electrostatic spinning on the obtained spinning precursor solutions with different ITIC concentrations, and carrying out primary curing treatment on each spinning precursor solution after spinning is completed to obtain a multi-concentration ITIC synergistic PEI and/or PESU blending base wet film;
the electrostatic spinning parameters in the step (2) are as follows: the advancing speed of the injector is 0.15mm/min, the speed of the receiver is 200r/min, the receiving distance is 15cm, the voltage applied to the needle of the injector is 5-7 KV, the voltage of the receiving end is-5-7 KV, the temperature is 20 ℃, the relative humidity is 10%, and the spinning time of each spinning precursor solution is 15min;
(3) Sequentially performing drying, step-type heat treatment and quenching treatment on the obtained wet film to obtain a high-temperature-resistant composite dielectric;
the drying treatment in the step (3) is as follows: firstly, drying for 1-2 h at the normal pressure and 60 ℃; drying at 80 deg.C under 0.04MPa for 4 hr, and standing in a fume hood for 10min; drying at 120 deg.C under 0.06MPa for 2 hr, and standing in a fume hood for 20min; drying at 150 deg.C under 0.08MPa for 2 hr, and standing in a fume hood for 30min; drying at 200 deg.C under 0.09MPa for 2 hr, and standing in a fume hood for 40min; finally, drying for 2 hours at 200 ℃ under 0.1MPa, and standing for 40 minutes in a fume hood;
the step heat treatment is as follows: placing the dried wet film between heating iron plates of a vulcanizing press, quickly heating to 250 ℃, slowly reducing the temperature to 215 ℃, preserving the heat for 30min, and performing step heat treatment, wherein the first stage is hot-pressed for 20min under 2.5Mpa and 200 ℃; in the second stage, 5Mpa, heating to 2 ℃ and hot-pressing for 20min; in the third stage, 7.5Mpa, heating to 2 ℃ and hot-pressing for 15min; fourth, heating to 2 deg.C under 10Mpa, and hot-pressing for 15min; in the fifth stage, 12.5Mpa, heating to 2 ℃ and hot-pressing for 10min; in the sixth stage, 15Mpa and 2 ℃ are heated, and hot pressing is carried out for 10min;
the quenching treatment comprises the following steps: cooling to 0-25 ℃ by a cold water treatment device after the stepped heat treatment is completed.
2. The method of manufacturing a high temperature resistant composite dielectric according to claim 1, wherein the dielectric comprises 5 ITIC concentrations of 0.25wt%, 0.2wt%, 0.15wt%, 0.1wt% and 0.05wt%, respectively.
3. The method of manufacturing a high temperature resistant composite dielectric according to claim 1, wherein the dielectric comprises 4 ITIC concentrations of 0.25wt%, 0.2wt%, 0.15wt% and 0.1wt%, respectively.
4. The method of manufacturing a high temperature resistant composite dielectric according to claim 1, wherein the dielectric comprises 3 ITIC concentrations of 0.25wt%, 0.2wt% and 0.15wt%, respectively.
5. The method of claim 1, wherein the mass ratio of PEI to PESU is 9:1, 8:2, 7:3 or 6:4.
6. The method of claim 1, wherein the injector needles of the spinning precursors of (2) of different ITIC concentrations are applied with different voltages.
7. Use of a high temperature resistant composite dielectric according to claim 1 for rapid charge and discharge applications.
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