CN115538215A - Corona-resistant mica/aramid fiber composite material for new energy automobile and preparation method thereof - Google Patents
Corona-resistant mica/aramid fiber composite material for new energy automobile and preparation method thereof Download PDFInfo
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Abstract
The application discloses a corona-resistant mica/aramid fiber composite material for a new energy automobile and a preparation method thereof, which belong to the technical field of mica composite materials, wherein the composite material is prepared from the following raw materials in percentage by weight: 40-60% of modified aramid fiber paper, 5-20% of adhesive and 40-60% of modified mica paper; wherein the weight ratio of the modified aramid fiber paper to the modified mica paper is (1-1.5): 1, the adhesive comprises one or more of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, polyether ether ketone and polyetherimide. According to the application, the modified aramid fiber paper and the modified mica paper are compounded by using the adhesive, and the modified mica paper and the modified aramid fiber paper with excellent corona resistance are matched, so that the overall compactness, paper insertion manufacturability, corona resistance, PDIV (polymer induced degradation) and temperature resistance level of the composite material are improved, and the material can obviously improve the electrical insulation property and long-term safe operation life of a new energy automobile motor.
Description
Technical Field
The application relates to a corona-resistant mica/aramid fiber composite material for a new energy automobile and a preparation method thereof, and belongs to the technical field of mica composite materials.
Background
Most of the high-temperature-resistant above-H-level slot insulation and interphase insulation paper for the existing new energy automobile motor is aramid fiber pure paper, or aramid fiber paper and a polyimide film are compounded by using a high-temperature-resistant adhesive, the typical composite paper structure is Nomex fiber paper/PI film/Nomex fiber paper (NHN), and the composite adhesive mainly adopts epoxy, polyurethane or polyacrylate adhesives.
The aramid fiber pure paper or the NHN composite paper has high heat resistance, the performance of the insulating structure of the 400V voltage platform motor for the new energy automobile is very excellent, however, for the 800V voltage platform motor, because the voltage level is high, the highest safety voltage of the aramid fiber pure paper or the NHN composite paper can reach 2300V or even higher due to the influence of pulse width modulation spike voltage and environmental factors, the highest safety voltage of the aramid fiber pure paper or the NHN composite paper is far higher than the Partial Discharge Initial Voltage (PDIV) of the insulating material for the existing conventional low-voltage motor, and the probability of generating partial discharge in the motor operation process is very high, so the corona resistance of the insulating material must be considered for the 800V voltage platform automobile motor.
In the prior art, mica components are added into organic aramid fiber paper, or epoxy, polyurethane or polyacrylate adhesives are used for compounding the aramid fiber paper and the mica paper, so that the corona resistance life of the composite paper is prolonged. However, the mica-containing composite paper prepared by the two methods generally has the problems of easy powder falling, easy fragmentation, easy layering and the like, and the corona resistance and the high temperature resistance are general, so that the process requirements of the mass application of new energy automobile motors cannot be met.
Disclosure of Invention
In order to solve the problems, the application provides a corona-resistant mica/aramid fiber composite material for a new energy automobile and a preparation method thereof, and modified aramid fiber paper and the modified mica paper are compounded in a hot-pressing manner by using PFA-tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, FEP-fluorinated ethylene propylene copolymer (F46, tetrafluoroethylene and hexafluoropropylene copolymer), ETFE-ethylene-tetrafluoroethylene copolymer, PEEK-polyether ether ketone, PEI-polyetherimide and other adhesives with high temperature resistance and low dielectric constant, and the modified mica paper and the modified aramid fiber paper with excellent corona resistance are matched at the same time, so that the overall compactness, paper insertion manufacturability, corona resistance, partial Discharge Initial Voltage (PDIV) and temperature resistance level of the composite material can be improved, and the electrical insulation performance and long-term safe operation life of a new energy automobile motor can be obviously improved by using the material as slot bottom insulation paper and phase insulation paper.
According to one aspect of the application, the corona-resistant mica/aramid fiber composite material for the new energy automobile is provided, and comprises the following raw materials in percentage by weight: 40-60% of modified aramid fiber paper, 5-20% of adhesive and 40-60% of modified mica paper;
wherein the weight ratio of the modified aramid fiber paper to the modified mica paper is (1-1.5): 1, the adhesive comprises one or more of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, polyether ether ketone and polyetherimide.
Preferably, the adhesive is FEP-fluorinated ethylene propylene copolymer (F46, tetrafluoroethylene and hexafluoropropylene copolymer); preferably, the adhesive comprises FEP-fluorinated ethylene propylene copolymer (F46, tetrafluoroethylene and hexafluoropropylene copolymer) and polyetheretherketone in a weight ratio of 3:1.
optionally, the modified mica paper is prepared from the following raw materials: mica powder, hydrochloric acid solution, ethanol, a silane coupling agent, methyl methacrylate, an initiator and toluene;
the mica powder consists of first mica powder, second mica powder and third mica powder, wherein the particle size of the first mica powder is 90-110 mu m, the particle size of the second mica powder is 130-150 mu m, and the particle size of the third mica powder is 200-230 mu m; the weight ratio of the first mica powder to the second mica powder to the third mica powder is 1: (3-5): (3-5).
Specifically, the concentration of the hydrochloric acid solution is 2mol/L.
Optionally, the weight ratio of the silane coupling agent to the mica powder is (0.05-0.08): 1, the weight ratio of the mica powder to the methyl methacrylate to the initiator is 1: (0.1-0.15): (0.002-0.005), the weight ratio of the mica powder to the ethanol and the toluene is 1: (6-8): (5-8).
Optionally, the preparation method of the modified mica paper comprises the following steps: adding a silane coupling agent into ethanol, adjusting the pH value to 4 by using a hydrochloric acid solution, adding mica powder, heating to 60-80 ℃, stirring for 1-3h, filtering, washing and drying, adding the mixture into toluene, adding methyl methacrylate and an initiator at the same time, reacting for 2-4h at 70-90 ℃, filtering, drying for 0.5-2h at 110-130 ℃, adding water, stirring uniformly to form a slurry, and making the modified mica paper by a paper sheet forming machine.
Specifically, the mass concentration of the slurry is 3-5%.
Alternatively, the silane coupling agent is a171, and the initiator is benzoyl peroxide.
Optionally, the modified aramid fiber paper is prepared from meta-aramid chopped fibers and meta-aramid fibrids, the lengths of the meta-aramid chopped fibers and the meta-aramid fibrids are both 2-3mm, and the weight ratio of the meta-aramid chopped fibers to the meta-aramid fibrids is 1: (2-2.5).
Optionally, the preparation method of the modified aramid fiber paper comprises the following steps: and (3) defibering and dispersing the meta-aramid chopped fibers and the meta-aramid fibrids, adding water to prepare slurry, and performing ultrasonic treatment and papermaking by a paper sheet forming machine to obtain the modified aramid fiber paper.
Specifically, the mass concentration of the slurry is 0.1-0.5%.
Optionally, the ultrasonic treatment step is ultrasonic treatment for 10s each time at intervals of 3s for 6-9min; ultrasonic parameters: the frequency is 10-20kHz, and the power is 500W.
According to another aspect of the application, a preparation method of the corona-resistant mica/aramid fiber composite material for the new energy automobile is provided, and the preparation method comprises the following steps:
(1) Unreeling two rolls of modified aramid fiber paper, and respectively coating adhesives on the surfaces of the two rolls of modified aramid fiber paper;
(2) Unreeling the modified mica paper, firstly attaching the modified mica paper to one piece of modified aramid fiber paper coated with the adhesive, then attaching the other piece of modified aramid fiber paper coated with the adhesive to the other side of the modified mica paper, and drying;
(3) And (3) carrying out hot-pressing on the dried composite material by a hot roller to finally obtain the corona-resistant mica/aramid fiber composite material for the new energy automobile.
Optionally, the drying temperature is 120 ℃, the hot pressing temperature is 265-310 ℃, and the hot pressing pressure is 20MPa.
Benefits of the present application include, but are not limited to:
1. according to the corona-resistant mica/aramid fiber composite material for the new energy automobile, firstly, PFA-tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, FEP-fluorinated ethylene propylene copolymer (F46, tetrafluoroethylene and hexafluoropropylene copolymer), ETFE-ethylene and tetrafluoroethylene copolymer, PEEK-polyether ether ketone, PEI-polyetherimide and other high temperature resistant and low dielectric constant adhesives are used for hot-pressing compounding modified aramid fiber paper and modified mica paper, and meanwhile, the modified mica paper and the modified aramid fiber paper with excellent corona resistance are matched, so that the overall compactness, paper insertion manufacturability, corona resistance, partial Discharge Initial Voltage (PDIV) and temperature resistant grade of the composite material can be improved.
2. According to the corona-resistant mica/aramid fiber composite material for the new energy automobile, mica powder is limited to be composed of three mica powders with different particle sizes, the respective proportions are limited, the mica powder layer with the large particle size is complete in sheet shape, a good stress transmission effect can be achieved, paper is prevented from being broken due to stress concentration, meanwhile, the paper is endowed with certain stiffness, mica with the small particle size and the small particle size, which accounts for a small proportion, is filled among large mica flakes, and the paper can be endowed with good strength performance;
meanwhile, the regular arrangement of two kinds of mica powder with larger grain diameter also endows paper with better smoothness, the mica powder has larger diameter-thickness ratio, the high insulation effect of the layer sheet in the Z direction has better barrier effect on current, the formation of a current channel is delayed, the electric arc spreading is effectively delayed, the fiber carbonization damage is reduced, the size area of a breakdown point is reduced, and the corona resistance is improved.
3. According to the corona-resistant mica/aramid fiber composite material for the new energy automobile, the mica paper is compositely modified by using the silane coupling agent and the polymer monomer, hydroxyl exists on the surface of mica powder, double bonds are introduced on the surface of the powder by using the silane coupling agent A171, then the monomer and the initiator are added into the mica powder liquid for polymerization reaction, and the vinyl on the surface of the mica powder is copolymerized with the monomer, so that the surface graft polymer is realized, the dispersibility of the mica/aramid fiber composite material in slurry is improved, and the interface bonding performance of the mica/aramid fiber composite material and the modified aramid fiber paper is finally improved.
4. According to the corona-resistant mica/aramid fiber composite material for the new energy automobile, the grafting rate of the surface of mica powder is improved by limiting the proportion of the silane coupling agent to the mica powder; the coating rate of the polymer is improved by limiting the proportion of mica powder, monomer and initiator.
5. According to the corona-resistant mica/aramid fiber composite material for the new energy automobile, meta-aramid chopped fibers and meta-aramid fibrid are used, the length and the proportion of the meta-aramid chopped fibers are limited, the chopped fibers are of a rod-shaped structure, the fibrid is light and thin film-shaped, in the proportion range, the fibrid can be adhered to the rod-shaped chopped fibers together, the chopped fibers are helped to form a support and become a trunk to which the fibrid is attached, when external force is applied, the action of stress transfer can be achieved, meanwhile, the density of the composite material is high due to a network structure interwoven by the chopped fibers, the corona resistance is excellent, and the service life is long.
6. According to the utility model provides a corona-resistant mica/aramid fiber combined material for new energy automobile, mix aramid fiber through the ultrasonic modification, can strengthen aramid fiber's the fine degree of fibrosis in surface, increase surface active group and surface energy, thereby improve aramid fiber chopped fiber's dispersion properties, enable aramid fiber specific surface area and surface roughness's improvement simultaneously, can increase chopped fiber and fibrid's interweaving power, make aramid fiber go out the fibrillation phenomenon, strengthen the mechanical interlocking effect between the fiber interface, thereby improve combined material's mechanical properties and high temperature resistance.
7. According to the preparation method of the corona-resistant mica/aramid fiber composite material for the new energy automobile, the chopped fibers and the precipitated fibers are sufficiently softened and bonded by high-temperature hot-press molding and limiting the hot-press temperature, and meanwhile, the adhesive is sufficiently permeated into pores of the modified aramid fiber paper and the modified mica paper to form an integrally compact composite material, so that the tensile strength of the composite material is improved, and the electrical performance is good.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a schematic structural diagram of a corona-resistant mica/aramid fiber composite material for a new energy automobile according to an embodiment of the application.
Reference numerals: 1. modifying aramid fiber powder; 2. an adhesive; 3. modified mica paper.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments of the methods and materials of this patent are illustrative only.
Experiment raw materials:
1. mica powder with three particle sizes: the mica raw materials with different grain diameters are prepared by wet grinding through a ball mill, the ball-material ratio is controlled to be 4, the matching mass ratio of medium and small balls is 1, the set rotating speed is 300rmp, and the grain diameter distribution of the mica are measured through a laser grain size analyzer to prepare three mica slurries with different grain diameters.
2. The instrument comprises: ball mill: TCXQM-2, tianchuang powder Co., ltd; laser particle size analyzer: BT-9300H, baite instruments, inc.; a presser: CHYZ-01, initially creating electromechanics; tensile strength tester: SE-062, lorentzen Wether, sweden; fluffer: ZQS4, lorentzen Wether, sweden; a paper sheet making and forming machine, shenzhen Puyun, PY-Y814B.
3. Reagent: mica: hubei safety electric materials, inc.; silane coupling agent a171, american mezzo; methyl methacrylate, shandongxin (r) shun new materials, ltd; benzoyl peroxide, jiangsu Qiangsheng functional chemistry GmbH; aramid fiber: the Japanese emperor.
Example 1 composite 1#
The composite material 1# is prepared from the following raw materials in percentage by weight: 40% of modified aramid fiber paper, 5% of adhesive and 40% of modified mica paper, wherein the adhesive is FEP-fluorinated ethylene propylene copolymer (F46, tetrafluoroethylene and hexafluoropropylene copolymer).
The modified mica paper is prepared from the following raw materials: mica powder, hydrochloric acid solution, ethanol, silane coupling agent, methyl methacrylate, initiator and toluene; the mica powder consists of first mica powder, second mica powder and third mica powder, wherein the particle size of the first mica powder is 90 mu m, the particle size of the second mica powder is 130 mu m, and the particle size of the third mica powder is 200 mu m; the weight ratio of the first mica powder to the second mica powder to the third mica powder is 1:3:3; the weight ratio of the silane coupling agent to the mica powder is 0.05:1, the weight ratio of mica powder to methyl methacrylate to initiator is 1:0.1:0.002, the weight ratio of mica powder to ethanol and toluene is 1:6:5; the preparation method of the modified mica paper comprises the following steps: adding a silane coupling agent A171 into ethanol, adjusting the pH value to 4 by using a hydrochloric acid solution, adding mica powder, heating to 60 ℃, stirring for 1h, filtering, washing and drying, adding the mixture into toluene, simultaneously adding methyl methacrylate and benzoyl peroxide, reacting for 2h at 70 ℃, drying for 0.5h at 110 ℃ after filtering, adding water, stirring uniformly to form slurry with the mass concentration of 3%, and making the slurry by a paper sheet forming machine to obtain the modified mica paper.
Wherein, modified aramid fiber paper is prepared by meta-position aramid chopped fiber and meta-position aramid fibrid, meta-position aramid chopped fiber and meta-position aramid fibrid are both 2mm in length, and the weight ratio of meta-position aramid chopped fiber to meta-position aramid fibrid is 1:2; the preparation method of the modified aramid fiber paper comprises the following steps: carrying out defibering and dispersing on meta-aramid chopped fibers and meta-aramid fibrids, adding water to prepare slurry with the mass concentration of 0.1%, and carrying out ultrasonic treatment and papermaking by a paper sheet forming machine to obtain modified aramid fiber paper, wherein the thickness of the aramid fiber paper is 0.05mm; the ultrasonic treatment step is ultrasonic treatment for 10s every time at intervals of 3s for 6min; ultrasonic parameters: the frequency was 10kHz and the power was 500W.
The preparation method of the composite material 1# comprises the following steps:
(1) Unreeling two rolls of modified aramid fiber paper, and respectively coating adhesives on the surfaces of the two rolls of modified aramid fiber paper;
(2) Unreeling the modified mica paper, firstly attaching the modified mica paper to one piece of modified aramid fiber paper coated with the adhesive, then attaching the other piece of modified aramid fiber paper coated with the adhesive to the other side of the modified mica paper, and drying;
(3) And (3) hot-pressing the dried composite material by a hot roller to finally obtain the corona-resistant mica/aramid fiber composite material 1# for the new energy automobile, wherein the thickness of the corona-resistant mica/aramid fiber composite material is 0.25mm.
Wherein the drying temperature is 120 ℃, the hot pressing temperature is 270 ℃, and the hot pressing pressure is 20MPa.
Example 2 composite 2#
The composite material 2# is prepared from the following raw materials in percentage by weight: 50% of modified aramid fiber paper, 10% of adhesive and 40% of modified mica paper, wherein the adhesive is FEP-fluorinated ethylene propylene copolymer (F46, tetrafluoroethylene and hexafluoropropylene copolymer).
The modified mica paper is prepared from the following raw materials: mica powder, hydrochloric acid solution, ethanol, a silane coupling agent, methyl methacrylate, an initiator and toluene; the mica powder consists of first mica powder, second mica powder and third mica powder, wherein the particle size of the first mica powder is 110 mu m, the particle size of the second mica powder is 150 mu m, and the particle size of the third mica powder is 230 mu m; the weight ratio of the first mica powder to the second mica powder to the third mica powder is 1:5:5; the weight ratio of the silane coupling agent to the mica powder is 0.08:1, the weight ratio of mica powder to methyl methacrylate to initiator is 1:0.15:0.005, the weight ratio of the mica powder to the ethanol and the toluene is 1:8:8; the preparation method of the modified mica paper comprises the following steps: adding a silane coupling agent A171 into ethanol, adjusting the pH value to 4 by using a hydrochloric acid solution, adding mica powder, heating to 80 ℃, stirring for 3 hours, filtering, washing and drying, adding the mixture into toluene, simultaneously adding methyl methacrylate and benzoyl peroxide, reacting for 4 hours at 90 ℃, drying for 2 hours at 130 ℃ after filtering, adding water, stirring uniformly to form slurry with the mass concentration of 4%, and making the slurry by a paper sheet forming machine to obtain the modified mica paper.
Wherein, modified aramid fiber paper is prepared by meta-position aramid chopped fiber and meta-position aramid fibrid, meta-position aramid chopped fiber and meta-position aramid fibrid are both 3mm in length, and the weight ratio of meta-position aramid chopped fiber to meta-position aramid fibrid is 1:2.5; the preparation method of the modified aramid fiber paper comprises the following steps: carrying out defibering and dispersing on meta-aramid chopped fibers and meta-aramid fibrids, adding water to prepare slurry with the mass concentration of 0.3%, carrying out ultrasonic treatment, and papermaking by a paper sheet forming machine to obtain modified aramid fiber paper, wherein the thickness of the aramid fiber paper is 0.05mm; the ultrasonic treatment step comprises ultrasonic treatment for 9min at intervals of 3s for 10s every time; ultrasonic parameters: the frequency was 20kHz and the power was 500W.
The preparation method of the composite material 2# comprises the following steps:
(1) Unreeling two rolls of modified aramid fiber paper, and respectively coating adhesives on the surfaces of the two rolls of modified aramid fiber paper;
(2) Unreeling the modified mica paper, firstly attaching the modified mica paper to one piece of modified aramid fiber paper coated with the adhesive, then attaching the other piece of modified aramid fiber paper coated with the adhesive to the other side of the modified mica paper, and drying;
(3) And (3) hot-pressing the dried composite material by using a hot roller to finally obtain the corona-resistant mica/aramid fiber composite material 2# for the new energy automobile, wherein the thickness of the corona-resistant mica/aramid fiber composite material is 0.25mm.
Wherein the drying temperature is 120 ℃, the hot pressing temperature is 265 ℃, and the hot pressing pressure is 20MPa.
Example 3 composite 3#
The composite material No. 3 is prepared from the following raw materials in percentage by weight: 60% of modified aramid fiber paper, 20% of adhesive and 40% of modified mica paper, wherein the adhesive is PFA-tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer.
The modified mica paper is prepared from the following raw materials: mica powder, hydrochloric acid solution, ethanol, silane coupling agent, methyl methacrylate, initiator and toluene; the mica powder consists of first mica powder, second mica powder and third mica powder, wherein the particle size of the first mica powder is 100 mu m, the particle size of the second mica powder is 140 mu m, and the particle size of the third mica powder is 220 mu m; the weight ratio of the first mica powder to the second mica powder to the third mica powder is 1:4:4; the weight ratio of the silane coupling agent to the mica powder is 0.06:1, the weight ratio of mica powder to methyl methacrylate to initiator is 1:0.12:0.003, the weight ratio of the mica powder to the ethanol and the toluene is 1:7:6; the preparation method of the modified mica paper comprises the following steps: adding a silane coupling agent A171 into ethanol, adjusting the pH value to 4 by using a hydrochloric acid solution, adding mica powder, heating to 70 ℃, stirring for 2 hours, filtering, washing and drying, adding the mixture into toluene, simultaneously adding methyl methacrylate and benzoyl peroxide, reacting for 3 hours at 80 ℃, drying for 1 hour at 120 ℃ after filtering, adding water, stirring uniformly to form slurry with the mass concentration of 5%, and making the slurry by a paper sheet forming machine to obtain the modified mica paper.
Wherein, modified aramid fiber paper is prepared by meta-position aramid chopped fiber and meta-position aramid fibrid, meta-position aramid chopped fiber and meta-position aramid fibrid are both 2mm in length, and the weight ratio of meta-position aramid chopped fiber to meta-position aramid fibrid is 1:2.2; the preparation method of the modified aramid fiber paper comprises the following steps: carrying out defibering and dispersing on meta-aramid chopped fibers and meta-aramid fibrids, adding water to prepare slurry with the mass concentration of 0.5%, carrying out ultrasonic treatment, and papermaking by a paper sheet forming machine to obtain modified aramid fiber paper, wherein the thickness of the aramid fiber paper is 0.05mm; the ultrasonic treatment step is ultrasonic treatment for 7min at intervals of 3s for 10s each time; ultrasonic parameters: the frequency was 15kHz and the power was 500W.
The preparation method of the composite material 3# comprises the following steps:
(1) Unreeling two rolls of modified aramid fiber paper, and respectively coating adhesives on the surfaces of the two rolls of modified aramid fiber paper;
(2) Unreeling the modified mica paper, firstly attaching the modified mica paper to one piece of modified aramid fiber paper coated with an adhesive, then attaching the other piece of modified aramid fiber paper coated with the adhesive to the other side of the modified mica paper, and drying;
(3) And (3) hot-pressing the dried composite material by using a hot roller to finally obtain the corona-resistant mica/aramid fiber composite material for the new energy automobile, wherein the thickness of the corona-resistant mica/aramid fiber composite material is 0.25mm.
Wherein the drying temperature is 120 ℃, the hot pressing temperature is 310 ℃, and the hot pressing pressure is 20MPa.
Example 4 composite 4#
Example 4 differs from example 1 in that: the adhesive in example 4 was a fluorinated ethylene propylene copolymer (F46, a copolymer of tetrafluoroethylene and hexafluoropropylene) and polyetheretherketone in a weight ratio of 3:1, which are the same as each other.
Comparative example 1 comparative composite 1#
Comparative example 1 differs from example 3 in that: in comparative example 1, the adhesive was a methylated amino resin, and the remainder was the same.
Comparative example 2 comparative composite 2#
Comparative example 2 differs from example 3 in that: in comparative example 2, the aramid fiber was not modified, and the rest was the same.
Comparative example 3 comparative composite No. 3
Comparative example 3 differs from example 3 in that: in comparative example 3, the mica powder has a particle size of 50 μm and 90 μm, and the weight ratio is 1.
Comparative example 4 comparative composite 4#
Comparative example 4 differs from example 3 in that: in comparative example 4, the weight ratio of the first mica powder to the second mica powder to the third mica powder is 1:1.5:1.2, the rest are the same.
Comparative example 5 comparative composite 5#
Comparative example 5 differs from example 3 in that: in comparative example 5, the weight ratio of the silane coupling agent to the mica powder was 0.12:1, the rest are the same.
Comparative example 6 comparative composite No. 6
Comparative example 6 differs from example 3 in that: in comparative example 6, mica powder was modified using only the silane coupling agent KH550, and the rest was the same.
Comparative example 7 comparative composite 7#
Comparative example 7 differs from example 3 in that: in comparative example 7, para-aramid fibrids were used as the aramid fibers, and the rest were the same.
Comparative example 8 comparative composite No. 8
Comparative example 8 differs from example 3 in that: in comparative example 8, the lengths of the meta-aramid chopped fiber and the meta-aramid fibrid were all 5mm, and the others were the same.
Comparative example 9 comparative composite 9#
Comparative example 9 differs from example 3 in that: comparative example 9 the weight ratio of the meta-aramid chopped fiber to the para-aramid fibrids was 1:1, the rest are the same.
Comparative example 10 comparative composite 10#
Comparative example 10 differs from example 3 in that: comparative example 10 the hot press molding temperature was 360 ℃, and the rest was the same.
Comparative example 11 comparative composite 11#
Comparative example 11 is a pure paper of meta-aramid fiber paper with a thickness of 0.25mm.
Comparative example 12 comparative composite 12#
Comparative example 12 is a composite material (commercially available material name NHN) prepared by laminating meta-aramid fiber paper having a thickness of 0.05mm on both surfaces of a polyimide film using polyurethane as an adhesive, and having a thickness of 0.25mm.
Examples of the experiments
1. Electrical performance
Breakdown voltage: the test is carried out according to the national standard GB/T1408.1-2006, the sample thickness is 0.25mm, a phi 25 mm/phi 75mm cylindrical electrode system is adopted, the test frequency is 5 times, and the average value is taken.
PDIV (partial discharge initiation voltage): the test is carried out according to the national standard GB/T7354-2018, and the frequency of the alternating voltage is as follows: 50hz; pressure rise speed: 50V/s; taking the partial discharge capacity of 10PC as an initial discharge voltage point; experiment temperature: 21-25 ℃, humidity: 45 to 55 percent.
2. Temperature resistance test
The experimental method comprises the following steps: the test is carried out according to the national standard GB/T4074.7-2009, and the heat resistance grade of the material is evaluated by adopting a three-point method.
3. Tensile strength
The experimental method comprises the following steps: the determination is carried out according to national standards GB/T20629.2-2013 and GB/T5591.2-2017.
4. Square wave corona resistance life
The experimental method comprises the following steps: the test is carried out according to the T/CEEIA 415-2019 standard, and the test conditions are as follows: the peak-to-peak voltage Vp-p =3000V, the temperature 155 + -3 ℃, the frequency =20KHz, the rising edge 100 + -10 ns and the duty ratio 50%.
The composite materials 1# -4# and the comparative composite materials 1# -12# were sampled to perform the above four experimental tests, and the experimental results are shown in table 1.
TABLE 1
From the experimental data, the composite material No. 1-4 prepared by the raw materials and the method defined in the application has the advantages of good electrical property, long corona resistance life of square waves, excellent high temperature resistance and excellent mechanical property.
Compared with the composite material 1#, the adhesive is a common adhesive sold in the market, and the final result is common in electrical property and high-temperature resistance; compared with the composite material 2# in which aramid fibers are not modified, the final result is general in electrical performance, and the analytical reason is that the aramid fibers have high inertia and poor interface bonding effect with other matrix materials.
Mica powder particle diameter is less than the scope that this application was prescribed a limit in the contrast combined material 3#, the end result electrical property is general, the breakdown voltage is low, the assay reason can produce more mica piece because the mica that the particle diameter is little, it adds to and mostly acts as "silt" component in the paper, anomalous arrangement leads to the paper structure loose, thickness increases, paper mixed structure receives destruction, the decline of paper mechanical properties, simultaneously the paper hole increases, when the paper receives external voltage to act on, the electron beam stops owing to reduced the high insulation in the big piece mica Z side, it punctures to lead to the fact the paper more easily.
The proportion of the small-particle-size mica powder in the comparative composite material No. 4 exceeds the range defined by the application, the final result is general electrical performance, and the analysis reason is that as the mica with smaller particle size increases, the integrity of mica layer sheets is damaged, the size of the mica layer sheets is increased in the longitudinal structure, the fine particles are increased and gradually gathered and accumulated, the arrangement of the mica sheets is changed from flat laying to inclined laying, and the mechanical performance is reduced; meanwhile, as the mica layer sheet is damaged, the mica with a large proportion and a small particle size is granular, and a large number of pores are formed by stacking the granules, so that the insulation effect of the mica is limited, and when the paper is subjected to electric breakdown, the current is blocked less and the current channel is shorter, so that the overall insulation performance of the paper is reduced.
Compared with the composite material 5# in which the ratio of the silane coupling agent to the mica powder exceeds the range defined in the application, the final result is general in electrical performance, the analysis reason is that the coupling efficiency is reduced due to condensation reaction when the using amount of the coupling agent is too large, the grafting rate is low, the modification effect is poor, and the coupling agent grafted on the surface is less when the using amount of the coupling agent is small.
Compared with the composite material No. 6 in which the mica powder is modified only by using the silane coupling agent, the final result is general in electrical performance, and the analysis reason is that the modified mica powder has limited dispersibility and low interface bonding performance with other materials.
Compared with the composite material 7# in which para-aramid fibrid is used, the final result is better in mechanical property, but general in electrical property, the analytical reasons are that the para-molecular structure shows excellent mechanical property, but the electrical property is poorer than that of a meta-structure, and meanwhile, the fibrid has poor short-cut fiber coating property.
The length of the fibers used in the comparative composite material No. 8 exceeds the range defined by the application, the final result is general in electrical performance, the analysis reason is that the fibers are lengthened, the probability of mutual entanglement among the fibers is increased, the fibers are not easy to disperse, the nonuniformity of the hot-pressed composite paper is increased, and the overall strength of the paper is further influenced.
Compared with the composite material 9#, the ratio of the fibrids to the chopped fibers is smaller than the range defined in the application, the final result is general electrical performance, the analysis reason is that the chopped fibers are inserted into the paper structure, so that the paper is easy to form pores, the bonding effect with the chopped fibers is poor due to the small ratio of the fibrids, and the electrical performance and the thermal performance are difficult to exert.
Compared with the composite material 10# in which the hot-press forming temperature is higher than the range defined in the application, the final result is general in electrical performance, and the analysis reason is that the raw material is aged due to overhigh temperature, and the bonding force of aramid fibers and fibrids is reduced. Compared with the common composite material sold in the market, the composite material 11# to 12# has the advantages of common high-temperature resistance and short corona resistance life.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The corona-resistant mica/aramid fiber composite material for the new energy automobile is characterized by comprising the following raw materials in percentage by weight: 40-60% of modified aramid fiber paper, 5-20% of adhesive and 40-60% of modified mica paper;
wherein the weight ratio of the modified aramid fiber paper to the modified mica paper is (1-1.5): 1, the adhesive comprises one or more of tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer, fluorinated ethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, polyether ether ketone and polyetherimide.
2. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 1, wherein the modified mica paper is prepared from the following raw materials: mica powder, hydrochloric acid solution, ethanol, silane coupling agent, methyl methacrylate, initiator and toluene;
the mica powder consists of first mica powder, second mica powder and third mica powder, wherein the particle size of the first mica powder is 90-110 mu m, the particle size of the second mica powder is 130-150 mu m, and the particle size of the third mica powder is 200-230 mu m; the weight ratio of the first mica powder to the second mica powder to the third mica powder is 1: (3-5): (3-5).
3. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 2, wherein the weight ratio of the silane coupling agent to the mica powder is (0.05-0.08): 1, the weight ratio of mica powder to methyl methacrylate to initiator is 1: (0.1-0.15): (0.002-0.005), the weight ratio of the mica powder to ethanol and toluene is 1: (6-8): (5-8).
4. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 3, wherein the preparation method of the modified mica paper comprises the following steps: adding a silane coupling agent into ethanol, adjusting the pH value to 4 by using a hydrochloric acid solution, adding mica powder, heating to 60-80 ℃, stirring for 1-3h, filtering, washing and drying, adding the mixture into toluene, simultaneously adding methyl methacrylate and an initiator, reacting for 2-4h at 70-90 ℃, drying for 0.5-2h at 110-130 ℃ after filtering, adding water, stirring uniformly to form a slurry, and making the modified mica paper by a paper sheet forming machine.
5. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 4, wherein the silane coupling agent is A171, and the initiator is benzoyl peroxide.
6. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 1, wherein the modified aramid fiber paper is prepared from meta-aramid chopped fibers and meta-aramid fibrids, the lengths of the meta-aramid chopped fibers and the meta-aramid fibrids are both 2-3mm, and the weight ratio of the meta-aramid chopped fibers to the meta-aramid fibrids is 1: (2-2.5).
7. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 6, wherein the preparation method of the modified aramid fiber paper comprises the following steps: and defibering and dispersing the meta-aramid chopped fibers and the meta-aramid fibrids, adding water to prepare slurry, performing ultrasonic treatment, and papermaking by a paper sheet forming machine to obtain the modified aramid fiber paper.
8. The corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in claim 7, wherein the ultrasonic treatment step is ultrasonic treatment for 10s each time at an interval of 3s for 6-9min; ultrasonic parameters: the frequency is 10-20kHz and the power is 500W.
9. The preparation method of the corona-resistant mica/aramid fiber composite material for the new energy automobile as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
(1) Unreeling two rolls of modified aramid fiber paper, and respectively coating adhesives on the surfaces of the two rolls of modified aramid fiber paper;
(2) Unreeling the modified mica paper, firstly attaching the modified mica paper to one piece of modified aramid fiber paper coated with the adhesive, then attaching the other piece of modified aramid fiber paper coated with the adhesive to the other side of the modified mica paper, and drying;
(3) And (3) carrying out hot-pressing on the dried composite material by using a hot roller to finally obtain the corona-resistant mica/aramid fiber composite material for the new energy automobile.
10. The method according to claim 9, wherein the drying temperature is 120 ℃, the hot pressing temperature is 265 to 310 ℃, and the hot pressing pressure is 20MPa.
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| PCT/CN2023/123390 WO2024082973A1 (en) | 2022-10-20 | 2023-10-08 | Corona-resistant mica/aramid fiber composite material for new-energy vehicles and preparation method therefor |
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| WO2024120545A1 (en) * | 2023-01-10 | 2024-06-13 | 天蔚蓝电驱动科技(江苏)有限公司 | Corona-resistant composite sheet for electric motor of new energy vehicle, and preparation method therefor |
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