CN114773825B - New energy automobile battery pack heat conduction insulating sheet and preparation method thereof - Google Patents
New energy automobile battery pack heat conduction insulating sheet and preparation method thereof Download PDFInfo
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Abstract
The application discloses a preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack, which comprises the following steps: (1) preparing reduced bisphenol A type polyaryletherketone; (2) preparing tungsten boride/tungsten carbide composite microspheres; (3) Preparing carboxylated ditungsten boride/tungsten carbide composite microspheres; (4) preparing modified tungsten boride/tungsten carbide composite microspheres; (5) preparation of modified polyphenyl esters: uniformly mixing the polyphenyl ester powder with modified tungsten boride/tungsten carbide composite microspheres to prepare modified polyphenyl ester; (6) preparing a heat conduction insulating sheet: and (3) carrying out compression molding on the modified polyphenyl ester to prepare the new energy automobile battery pack heat-conducting insulating sheet. The application prepares the heat-conducting insulating sheet which can be suitable for the battery pack of the new energy automobile, the thickness of the heat-conducting insulating sheet is thinner than that of the conventional heat-conducting silicon sheet, and the heat-conducting insulating sheet has excellent hardness, heat conductivity, high temperature resistance and various mechanical properties.
Description
Technical Field
The application relates to the field of new energy automobiles, in particular to a new energy automobile battery pack heat-conducting insulating sheet and a preparation method thereof.
Background
The China is in the economic high-speed development period, the demand for energy is increasing, meanwhile, the reserves of fossil energy such as coal mine, petroleum, natural gas and the like in China are limited, and the national energy crisis is becoming serious. Therefore, under such environmental driving, the development of new energy automobiles is greatly becoming one of the best solutions for improving urban air quality, reducing fossil fuel use, and improving energy utilization. The power battery pack of the new energy automobile is used as the main energy source of the new energy automobile, and then more attention is paid.
Because of the high expected performance of new energy automobiles, power battery systems of new energy automobiles must be equipped with hundreds to thousands of power batteries with high specific energy, such as lithium ion batteries or nickel hydrogen batteries, to meet the power requirements of new energy automobiles. The battery is similar to a catalytic chemical reactor, has very sensitive reaction to temperature change, has great influence on the electrochemical reaction process in the battery due to the heating power and the ambient temperature of the battery, and is directly related to the stability of the battery performance. Once the new energy automobile battery is thermally unbalanced, short-term and long-term negative effects are caused on the automobile battery system, according to Arrhenius law of battery electrochemistry, the reaction rate of the battery increases exponentially with the temperature of the battery, the battery units with higher temperature age quickly, the service life of the whole battery pack is shortened by the overheated battery units, and the power battery pack is seriously ignited or even exploded. The heat conducting insulating sheet is designed to avoid the failure of the battery parts caused by short circuit, breakdown and the like, reduce the risk of ignition of the battery parts and ensure the normal operation of the battery. However, most of the existing heat-conducting insulating sheets are heat-conducting silica gel sheets, and although the heat-conducting silica gel sheets have a certain application market in the traditional battery, as the battery is finer, the sheet requirement is thinner and thinner, the heat-conducting property of the heat-conducting silica gel sheets cannot meet the requirement, and the heat-conducting silica gel sheets are easy to puncture due to smaller mechanical strength, so that the heat conductivity of the heat-conducting silica gel sheets can be influenced, and the problem of safety is also concerned, so that a novel heat-conducting insulating sheet with good heat-conducting effect and high sheet strength is needed.
Disclosure of Invention
Aiming at the problems in the prior art, the application aims to provide a new energy automobile battery pack heat-conducting and insulating sheet with good heat-conducting effect and high sheet strength and a preparation method thereof.
The aim of the application is realized by adopting the following technical scheme:
in a first aspect, the application provides a method for preparing a heat-conducting and insulating sheet of a battery pack of a new energy automobile, which comprises the following steps:
(1) Preparing reduced bisphenol A type polyaryletherketone:
reacting bisphenol A type polyaryletherketone under the action of sodium borohydride to obtain reduced bisphenol A type polyaryletherketone;
(2) Preparing tungsten boride/tungsten carbide composite microspheres:
sucrose is used as a carbon source, ammonium metatungstate is used as a tungsten source, a tungsten carbide blank is obtained through high-temperature reaction, then the tungsten carbide blank is ball-milled with ditungsten boride nano powder in a wet method, and then ditungsten boride/tungsten carbide composite microspheres are obtained through high-temperature sintering;
(3) Preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
carboxylating and modifying the tungsten boride/tungsten carbide composite microsphere under the action of hydrogen peroxide and potassium permanganate solution to obtain carboxylated tungsten boride/tungsten carbide composite microsphere;
(4) Preparing modified tungsten boride/tungsten carbide composite microspheres:
carrying out condensation reaction on the carboxylated ditungsten boride/tungsten carbide composite microsphere and reduced bisphenol A type polyaryletherketone under the action of 4-dimethylaminopyridine and dicyclohexylcarbodiimide to obtain modified ditungsten boride/tungsten carbide composite microsphere;
(5) Preparing modified polyphenyl ester:
uniformly mixing the polyphenyl ester powder with modified tungsten boride/tungsten carbide composite microspheres to prepare modified polyphenyl ester;
(6) Preparing a heat conduction insulating sheet:
and (3) carrying out compression molding on the modified polyphenyl ester to prepare the new energy automobile battery pack heat-conducting insulating sheet.
Preferably, in the step (1), after uniformly mixing sodium borohydride and dimethyl sulfoxide, adding bisphenol A type polyaryletherketone; wherein the mass ratio of the sodium borohydride to the bisphenol A type polyaryletherketone to the dimethyl sulfoxide is 1:8-12:100-150.
Preferably, in the step (1), the reaction temperature is 130-140 ℃, the reaction time is 1.5-2.5h, and the reaction is finished and then the filtration, washing and drying treatment are carried out.
Preferably, in the step (2), sucrose is dissolved in deionized water, ammonium metatungstate is slowly added while stirring, and then the mixture is poured into a reaction kettle for reaction at the temperature of 200-220 ℃ for 24-48 hours, and after the reaction is finished, the mixture is subjected to filtration, washing, drying and crushing treatment; wherein the mass ratio of the sucrose to the ammonium meta-tungstate to the deionized water is 1:0.25-0.3:10-15.
Preferably, in the step (2), the particle size of the tungsten boride nano powder is 200-500nm, ethanol is added as a medium in the wet ball milling process, the ball material ratio is 5-8:1, and the mass ratio of the tungsten boride nano powder, the tungsten carbide blank and the ethanol is 1:2-4:3-5.
Preferably, in the step (3), the ditungsten boride/tungsten carbide composite microsphere is firstly treated in hydrogen peroxide for 2-4 hours, then is added into potassium permanganate solution for treatment, and is then subjected to filtration, washing and drying treatment; wherein the mass fraction of the hydrogen peroxide is 30% -40%, and the concentration of the potassium permanganate solution is 0.2-0.4mol/L.
Preferably, in the step (4), the carboxylated tungsten boride/tungsten carbide composite microsphere and the N, N-dimethylformamide are prepared into a first mixed solution; preparing a second mixed solution from reduced bisphenol A type polyaryletherketone, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and N, N-dimethylformamide; the first mixed solution and the second mixed solution are mixed and reacted.
More preferably, in the first mixed solution, the mass ratio of the tungsten carboxylated boride/tungsten carbide composite microspheres to the N, N-dimethylformamide is 1:50-70; in the second mixed solution, the mass ratio of the reduced bisphenol A type polyaryletherketone, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and N, N-dimethylformamide is 1:0.12-0.18:0.8-1.2:30-50; the mass ratio of the first mixed solution to the second mixed solution is 1:3-5.
Preferably, in the step (5), the polyphenyl ester powder and the absolute ethyl alcohol are uniformly mixed, and then the modified tungsten boride/tungsten carbide composite microsphere is added; wherein the mass ratio of the polyphenyl ester powder to the modified tungsten boride/tungsten carbide composite microsphere to the absolute ethyl alcohol is 1:0.1-0.3:20-40.
Preferably, in the step (6), the temperature of the compression molding is 360-400 ℃ and the pressure is 500-800kg/cm 2 The dwell time is 3-5min.
In a second aspect, the application provides a new energy automobile battery pack heat-conducting insulating sheet, which is prepared by the preparation method.
Preferably, the thickness of the heat-conducting insulating sheet of the new energy automobile battery pack is 0.3-0.6mm.
The beneficial effects of the application are as follows:
1. the application prepares the heat-conducting insulating sheet which can be suitable for the battery pack of the new energy automobile, the thickness of the heat-conducting insulating sheet is thinner than that of the conventional heat-conducting silicon sheet, and the heat-conducting insulating sheet has excellent hardness, heat conductivity, high temperature resistance and various mechanical properties.
2. According to the application, the modified polyphenyl ester is prepared by modifying the polyphenyl ester by using modified tungsten boride/tungsten carbide composite microspheres, and the heat-conducting insulating sheet is obtained by compression molding.
3. The heat-conducting insulating sheet prepared by the application takes the polyphenyl ester as a base material, and the self-made modified tungsten boride/tungsten carbide composite microsphere is added to modify the polyphenyl ester, so that the defects of high brittleness, insufficient mechanical strength, poor impact toughness and high abrasion loss of the polyphenyl ester are overcome, and the obtained material has more excellent performance.
4. The polyaryletherketone has the advantages of high rigidity, high heat resistance, flame resistance, high strength, excellent electrical performance and the like, but has high molecular inertia, insufficient bonding property with other materials (such as polyphenyl ester), poor conventional modification treatment effect and incapability of playing the advantages of the mixed materials. The application uses the derivative bisphenol A type polyaryletherketone of the polyaryletherketone as an initial material, firstly carries out reductive treatment on the polyaryletherketone to activate the polyaryletherketone, then grafts and coats the surface of the tungsten boride/tungsten carbide composite microsphere, and finally carries out compositing with the polyphenyl ester, and the result proves that the polyaryletherketone has better compatibility with the polyphenyl ester, thus not only greatly improving the heat conductivity of the polyphenyl ester, but also enhancing the impact toughness, the mechanical strength and the wear resistance of the polyphenyl ester, so that the polyaryletherketone can be suitable for being used as a heat-conducting insulating sheet of a battery pack.
Drawings
The application will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the application, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is an SEM image of a tungsten boride/tungsten carbide composite microsphere prepared according to example 1 of the present application;
FIG. 2 is an SEM image of modified tungsten boride/tungsten carbide composite microsphere prepared according to example 1 of the present application.
Detailed Description
The technical features, objects and advantages of the present application will be more clearly understood from the following detailed description of the technical aspects of the present application, but should not be construed as limiting the scope of the application.
The polyphenyl ester (POB), namely the poly (p-hydroxybenzoic acid) is high-temperature-resistant special engineering plastic, has the advantage of high temperature resistance, and also has better heat stability, heat capacity, self-lubricating property, hardness, electrical insulation property and wear resistance. However, the polystyrene has low molecular surface energy, high brittleness, poor mechanical strength and impact toughness, and high abrasion loss, and is generally used as a filler, and if the filler is molded alone, the filler is brittle.
In the application, the preparation process of the modified tungsten boride/tungsten carbide composite microsphere comprises the following steps: firstly, preparing reduced bisphenol A type polyaryletherketone; the second step is to prepare the tungsten boride/tungsten carbide composite microsphere, and the third step is to modify the tungsten boride/tungsten carbide composite microsphere by using reduced bisphenol A type polyaryletherketone.
The first step is to reduce an inactive carbonyl group in bisphenol A type polyaryletherketone into a hydroxyl group by taking dimethyl sulfoxide as a solvent under the protection of rare gas under the action of sodium borohydride on the basis of bisphenol A type polyaryletherketone, so as to obtain reduced bisphenol A type polyaryletherketone, wherein the specific reaction is as follows:
the second step is to add ditungsten Boride (BW) in the process of preparing tungsten carbide 2 ) Then preparing the tungsten boride/tungsten carbide composite microsphere; tungsten carbide is a gap compound formed by filling carbon atoms into tungsten crystal lattices, has the advantages of high strength, high hardness, high temperature resistance, corrosion resistance, abrasion resistance, good heat conduction and the like, but has the defects of high brittleness and poor toughness; the ditungsten boride is hexagonal crystal powder, has the advantages of high melting point, high hardness, high heat conduction and chemical stability, and most importantly, has higher toughness. Therefore, the application combines the two, adds the ditungsten boride after synthesizing the precursor (blank) of the tungsten carbide to prepare the microsphere structure, so that the obtained microsphere has the advantages of the twoThe point is not easy to collapse, and the structure is more stable.
The third step is that firstly, carboxylating the ditungsten boride/tungsten carbide composite microsphere, then, combining the modified ditungsten boride/tungsten carbide composite microsphere with reduced bisphenol A type polyaryletherketone to react, and grafting the reduced bisphenol A type polyaryletherketone on the surface of the ditungsten boride/tungsten carbide composite microsphere, thus obtaining the modified ditungsten boride/tungsten carbide composite microsphere, and the process is as follows:
the starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The application will be further described with reference to the following examples.
Example 1
A preparation method of a new energy automobile battery pack heat-conducting and insulating sheet comprises the following steps:
(1) Preparing reduced bisphenol A type polyaryletherketone:
weighing sodium borohydride and dimethyl sulfoxide, mixing the sodium borohydride and the dimethyl sulfoxide in a reaction bottle, introducing rare gas as shielding gas, stirring for 0.5h in a dark place, slowly adding bisphenol A type polyaryletherketone, stirring continuously while adding, heating to 135 ℃, stirring for reacting for 2h, naturally cooling to room temperature, pouring the reaction solution into prepared n-amyl alcohol, filtering out solid, washing with acetone for three times, washing with pure water for three times, and vacuum drying to obtain reduced bisphenol A type polyaryletherketone; wherein, the mass ratio of the sodium borohydride to the bisphenol A type polyaryletherketone to the dimethyl sulfoxide is 1:10:120;
(2) Preparing tungsten boride/tungsten carbide composite microspheres:
s1, dissolving sucrose in deionized water, slowly adding ammonium metatungstate while stirring, continuously stirring for 0.5h after all adding, pouring into a polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, placing into an insulation box, heating the insulation box to 210 ℃, performing heat preservation treatment for 36h, naturally cooling to room temperature, filtering the reaction liquid, collecting filtered solid, washing with acetone for three times, washing with pure water for three times, vacuum drying, and crushing to obtain a tungsten carbide blank; wherein the mass ratio of sucrose to ammonium metatungstate to deionized water is 1:0.28:12;
s2, mixing the tungsten boride nano powder with the particle size of 200-500nm with a tungsten carbide blank in a planetary ball mill, performing wet ball milling treatment by taking ethanol as a medium, performing ball milling for 10 hours at a ball-to-material ratio of 6:1, and performing vacuum drying to obtain a tungsten boride/tungsten carbide blank mixed material; wherein, the mass ratio of the tungsten boride nano powder, the tungsten carbide blank and the ethanol is 1:3:4;
s3, spreading the mixed material of the tungsten boride/tungsten carbide blank in a quartz crucible, placing the quartz crucible in a graphite furnace, taking rare gas as protective gas, heating the graphite furnace to 900 ℃, preserving heat for 1.5 hours, introducing hydrogen to enable the hydrogen to be 1/4 of the gas volume in the graphite furnace, then continuing to preserve heat for 4 hours, naturally cooling to room temperature, and collecting powder to obtain the tungsten boride/tungsten carbide composite microspheres;
(3) Preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
mixing the tungsten boride/tungsten carbide composite microspheres into 35% hydrogen peroxide by mass fraction, carrying out ultrasonic treatment at 40 ℃ for 3 hours, filtering out solids, adding the solids into a potassium permanganate solution with the concentration of 0.3mol/L, then placing the mixture into a water bath with the temperature of 60 ℃ for stirring for 2 hours, naturally cooling to room temperature, filtering the reaction solution, collecting the filtered solids, washing the filtered solids with pure water for at least three times, and then drying to obtain the tungsten boride/tungsten carbide composite microspheres; wherein, the mass ratio of the tungsten boride/tungsten carbide composite microsphere to the hydrogen peroxide solution to the potassium permanganate solution is 1:8:12;
(4) Preparing modified tungsten boride/tungsten carbide composite microspheres:
p1, mixing carboxylated tungsten boride/tungsten carbide composite microspheres and N, N-dimethylformamide into a beaker, and performing ultrasonic treatment at room temperature for 0.5h to obtain a first mixed solution; wherein, the mass ratio of the tungsten boride carboxylation/tungsten carbide composite microsphere to the N, N-dimethylformamide is 1:60;
p2 mixing the reduced bisphenol A type polyaryletherketone, 4-Dimethylaminopyridine (DMAP), dicyclohexylcarbodiimide (DCC) and N, N-dimethylformamide into a reaction bottle to obtain a second mixed solution; wherein the mass ratio of the reduced bisphenol A type polyaryletherketone to the 4-dimethylaminopyridine to the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.15:1:40;
p3, pouring the first mixed solution into the second mixed solution, filling rare gas to replace air in a reaction bottle, then placing the reaction bottle in a water bath at 50 ℃ for stirring for 72 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction solution, collecting filtered solid, washing for at least three times by using N-methylpyrrolidone, and then drying in vacuum to obtain the modified tungsten boride/tungsten carbide composite microsphere; wherein the mass ratio of the first mixed solution to the second mixed solution is 1:4.
(5) Preparing modified polyphenyl ester:
weighing polyphenyl ester powder, adding the polyphenyl ester powder into absolute ethyl alcohol, fully stirring and mixing, adding modified tungsten boride/tungsten carbide composite microspheres, stirring and dispersing for 3 hours at room temperature, heating to 75 ℃, continuously stirring until the ethanol is evaporated to dryness, and obtaining modified polyphenyl ester; wherein the mass ratio of the polyphenyl ester powder to the modified tungsten boride/tungsten carbide composite microsphere to the absolute ethyl alcohol is 1:0.2:30;
(6) Preparing a heat conduction insulating sheet:
the modified polyphenyl ester is subjected to compression molding to prepare a new energy automobile battery pack heat-conducting insulating sheet; wherein the temperature of compression molding is 380 ℃ and the pressure is 600kg/cm 2 The dwell time was 4min.
Example 2
A preparation method of a new energy automobile battery pack heat-conducting and insulating sheet comprises the following steps:
(1) Preparing reduced bisphenol A type polyaryletherketone:
weighing sodium borohydride and dimethyl sulfoxide, mixing the sodium borohydride and the dimethyl sulfoxide in a reaction bottle, introducing rare gas as shielding gas, stirring for 0.5h in a dark place, slowly adding bisphenol A type polyaryletherketone, stirring continuously while adding, heating to 130 ℃, stirring for reacting for 1.5h, naturally cooling to room temperature, pouring the reaction solution into prepared n-amyl alcohol, filtering out solid, washing with acetone for three times, washing with pure water for three times, and vacuum drying to obtain reduced bisphenol A type polyaryletherketone; wherein, the mass ratio of the sodium borohydride to the bisphenol A type polyaryletherketone to the dimethyl sulfoxide is 1:8:100;
(2) Preparing tungsten boride/tungsten carbide composite microspheres:
s1, dissolving sucrose in deionized water, slowly adding ammonium metatungstate while stirring, continuously stirring for 0.5h after all adding, pouring into a polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, placing into an insulation box, heating the insulation box to 200 ℃, performing heat preservation treatment for 24h, naturally cooling to room temperature, filtering the reaction liquid, collecting filtered solid, washing with acetone for three times, washing with pure water for three times, vacuum drying, and crushing to obtain a tungsten carbide blank; wherein the mass ratio of sucrose to ammonium metatungstate to deionized water is 1:0.25:10;
s2, mixing the tungsten boride nano powder with the particle size of 200-500nm with a tungsten carbide blank in a planetary ball mill, performing wet ball milling treatment by taking ethanol as a medium, performing ball milling for 8 hours at a ball-to-material ratio of 5:1, and performing vacuum drying to obtain a tungsten boride/tungsten carbide blank mixed material; wherein, the mass ratio of the tungsten boride nano powder, the tungsten carbide blank and the ethanol is 1:2:3;
s3, spreading the mixed material of the tungsten boride/tungsten carbide blank in a quartz crucible, placing the quartz crucible in a graphite furnace, taking rare gas as protective gas, heating the graphite furnace to 800 ℃, keeping the temperature for 1h, introducing hydrogen to enable the hydrogen to be 1/4 of the gas volume in the graphite furnace, then continuing to keep the temperature for 3h, naturally cooling to room temperature, and collecting powder to obtain the tungsten boride/tungsten carbide composite microsphere;
(3) Preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
mixing the tungsten boride/tungsten carbide composite microspheres into 30% hydrogen peroxide by mass fraction, carrying out ultrasonic treatment at 35 ℃ for 2 hours, filtering out solids, adding the solids into a potassium permanganate solution with the concentration of 0.2mol/L, then placing the mixture into a water bath with the concentration of 55 ℃ for stirring for 1 hour, naturally cooling to room temperature, filtering the reaction solution, collecting the filtered solids, washing the filtered solids with pure water for at least three times, and then drying to obtain the tungsten boride/tungsten carbide composite microspheres; wherein, the mass ratio of the tungsten boride/tungsten carbide composite microsphere to the hydrogen peroxide solution to the potassium permanganate solution is 1:6:10;
(4) Preparing modified tungsten boride/tungsten carbide composite microspheres:
p1, mixing carboxylated tungsten boride/tungsten carbide composite microspheres and N, N-dimethylformamide into a beaker, and performing ultrasonic treatment at room temperature for 0.5h to obtain a first mixed solution; wherein, the mass ratio of the carboxylated tungsten boride/tungsten carbide composite microsphere to the N, N-dimethylformamide is 1:50;
p2 mixing the reduced bisphenol A type polyaryletherketone, 4-Dimethylaminopyridine (DMAP), dicyclohexylcarbodiimide (DCC) and N, N-dimethylformamide into a reaction bottle to obtain a second mixed solution; wherein the mass ratio of the reduced bisphenol A type polyaryletherketone to the 4-dimethylaminopyridine to the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.12:0.8:30;
p3, pouring the first mixed solution into the second mixed solution, filling rare gas to replace air in a reaction bottle, then placing the reaction bottle in a water bath at 45 ℃ for stirring for 48 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction solution, collecting filtered solid, washing for at least three times by using N-methylpyrrolidone, and then drying in vacuum to obtain the modified tungsten boride/tungsten carbide composite microsphere; wherein the mass ratio of the first mixed solution to the second mixed solution is 1:3.
(5) Preparing modified polyphenyl ester:
weighing polyphenyl ester powder, adding the polyphenyl ester powder into absolute ethyl alcohol, fully stirring and mixing, adding modified tungsten boride/tungsten carbide composite microspheres, stirring and dispersing for 2 hours at room temperature, heating to 75 ℃, continuously stirring until the ethanol is evaporated to dryness, and obtaining modified polyphenyl ester; wherein the mass ratio of the polyphenyl ester powder to the modified tungsten boride/tungsten carbide composite microsphere to the absolute ethyl alcohol is 1:0.1:20;
(6) Preparing a heat conduction insulating sheet:
the modified polyphenyl ester is subjected to compression molding to prepare a new energy automobile battery pack heat-conducting insulating sheet; wherein the temperature of compression molding is 360 ℃ and the pressure is 500kg/cm 2 The dwell time was 3min.
Example 3
A preparation method of a new energy automobile battery pack heat-conducting and insulating sheet comprises the following steps:
(1) Preparing reduced bisphenol A type polyaryletherketone:
weighing sodium borohydride and dimethyl sulfoxide, mixing the sodium borohydride and the dimethyl sulfoxide in a reaction bottle, introducing rare gas as shielding gas, stirring for 1h in a dark place, slowly adding bisphenol A type polyaryletherketone, stirring continuously while adding, heating to 140 ℃ after uniform mixing, stirring for 2.5h, naturally cooling to room temperature, pouring the reaction solution into prepared n-amyl alcohol, filtering out solid, washing with acetone for three times, washing with pure water for three times, and vacuum drying to obtain reduced bisphenol A type polyaryletherketone; wherein, the mass ratio of sodium borohydride, bisphenol A type polyaryletherketone and dimethyl sulfoxide is 1:12:150;
(2) Preparing tungsten boride/tungsten carbide composite microspheres:
s1, dissolving sucrose in deionized water, slowly adding ammonium metatungstate while stirring, continuously stirring for 1h after all adding, pouring into a polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, placing into an insulation box, heating the insulation box to 220 ℃, performing heat preservation treatment for 48h, naturally cooling to room temperature, filtering the reaction liquid, collecting filtered solid, washing with acetone for three times, washing with pure water for three times, vacuum drying, and crushing to obtain a tungsten carbide blank; wherein the mass ratio of sucrose to ammonium metatungstate to deionized water is 1:0.3:15;
s2, mixing the tungsten boride nano powder with the particle size of 200-500nm with a tungsten carbide blank in a planetary ball mill, performing wet ball milling treatment by taking ethanol as a medium, performing ball milling for 12 hours at a ball-to-material ratio of 8:1, and performing vacuum drying to obtain a tungsten boride/tungsten carbide blank mixed material; wherein, the mass ratio of the tungsten boride nano powder, the tungsten carbide blank and the ethanol is 1:4:5;
s3, spreading the mixed material of the tungsten boride/tungsten carbide blank in a quartz crucible, placing the quartz crucible in a graphite furnace, taking rare gas as protective gas, heating the graphite furnace to 1000 ℃, keeping the temperature for 2 hours, introducing hydrogen to enable the hydrogen to be 1/3 of the gas volume in the graphite furnace, then continuing to keep the temperature for 5 hours, naturally cooling to room temperature, and collecting powder to obtain the tungsten boride/tungsten carbide composite microsphere;
(3) Preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
mixing the tungsten boride/tungsten carbide composite microspheres into 40% hydrogen peroxide by mass fraction, carrying out ultrasonic treatment at 45 ℃ for 4 hours, filtering out solids, adding the solids into a potassium permanganate solution with the concentration of 0.4mol/L, then placing the mixture into a water bath with the concentration of 65 ℃ for stirring for 2 hours, naturally cooling to room temperature, filtering the reaction solution, collecting the filtered solids, washing the filtered solids with pure water for at least three times, and then drying to obtain the tungsten boride/tungsten carbide composite microspheres; wherein, the mass ratio of the tungsten boride/tungsten carbide composite microsphere to the hydrogen peroxide solution to the potassium permanganate solution is 1:10:15;
(4) Preparing modified tungsten boride/tungsten carbide composite microspheres:
p1, mixing carboxylated tungsten boride/tungsten carbide composite microspheres and N, N-dimethylformamide into a beaker, and performing ultrasonic treatment at room temperature for 1h to obtain a first mixed solution; wherein, the mass ratio of the tungsten boride carboxylation/tungsten carbide composite microsphere to the N, N-dimethylformamide is 1:70;
p2 mixing the reduced bisphenol A type polyaryletherketone, 4-Dimethylaminopyridine (DMAP), dicyclohexylcarbodiimide (DCC) and N, N-dimethylformamide into a reaction bottle to obtain a second mixed solution; wherein the mass ratio of the reduced bisphenol A type polyaryletherketone to the 4-dimethylaminopyridine to the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.18:1.2:50;
p3, pouring the first mixed solution into the second mixed solution, filling rare gas to replace air in a reaction bottle, then placing the reaction bottle in a water bath at 55 ℃ for stirring for 96 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction solution, collecting filtered solid, washing for at least three times by using N-methylpyrrolidone, and then drying in vacuum to obtain the modified tungsten boride/tungsten carbide composite microsphere; wherein the mass ratio of the first mixed solution to the second mixed solution is 1:5.
(5) Preparing modified polyphenyl ester:
weighing polyphenyl ester powder, adding the polyphenyl ester powder into absolute ethyl alcohol, fully stirring and mixing, adding modified tungsten boride/tungsten carbide composite microspheres, stirring and dispersing for 5 hours at room temperature, heating to 80 ℃, continuously stirring until the ethanol is evaporated to dryness, and obtaining modified polyphenyl ester; wherein the mass ratio of the polyphenyl ester powder to the modified tungsten boride/tungsten carbide composite microsphere to the absolute ethyl alcohol is 1:0.3:40;
(6) Preparing a heat conduction insulating sheet:
the modified polyphenyl ester is subjected to compression molding to prepare a new energy automobile battery pack heat-conducting insulating sheet; wherein the temperature of compression molding is 400 ℃ and the pressure is 800kg/cm 2 The dwell time was 5min.
Comparative example 1
The preparation method of the heat-conducting and insulating sheet for the battery pack of the new energy automobile is the same as that of the embodiment 1, except that the ditungsten boride/tungsten carbide composite microsphere in the embodiment 1 is replaced by a tungsten carbide microsphere, namely, the ditungsten boride is not added in the preparation process of the tungsten carbide.
Comparative example 2
The preparation method of the heat-conducting insulating sheet for the battery pack of the new energy automobile is the same as that of the embodiment 1, except that the modified ditungsten boride/tungsten carbide composite microsphere in the embodiment 1 is replaced by the ditungsten boride/tungsten carbide composite microsphere, namely, the modification treatment is not carried out on the ditungsten boride/tungsten carbide composite microsphere.
Comparative example 3
A preparation method of a heat-conducting insulating sheet for a new energy automobile battery pack is the same as that of the embodiment 1, except that modified ditungsten boride/tungsten carbide composite microspheres are replaced by reduced bisphenol A type polyaryletherketone, namely, ditungsten boride/tungsten carbide composite microspheres are not added.
In the application, electron microscope scanning is carried out on the product prepared in the embodiment 1, and fig. 1 is an SEM image of a tungsten boride/tungsten carbide composite microsphere prepared in the embodiment 1, thus the microsphere has a smoother surface; fig. 2 is an SEM image of the modified ditungsten boride/tungsten carbide composite microsphere prepared in example 1 of the present application, and it can be seen that a coating structure is formed on the surface of the microsphere, which indicates that the microsphere is successfully coated and modified.
In order to more clearly illustrate the application, the heat-conducting insulating sheets with the thickness of 0.4+/-0.01 mm prepared in the embodiment 1 and the comparative examples 1-3 are tested and compared in performance, the tensile strength and the elongation at break are tested according to the standard GB/T1040.2-2006, the compressive strength is tested according to the standard GB/T1041-2008, the notch impact strength is tested according to the standard GB/T1843-2008, the friction coefficient and the wear rate are tested according to the standard ASTM G033-2005, the heat conductivity is tested according to the standard GB/T22588-2008, the volume resistivity is tested according to the standard GB/T1410-2006, and the heat deformation temperature is tested according to the standard ASTM D648.
The results are shown in table 1 below:
TABLE 1 comparison of the Performance of different thermally conductive insulating sheets
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Tensile Strength (MPa) | 23.2 | 21.7 | 16.2 | 17.3 |
| Elongation at break (%) | 62 | 65 | 51 | 57 |
| Compressive Strength (MPa) | 42.5 | 40.7 | 36.1 | 32.5 |
| Notched impact Strength (kJ/m) 2 ) | 27.3 | 25.1 | 18.1 | 19.6 |
| Coefficient of friction | 0.26 | 0.27 | 0.29 | 0.17 |
| Wear amount (mm) 3 ) | 0.08 | 0.10 | 0.23 | 0.18 |
| Coefficient of thermal conductivity (W/(m.K)) | 1.85 | 1.53 | 1.62 | 0.71 |
| Volume resistivity (Ω. M) | 1.32×10 15 | 1.46×10 15 | 5.41×10 13 | 1.79×10 15 |
| Heat distortion temperature (DEG C) | 330 | 322 | 251 | 283 |
As can be seen from table 1, the heat conductive insulating sheet prepared in example 1 of the present application has higher tensile strength, elongation at break and compressive strength, which indicates that the mechanical properties are better; the product has higher notch impact strength, which indicates that the toughness is better; although the friction coefficient is slightly high, the wear resistance is relatively low, which means that the wear resistance is relatively good; the heat conductivity coefficient can reach 1.85W/(m.K), which shows that the heat conductivity is high; meanwhile, the volume resistivity can be kept in the same order of magnitude as that of a common insulating sheet, which indicates that the insulating performance can also meet the requirements; in addition, the heat distortion temperature is as high as 330 ℃, which shows that the heat resistance is better and the deformation is less easy. In summary, it can be proved that the heat conducting and insulating sheet prepared in the embodiment 1 of the application can better play roles in insulating, heat conducting and protecting in an automobile battery pack.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present application without departing from the spirit and scope of the technical solution of the present application.
Claims (10)
1. The preparation method of the heat-conducting and insulating sheet of the new energy automobile battery pack is characterized by comprising the following steps of:
(1) Preparing reduced bisphenol A type polyaryletherketone:
reacting bisphenol A type polyaryletherketone under the action of sodium borohydride to obtain reduced bisphenol A type polyaryletherketone;
(2) Preparing tungsten boride/tungsten carbide composite microspheres:
sucrose is used as a carbon source, ammonium metatungstate is used as a tungsten source, a tungsten carbide blank is obtained through high-temperature reaction, then the tungsten carbide blank is ball-milled with ditungsten boride nano powder in a wet method, and then ditungsten boride/tungsten carbide composite microspheres are obtained through high-temperature sintering;
(3) Preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
carboxylating and modifying the tungsten boride/tungsten carbide composite microsphere under the action of hydrogen peroxide and potassium permanganate solution to obtain carboxylated tungsten boride/tungsten carbide composite microsphere;
(4) Preparing modified tungsten boride/tungsten carbide composite microspheres:
carrying out condensation reaction on the carboxylated ditungsten boride/tungsten carbide composite microsphere and reduced bisphenol A type polyaryletherketone under the action of 4-dimethylaminopyridine and dicyclohexylcarbodiimide to obtain modified ditungsten boride/tungsten carbide composite microsphere;
(5) Preparing modified polyphenyl ester:
uniformly mixing the polyphenyl ester powder with modified tungsten boride/tungsten carbide composite microspheres to prepare modified polyphenyl ester;
(6) Preparing a heat conduction insulating sheet:
and (3) carrying out compression molding on the modified polyphenyl ester to prepare the new energy automobile battery pack heat-conducting insulating sheet.
2. The preparation method of the heat-conducting and insulating sheet for the battery pack of the new energy automobile according to claim 1, wherein in the step (1), after sodium borohydride and dimethyl sulfoxide are uniformly mixed, bisphenol A type polyaryletherketone is added, the reaction temperature is 130-140 ℃, the reaction time is 1.5-2.5 hours, and after the reaction is finished, the filtration, the washing and the drying treatment are carried out; wherein the mass ratio of the sodium borohydride to the bisphenol A type polyaryletherketone to the dimethyl sulfoxide is 1:8-12:100-150.
3. The method for preparing the heat-conducting and insulating sheet for the battery pack of the new energy automobile according to claim 1, wherein in the step (2), sucrose is firstly dissolved in deionized water, then ammonium metatungstate is slowly added while stirring, then the mixture is poured into a reaction kettle for reaction at the temperature of 200-220 ℃ for 24-48 hours, and after the reaction is finished, the mixture is subjected to filtering, washing, drying and crushing treatment.
4. The preparation method of the heat-conducting insulating sheet for the battery pack of the new energy automobile, which is disclosed in claim 1, is characterized in that in the step (2), ethanol is added as a medium in the wet ball milling process, the ball-to-material ratio is 5-8:1, and the mass ratio of the tungsten boride nano powder, the tungsten carbide blank and the ethanol is 1:2-4:3-5.
5. The preparation method of the heat-conducting and insulating sheet for the battery pack of the new energy automobile according to claim 1, wherein in the step (3), the ditungsten boride/tungsten carbide composite microsphere is firstly treated in hydrogen peroxide for 2-4 hours, then is added into a potassium permanganate solution for treatment, and then is subjected to filtration, washing and drying treatment; wherein the mass fraction of the hydrogen peroxide is 30% -40%, and the concentration of the potassium permanganate solution is 0.2-0.4mol/L.
6. The method for preparing the heat-conducting and insulating sheet for the battery pack of the new energy automobile according to claim 1, wherein in the step (4), modified tungsten boride/tungsten carbide composite microspheres and N, N-dimethylformamide are prepared into a first mixed solution; preparing a second mixed solution from reduced bisphenol A type polyaryletherketone, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and N, N-dimethylformamide; the first mixed solution and the second mixed solution are mixed and reacted.
7. The method for preparing the heat-conducting and insulating sheet for the battery pack of the new energy automobile according to claim 1, wherein in the step (5), after the polyphenyl ester powder and the absolute ethyl alcohol are uniformly mixed, modified ditungsten boride/tungsten carbide composite microspheres are added; wherein the mass ratio of the polyphenyl ester powder to the modified tungsten boride/tungsten carbide composite microsphere to the absolute ethyl alcohol is 1:0.1-0.3:20-40.
8. According to claim 1The preparation method of the new energy automobile battery pack heat-conducting and insulating sheet is characterized in that in the step (6), the temperature of compression molding is 360-400 ℃ and the pressure is 500-800kg/cm 2 The dwell time is 3-5min.
9. A new energy automobile battery pack heat-conducting and insulating sheet, which is characterized by being prepared by the preparation method of the new energy automobile battery pack heat-conducting and insulating sheet according to any one of claims 1-8.
10. The heat conducting and insulating sheet for a battery pack of a new energy automobile according to claim 9, wherein the thickness of the heat conducting and insulating sheet for a battery pack of a new energy automobile is 0.3-0.6mm.
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| CN103805078A (en) * | 2014-02-25 | 2014-05-21 | 黑龙江省科学院石油化学研究院 | High-toughness adhesive film using modified cyanate ester structure for long time at 250 DEG C and preparation method for same |
| CN112940332A (en) * | 2021-04-13 | 2021-06-11 | 吉林大学 | Polyaryletherketone containing amino side chain and preparation method and application thereof |
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| KR20130040440A (en) * | 2011-10-14 | 2013-04-24 | 한양대학교 에리카산학협력단 | Electrically insulative and thermally conductive ceramic/polymer composit powder and method for preparatin the same |
| CN103805078A (en) * | 2014-02-25 | 2014-05-21 | 黑龙江省科学院石油化学研究院 | High-toughness adhesive film using modified cyanate ester structure for long time at 250 DEG C and preparation method for same |
| CN112940332A (en) * | 2021-04-13 | 2021-06-11 | 吉林大学 | Polyaryletherketone containing amino side chain and preparation method and application thereof |
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