CN114773825A - Heat-conducting insulating sheet of new energy automobile battery pack and preparation method - Google Patents
Heat-conducting insulating sheet of new energy automobile battery pack and preparation method Download PDFInfo
- Publication number
- CN114773825A CN114773825A CN202210463078.1A CN202210463078A CN114773825A CN 114773825 A CN114773825 A CN 114773825A CN 202210463078 A CN202210463078 A CN 202210463078A CN 114773825 A CN114773825 A CN 114773825A
- Authority
- CN
- China
- Prior art keywords
- tungsten carbide
- heat
- tungsten
- carbide composite
- composite microspheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack, which comprises the following steps of: (1) preparing reduced bisphenol A type polyaryletherketone; (2) preparing the tungsten diboride/tungsten carbide composite microspheres; (3) preparing carboxylated tungsten diboride/tungsten carbide composite microspheres; (4) preparing modified tungsten diboride/tungsten carbide composite microspheres; (5) preparing modified polyphenyl ester: mixing the polyphenyl ester powder and the modified tungsten diboride/tungsten carbide composite microspheres uniformly to prepare modified polyphenyl ester; (6) preparing a heat-conducting insulating sheet: and carrying out compression molding on the modified polyphenyl ester to prepare the heat-conducting insulating sheet of the new energy automobile battery pack. The heat-conducting insulating sheet prepared by the invention can be suitable for being used on a new energy automobile battery pack, is thinner than a conventional heat-conducting silica gel sheet in thickness, and has excellent hardness, heat conductivity, high temperature resistance and various mechanical properties.
Description
Technical Field
The invention relates to the field of new energy automobiles, in particular to a heat-conducting insulating sheet of a battery pack of a new energy automobile and a preparation method thereof.
Background
The China is in the economic high-speed development stage, the demand on energy is increasing day by day, meanwhile, the reserves of fossil energy such as coal mines, petroleum, natural gas and the like are limited in China, and the energy crisis of China is becoming serious day by day. Therefore, under such environmental driving, the research and development of new energy vehicles is vigorously made as one of the best solutions for improving the urban air quality, reducing the use of fossil fuels, and improving the energy utilization rate. The new energy automobile power battery pack is used as a main energy source of the new energy automobile, and bears more attention.
Due to the high expected value of new energy automobile performance, the power battery system of new energy automobile 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 demand of new energy automobile. The battery is similar to a catalytic chemical reactor, has very sensitive reaction to temperature change, and the heating power and the ambient temperature of the battery have great influence on the electrochemical reaction process in the battery, and also have direct relation to the stability of the battery performance. Once the batteries of the new energy automobile are thermally unbalanced, short-term and long-term negative effects are caused to the automobile battery system, according to the Arrhenius law of battery electrochemistry, the reaction rate of the batteries rises exponentially with the rise of the temperature of the batteries, the battery units with higher temperature age quickly, the overheated battery units shorten the service life of the whole battery pack, and the ignition and even explosion of the power battery pack can be seriously caused. The heat-conducting insulating sheet is designed to avoid the failure of battery parts caused by short circuit, breakdown and the like, and reduce the risk of ignition of the battery parts, thereby ensuring the normal operation of the battery. However, the majority of the existing heat-conducting insulating sheets are heat-conducting silicone sheets, and the heat-conducting silicone sheets have certain application markets in the traditional batteries, however, the sheet requirements are also increasingly thin along with the more fine batteries, and the heat-conducting performance of the heat-conducting silicone sheets is also increasingly unable to meet the requirements, and the heat-conducting silicone sheets are very easily pierced due to the smaller mechanical strength, which not only affects the heat conductivity thereof, but also concerns the safety problem, therefore, 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 invention aims to provide a new energy automobile battery pack heat-conducting insulating sheet with good heat-conducting effect and high sheet strength and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack, which comprises the following steps:
(1) preparation of 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 the ditungsten boride/tungsten carbide composite microspheres:
taking sucrose as a carbon source and ammonium metatungstate as a tungsten source, performing high-temperature reaction to obtain a tungsten carbide blank, then performing wet ball milling with ditungsten boride nano powder, and then sintering at high temperature to obtain ditungsten boride/tungsten carbide composite microspheres;
(3) preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
performing carboxylation modification on the ditungsten boride/tungsten carbide composite microspheres under the action of hydrogen peroxide and potassium permanganate solution to obtain carboxylated ditungsten boride/tungsten carbide composite microspheres;
(4) preparing modified tungsten diboride/tungsten carbide composite microspheres:
performing condensation reaction on the carboxylated ditungsten boride/tungsten carbide composite microspheres and reduced bisphenol A polyaryletherketone under the action of 4-dimethylaminopyridine and dicyclohexylcarbodiimide to obtain modified ditungsten boride/tungsten carbide composite microspheres;
(5) preparing modified polyphenyl ester:
mixing the polyphenyl ester powder and the modified tungsten diboride/tungsten carbide composite microspheres uniformly to prepare modified polyphenyl ester;
(6) preparing a heat-conducting insulating sheet:
and carrying out compression molding on the modified polyphenyl ester to prepare the heat-conducting insulating sheet of the new energy automobile battery pack.
Preferably, in the step (1), after sodium borohydride and dimethyl sulfoxide are uniformly mixed, bisphenol A type polyaryletherketone is added; wherein the mass ratio of the sodium borohydride, the bisphenol A type polyaryletherketone and the dimethyl sulfoxide is 1:8-12: 100-150.
Preferably, in the step (1), the reaction temperature is 130-.
Preferably, 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 reaction temperature of 200-; wherein the mass ratio of the sucrose to the ammonium metatungstate to the deionized water is 1:0.25-0.3: 10-15.
Preferably, in the step (2), the particle size of the ditungsten boride nano powder is 200-500nm, 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 ditungsten boride nano powder, the tungsten carbide blank and the ethanol is 1:2-4: 3-5.
Preferably, in the step (3), the tungsten diboride/tungsten carbide composite microspheres are firstly treated in hydrogen peroxide for 2 to 4 hours, then added into a potassium permanganate solution for treatment, and then filtered, washed and dried; wherein the mass fraction of the hydrogen peroxide is 30-40%, and the concentration of the potassium permanganate solution is 0.2-0.4 mol/L.
Preferably, in the step (4), the carboxylated tungsten diboride/tungsten carbide composite microspheres and the N, N-dimethylformamide are prepared into a first mixed solution; reducing bisphenol A polyaryletherketone, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and N, N-dimethylformamide to prepare a second mixed solution; the first mixed solution and the second mixed solution are mixed and react.
More preferably, in the first mixed solution, the mass ratio of the carboxylated ditungsten boride/tungsten carbide composite microspheres to the N, N-dimethylformamide is 1: 50-70; in the second mixed liquid, the mass ratio of the reduced bisphenol A type polyaryletherketone, the 4-dimethylaminopyridine, the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.12-0.18:0.8-1.2: 30-50; the mass ratio of the first mixed liquid to the second mixed liquid 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 diboride/tungsten carbide composite microspheres are added; wherein the mass ratio of the polyphenyl ester powder, the modified tungsten diboride/tungsten carbide composite microspheres to the absolute ethyl alcohol is 1:0.1-0.3: 20-40.
Preferably, in the step (6), the temperature for compression molding is 360-2The dwell time is 3-5 min.
In a second aspect, the invention provides a heat-conducting insulating sheet for a new energy automobile battery pack, which is prepared by the preparation method.
Preferably, the thickness of the heat-conducting insulating sheet of the new energy automobile battery pack is 0.3-0.6 mm.
The beneficial effects of the invention are as follows:
1. the heat-conducting insulating sheet prepared by the invention can be suitable for being used on a new energy automobile battery pack, is thinner than a conventional heat-conducting silica gel sheet in thickness, and has excellent hardness, heat conductivity, high temperature resistance and various mechanical properties.
2. The invention uses modified tungsten diboride/tungsten carbide composite microspheres to modify the polyphenyl ester to prepare modified polyphenyl ester, and the heat-conducting insulating sheet is obtained by compression molding.
3. The heat-conducting insulating sheet prepared by the invention takes the polyphenyl ester as a base material, and the self-made modified ditungsten boride/tungsten carbide composite microspheres are added to modify the polyphenyl ester, so that the defects of high polyphenyl ester brittleness, insufficient mechanical strength, poor impact toughness and high abrasion loss are overcome, and the obtained material has more excellent performance in performance.
4. The polyaryletherketone has the advantages of high rigidity, high heat resistance, flame retardancy, high strength, high electrical property and the like, but the polyaryletherketone has high molecular inertness, is not sufficient in binding with other materials (such as polyphenyl ester), is not good in conventional modification treatment effect, and cannot exert the advantages of a mixed material. The application uses bisphenol A type polyaryletherketone derivatives as initial materials, the initial materials are subjected to reductive treatment to be activated, then the surfaces of the boronized ditungsten/tungsten carbide composite microspheres are coated with grafts and finally compounded with the polyphenyl ester, and the results prove that the polyphenyl ester-bisphenol A type polyaryletherketone derivatives are good in compatibility with the polyphenyl ester, so that the thermal conductivity of the polyphenyl ester is greatly improved, and the impact toughness, the mechanical strength and the wear resistance of the polyphenyl ester are enhanced, so that the polyphenyl ester-bisphenol A type polyaryletherketone derivatives can be used as a thermal insulation sheet of a battery pack.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is an SEM image of a ditungsten boride/tungsten carbide composite microsphere prepared in example 1 of the invention;
FIG. 2 is an SEM image of modified ditungsten boride/tungsten carbide composite microspheres prepared in example 1 of the invention.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but the present invention should not be construed as being limited to the implementable scope of the present invention.
Polyphenyl ester (POB), namely poly (p-hydroxy phenyl benzoate), is a high-temperature resistant special engineering plastic, and has the advantages of high temperature resistance, good thermal stability, heat capacity, self-lubricating property, hardness, electrical insulation and abrasion resistance. However, the polybenzoate has low molecular surface energy, high brittleness, poor mechanical strength and impact toughness, and high abrasion loss, and is generally used as a filling material, and if the polybenzoate is molded alone, the polybenzoate is very brittle.
In the invention, the preparation process of the modified tungsten diboride/tungsten carbide composite microspheres comprises the following steps: the first step, preparing reduced bisphenol A type polyaryletherketone; the second step is to prepare the tungsten diboride/tungsten carbide composite microspheres, and the third step is to modify the microspheres by using reduced bisphenol A polyaryletherketone.
The first step is that on the basis of bisphenol A polyaryletherketone, dimethyl sulfoxide is used as a solvent, under the protection of rare gas and the action of sodium borohydride, an inactive carbonyl group in the bisphenol A polyaryletherketone is reduced into a hydroxyl group, and thus the reduced bisphenol A polyaryletherketone is obtained, and the specific reaction is as follows:
the second step is to add ditungsten Boride (BW) in the process of preparing tungsten carbide2) Then preparing the composite microspheres of the tungsten diboride/tungsten carbide; 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, wear resistance, good heat conduction and the like, but has the defects of high brittleness and poor toughness; the tungsten boride is hexagonal crystal powder, has the advantages of high melting point, high hardness, high heat conductivity and chemical stability, and most importantly, has higher toughness. Therefore, the invention combines the two, and after synthesizing the precursor (blank) of the tungsten carbide, the tungsten diboride is added to prepare the microsphere structure, so that the obtained microsphere not only has the advantages of the two, but also is not easy to collapse and has more stable structure.
The third step is that the compound microsphere of the tungsten diboride/tungsten carbide is firstly carried out carboxylation treatment, and then the carboxylation treatment is carried out on the compound microsphere of the tungsten diboride/tungsten carbide, and the compound microsphere of the tungsten diboride/tungsten carbide is combined with the reduction bisphenol A type polyaryletherketone to react, so that the reduction bisphenol A type polyaryletherketone is grafted on the surface of the compound microsphere of the tungsten diboride/tungsten carbide, and the modified compound microsphere of the tungsten diboride/tungsten carbide is obtained, and the process is as follows:
the starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The invention is further described with reference to the following examples.
Example 1
A preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack comprises the following steps:
(1) preparation of 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 protective gas, stirring for 0.5h in a dark place, slowly adding bisphenol A type polyaryletherketone, stirring continuously while adding, uniformly mixing, heating to 135 ℃, stirring for reacting for 2h, naturally cooling to room temperature, pouring a reaction solution into prepared n-amyl alcohol, filtering out a solid, washing with acetone for three times, washing with pure water for three times, and then drying in vacuum to obtain reduced bisphenol A type polyaryletherketone; wherein the mass ratio of the sodium borohydride to the bisphenol A polyaryletherketone to the dimethyl sulfoxide is 1:10: 120;
(2) preparing the ditungsten boride/tungsten carbide composite microspheres:
s1, weighing sucrose, dissolving the sucrose in deionized water, slowly adding ammonium metatungstate while stirring, continuously stirring for 0.5h after all the materials are added, pouring the mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an insulation box, heating the insulation box to 210 ℃, naturally cooling to room temperature after insulation treatment for 36h, filtering reaction liquid, collecting filtered solids, washing the solids for three times by using acetone, then washing the solids for three times by using pure water, drying the solids in vacuum, and crushing the solids to obtain a tungsten carbide green body; wherein the mass ratio of the sucrose to the ammonium metatungstate to the deionized water is 1:0.28: 12;
s2, mixing the ditungsten boride nano powder with the particle size of 200-500nm and a tungsten carbide blank in a planetary ball mill, performing wet ball milling treatment by taking ethanol as a medium, wherein the ball-material ratio is 6:1, performing ball milling for 10 hours, and performing vacuum drying to obtain a ditungsten boride/tungsten carbide blank mixed material; wherein the mass ratio of the tungsten diboride nano powder to the tungsten carbide green body to the ethanol is 1:3: 4;
s3, paving the mixed material of the tungsten diboride/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 1.5h, introducing hydrogen to enable the hydrogen to be 1/4 of the gas volume in the graphite furnace, continuing preserving heat for 4h, naturally cooling to room temperature, collecting powder, and obtaining the tungsten diboride/tungsten carbide composite microspheres;
(3) preparing carboxylated tungsten diboride/tungsten carbide composite microspheres:
mixing the ditungsten boride/tungsten carbide composite microspheres into 35% hydrogen peroxide by mass, performing 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 solution in a water bath at 60 ℃ for stirring for 2 hours, naturally cooling the solution to room temperature, filtering the reaction solution, collecting the filtered solids, washing the solids with pure water for at least three times, and then drying the solids to obtain the carboxylated ditungsten boride/tungsten carbide composite microspheres; wherein the mass ratio of the tungsten diboride/tungsten carbide composite microspheres to the hydrogen peroxide to the potassium permanganate solution is 1:8: 12;
(4) preparing modified tungsten diboride/tungsten carbide composite microspheres:
p1, mixing the carboxylated ditungsten 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 diboride/tungsten carbide composite microspheres to the N, N-dimethylformamide is 1: 60;
p2, mixing reduced bisphenol A 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 polyaryletherketone, the 4-dimethylaminopyridine, the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.15:1: 40;
p3, pouring the first mixed liquid into the second mixed liquid, filling rare gas to replace air in the reaction bottle, then placing the reaction bottle in a water bath at 50 ℃ to stir for 72 hours, naturally cooling to room temperature after the reaction is finished, filtering the reaction liquid, collecting the filtered solid, washing at least three times by using N-methyl pyrrolidone, and then drying in vacuum to obtain the modified tungsten diboride/tungsten carbide composite microspheres; wherein the mass ratio of the first mixed liquid to the second mixed liquid 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 the modified tungsten diboride/tungsten carbide composite microspheres, stirring and dispersing for 3 hours at room temperature, then heating to 75 ℃, and continuously stirring until the ethyl alcohol is evaporated to dryness to obtain modified polyphenyl ester; wherein the mass ratio of the polyphenyl ester powder, the modified tungsten diboride/tungsten carbide composite microspheres to the absolute ethyl alcohol is 1:0.2: 30;
(6) preparing a heat-conducting insulating sheet:
carrying out compression molding on the modified polyphenyl ester to prepare a new energy automobile battery pack heat-conducting insulating sheet; wherein the compression molding temperature is 380 deg.C, and the pressure is 600kg/cm2The dwell time was 4 min.
Example 2
A preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack comprises the following steps:
(1) preparation of 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 protective gas, stirring for 0.5h in a dark place, slowly adding bisphenol A polyaryletherketone, continuously stirring while adding, uniformly mixing, heating to 130 ℃, stirring for reaction for 1.5h, naturally cooling to room temperature, pouring reaction liquid into prepared n-amyl alcohol, filtering to obtain solid, washing with acetone for three times, washing with pure water for three times, and drying in vacuum to obtain reduced bisphenol A polyaryletherketone; wherein the mass ratio of the sodium borohydride to the bisphenol A polyaryletherketone to the dimethyl sulfoxide is 1:8: 100;
(2) preparing the ditungsten boride/tungsten carbide composite microspheres:
s1, weighing sucrose, dissolving the sucrose in deionized water, slowly adding ammonium metatungstate while stirring, continuously stirring for 0.5h after all the materials are added, pouring the mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an insulation box, heating the insulation box to 200 ℃, naturally cooling to room temperature after heat preservation treatment is carried out for 24h, filtering reaction liquid, collecting filtered solids, washing the solids for three times by using acetone, then washing the solids for three times by using pure water, carrying out vacuum drying, and crushing to obtain a tungsten carbide green body; wherein the mass ratio of the sucrose to the ammonium metatungstate to the deionized water is 1:0.25: 10;
s2, mixing the ditungsten boride nano powder with the particle size of 200-500nm and a tungsten carbide blank in a planetary ball mill, performing wet ball milling treatment by taking ethanol as a medium, wherein the ball-material ratio is 5:1, performing ball milling for 8 hours, and performing vacuum drying to obtain a ditungsten boride/tungsten carbide blank mixed material; wherein the mass ratio of the ditungsten boride nano powder to the tungsten carbide green body to the ethanol is 1:2: 3;
s3, paving the mixed material of the tungsten diboride/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 ℃, preserving heat for 1h, introducing hydrogen to enable the hydrogen to be 1/4 of the gas volume in the graphite furnace, then continuing preserving heat for 3h, naturally cooling to room temperature, collecting powder, and obtaining the tungsten diboride/tungsten carbide composite microspheres;
(3) preparing carboxylated ditungsten boride/tungsten carbide composite microspheres:
mixing the ditungsten boride/tungsten carbide composite microspheres into 30% hydrogen peroxide by mass, performing ultrasonic treatment at 35 ℃ for 2 hours, filtering out solids, adding the solids into 0.2mol/L potassium permanganate solution, then placing the solution in a water bath at 55 ℃ for stirring for 1 hour, naturally cooling to room temperature, filtering the reaction solution, collecting the filtered solids, washing the solids with pure water for at least three times, and then performing drying treatment to obtain carboxylated ditungsten boride/tungsten carbide composite microspheres; wherein the mass ratio of the tungsten diboride/tungsten carbide composite microspheres to the hydrogen peroxide to the potassium permanganate solution is 1:6: 10;
(4) preparing modified tungsten diboride/tungsten carbide composite microspheres:
p1, mixing the carboxylated tungsten diboride/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 diboride/tungsten carbide composite microspheres to the N, N-dimethylformamide is 1: 50;
p2, mixing reduced bisphenol A 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 polyaryletherketone, the 4-dimethylaminopyridine, the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.12:0.8: 30;
and P3, pouring the first mixed liquid into the second mixed liquid, filling rare gas to replace air in the 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 liquid, collecting filtered solid, washing at least three times by using N-methyl pyrrolidone, and then carrying out vacuum drying to obtain the modified tungsten boride/tungsten carbide composite microspheres; wherein the mass ratio of the first mixed liquid to the second mixed liquid 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 diboride/tungsten carbide composite microspheres, stirring and dispersing for 2 hours at room temperature, then heating to 75 ℃, and continuously stirring until the ethyl alcohol is evaporated to dryness to obtain modified polyphenyl ester; wherein the mass ratio of the polyphenyl ester powder, the modified tungsten diboride/tungsten carbide composite microspheres to the absolute ethyl alcohol is 1:0.1: 20;
(6) preparing a heat-conducting insulating sheet:
carrying out compression molding on the modified polyphenyl ester to prepare a new energy automobile battery pack heat-conducting insulating sheet; wherein the compression molding temperature is 360 deg.C, and the pressure is 500kg/cm2The dwell time was 3 min.
Example 3
A preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack 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 protective gas, stirring the mixture for 1 hour in a dark place, slowly adding bisphenol A type polyaryletherketone, stirring the mixture continuously while adding the mixture, uniformly mixing the mixture, heating the mixture to 140 ℃, stirring the mixture for reaction for 2.5 hours, naturally cooling the mixture to room temperature, pouring the reaction solution into prepared n-amyl alcohol, filtering out solid, washing the solid with acetone for three times, then washing the solid with pure water for three times, and drying the solid in a vacuum way to obtain reduced bisphenol A type polyaryletherketone; wherein the mass ratio of the sodium borohydride to the bisphenol A polyaryletherketone to the dimethyl sulfoxide is 1:12: 150;
(2) preparing the ditungsten boride/tungsten carbide composite microspheres:
s1, weighing sucrose, dissolving the sucrose in deionized water, slowly adding ammonium metatungstate while stirring, continuously stirring for 1h after all the materials are added, pouring the materials into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an insulation can, heating the insulation can to 220 ℃, carrying out insulation treatment for 48h, naturally cooling to room temperature, filtering the reaction solution, collecting filtered solids, washing the solids for three times by using acetone, then washing the solids for three times by using pure water, carrying out vacuum drying, and crushing to obtain a tungsten carbide green body; wherein the mass ratio of the sucrose to the ammonium metatungstate to the deionized water is 1:0.3: 15;
s2, mixing the ditungsten boride nano powder with the particle size of 200-500nm and a tungsten carbide blank in a planetary ball mill, performing wet ball milling treatment by taking ethanol as a medium, wherein the ball-material ratio is 8:1, performing ball milling for 12 hours, and performing vacuum drying to obtain a ditungsten boride/tungsten carbide blank mixed material; wherein the mass ratio of the ditungsten boride nano powder to the tungsten carbide green body to the ethanol is 1:4: 5;
s3, paving the mixed material of the tungsten diboride/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 ensure that the hydrogen is 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 diboride/tungsten carbide composite microspheres;
(3) preparing carboxylated tungsten diboride/tungsten carbide composite microspheres:
mixing the ditungsten boride/tungsten carbide composite microspheres into hydrogen peroxide with the mass fraction of 40%, performing 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 potassium permanganate solution in a water bath at 65 ℃ for stirring for 2 hours, naturally cooling to room temperature, filtering the reaction solution, collecting the filtered solids, washing the solids with pure water for at least three times, and then performing drying treatment to obtain carboxylated ditungsten boride/tungsten carbide composite microspheres; wherein the mass ratio of the tungsten diboride/tungsten carbide composite microspheres to the hydrogen peroxide to the potassium permanganate solution is 1:10: 15;
(4) preparing modified tungsten diboride/tungsten carbide composite microspheres:
p1, mixing the carboxylated tungsten diboride/tungsten carbide composite microspheres and N, N-dimethylformamide into a beaker, and carrying out ultrasonic treatment at room temperature for 1 hour to obtain a first mixed solution; wherein the mass ratio of the carboxylated ditungsten boride/tungsten carbide composite microspheres to the N, N-dimethylformamide is 1: 70;
p2, mixing reduced bisphenol A 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 polyaryletherketone, the 4-dimethylaminopyridine, the dicyclohexylcarbodiimide to the N, N-dimethylformamide is 1:0.18:1.2: 50;
and P3, pouring the first mixed liquid into the second mixed liquid, filling rare gas to replace air in the 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 liquid, collecting the filtered solid, washing at least three times by using N-methyl pyrrolidone, and then drying in vacuum to obtain the modified tungsten boride/tungsten carbide composite microspheres; wherein the mass ratio of the first mixed liquid to the second mixed liquid 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 diboride/tungsten carbide composite microspheres, stirring and dispersing for 5 hours at room temperature, then heating to 80 ℃, and continuously stirring until the ethyl alcohol is evaporated to dryness to obtain modified polyphenyl ester; wherein the mass ratio of the polyphenyl ester powder, the modified tungsten diboride/tungsten carbide composite microspheres to the absolute ethyl alcohol is 1:0.3: 40;
(6) preparing a heat-conducting insulating sheet:
carrying out compression molding on the modified polyphenyl ester to prepare a new energy automobile battery pack heat-conducting insulating sheet; wherein the compression molding temperature is 400 ℃ and the pressure is 800kg/cm2And the pressure maintaining time is 5 min.
Comparative example 1
The preparation method of the heat-conducting insulating sheet for the new energy automobile battery pack is the same as that in the embodiment 1, and is different from the embodiment 1 in that the ditungsten boride/tungsten carbide composite microspheres in the embodiment 1 are replaced by tungsten carbide microspheres, namely, the ditungsten boride is not added in the preparation process of tungsten carbide.
Comparative example 2
The preparation method of the new energy automobile battery pack heat-conducting insulating sheet is the same as that in example 1, except that the modified ditungsten boride/tungsten carbide composite microspheres in example 1 are replaced with ditungsten boride/tungsten carbide composite microspheres, that is, the ditungsten boride/tungsten carbide composite microspheres are not modified.
Comparative example 3
A preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack is the same as that in example 1, and is different in that modified ditungsten boride/tungsten carbide composite microspheres are replaced by reduced bisphenol A type polyaryletherketone, namely the ditungsten boride/tungsten carbide composite microspheres are not added.
The invention carries out electron microscope scanning on the product prepared in example 1, and FIG. 1 is an SEM image of the ditungsten boride/tungsten carbide composite microsphere prepared in example 1 of the invention, so that the surface of the microsphere is smoother; fig. 2 is an SEM image of the modified tungsten diboride/tungsten carbide composite microspheres prepared in example 1 of the present invention, and it can be seen that a coating structure is formed on the surface of the microspheres, which indicates that the microspheres are successfully coated and modified.
In order to more clearly illustrate the invention, the thermal insulation sheets with the thickness of 0.4 +/-0.01 mm prepared in example 1 and comparative examples 1-3 of the invention are subjected to performance detection and comparison, the tensile strength and the elongation at break are detected according to the standard GB/T1040.2-2006, the compressive strength is detected according to the standard GB/T1041-2008, the notched impact strength is detected according to the standard GB/T1843-2008, the friction coefficient and the wear rate are detected according to the standard ASTM G033-2005, the thermal conductivity coefficient is detected according to the standard GB/T22588-2008, the volume resistivity is detected according to the standard GB/T1410-2006, and the heat deformation temperature is detected according to the ASTM D648 standard.
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 |
| Amount of wear (mm)3) | 0.08 | 0.10 | 0.23 | 0.18 |
| Thermal conductivity (W/(m.K)) | 1.85 | 1.53 | 1.62 | 0.71 |
| Volume resistivity (omega. m) | 1.32×1015 | 1.46×1015 | 5.41×1013 | 1.79×1015 |
| Heat distortion temperature (. degree. C.) | 330 | 322 | 251 | 283 |
As can be seen from table 1, the heat-conducting insulating sheet prepared in example 1 of the present invention 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 better due to the lower wear loss; the thermal conductivity can reach 1.85W/(m.K), which shows that the thermal conductivity is high; meanwhile, the volume resistivity can be kept at the same order of magnitude as that of a common insulating sheet, which shows that the insulating performance of the insulating sheet can also meet the requirement; in addition, the heat distortion temperature is as high as 330 ℃, which shows that the heat resistance is better and the material is not easy to deform. In summary, it can be proved that the heat-conducting insulating sheet prepared in embodiment 1 of the present invention can better perform the functions of insulating, heat-conducting and protecting in the automobile battery pack.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is 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 solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a heat-conducting insulating sheet of a new energy automobile battery pack is characterized by comprising the following steps:
(1) preparing reduced bisphenol A type polyaryletherketone:
reacting bisphenol A polyaryletherketone under the action of sodium borohydride to obtain reduced bisphenol A polyaryletherketone;
(2) preparing the ditungsten boride/tungsten carbide composite microspheres:
taking sucrose as a carbon source and ammonium metatungstate as a tungsten source, performing high-temperature reaction to obtain a tungsten carbide blank, performing wet ball milling on the tungsten carbide blank and the tungsten boride nano powder, and performing high-temperature sintering to obtain the tungsten boride/tungsten carbide composite microspheres;
(3) preparing carboxylated tungsten diboride/tungsten carbide composite microspheres:
performing carboxylation modification on the ditungsten boride/tungsten carbide composite microspheres under the action of hydrogen peroxide and potassium permanganate solution to obtain carboxylated ditungsten boride/tungsten carbide composite microspheres;
(4) preparing modified tungsten diboride/tungsten carbide composite microspheres:
performing condensation reaction on the carboxylated ditungsten boride/tungsten carbide composite microspheres and reduced bisphenol A polyaryletherketone under the action of 4-dimethylaminopyridine and dicyclohexylcarbodiimide to obtain modified ditungsten boride/tungsten carbide composite microspheres;
(5) preparing modified polyphenyl ester:
mixing the polyphenyl ester powder and the modified tungsten diboride/tungsten carbide composite microspheres uniformly to prepare modified polyphenyl ester;
(6) preparing a heat-conducting insulating sheet:
and carrying out compression molding on the modified polyphenyl ester to prepare the heat-conducting insulating sheet of the new energy automobile battery pack.
2. The method for preparing the heat-conducting insulating sheet for the new energy automobile battery pack 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 1.5-2.5h, and after the reaction is finished, the heat-conducting insulating sheet is filtered, washed and dried; wherein the mass ratio of the sodium borohydride, the bisphenol A type polyaryletherketone and the dimethyl sulfoxide is 1:8-12: 100-150.
3. The method for preparing the heat-conducting insulating sheet for the new energy automobile battery pack according to claim 1, wherein in the step (2), sucrose is dissolved in deionized water, ammonium metatungstate is slowly added while stirring, the mixture is poured into a reaction kettle for reaction at a temperature of 200 ℃ and 220 ℃ for 24-48h, and the mixture is filtered, washed, dried and crushed after the reaction.
4. The preparation method of the heat-conducting insulating sheet for the new energy automobile battery pack according to claim 1, wherein in the step (2), ethanol is added as a medium in a wet ball milling process, the ball-to-material ratio is 5-8:1, and the mass ratio of the tungsten diboride nanopowder to the tungsten carbide green body to the ethanol is 1:2-4: 3-5.
5. The preparation method of the heat-conducting insulating sheet for the new energy automobile battery pack according to claim 1, wherein in the step (3), the ditungsten boride/tungsten carbide composite microspheres are treated in hydrogen peroxide for 2-4 hours, then are added into potassium permanganate solution for treatment, and then are 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 0.2-0.4 mol/L.
6. The preparation method of the heat-conducting insulating sheet for the new energy automobile battery pack according to claim 1, wherein in the step (4), the modified tungsten diboride/tungsten carbide composite microspheres and N, N-dimethylformamide are prepared into a first mixed solution; reducing bisphenol A type polyaryletherketone, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and N, N-dimethylformamide to prepare a second mixed solution; the first mixed liquid and the second mixed liquid are mixed and react.
7. The preparation method of the heat-conducting insulating sheet for the new energy automobile battery pack according to claim 1, wherein in the step (5), the polyphenyl ester powder is uniformly mixed with the absolute ethyl alcohol, and then the modified tungsten diboride/tungsten carbide composite microspheres are added; wherein the mass ratio of the polyphenyl ester powder, the modified tungsten diboride/tungsten carbide composite microspheres to the absolute ethyl alcohol is 1:0.1-0.3: 20-40.
8. The method as claimed in claim 1, wherein the step (6) comprises molding at a temperature of 360-400 ℃ and a pressure of 500-800kg/cm2The dwell time is 3-5 min.
9. A new energy automobile battery pack heat conduction insulation sheet is characterized by being prepared by the preparation method of the new energy automobile battery pack heat conduction insulation sheet according to any one of claims 1 to 8.
10. The heat-conducting insulating sheet for the new energy automobile battery pack according to claim 9, wherein the thickness of the heat-conducting insulating sheet for the new energy automobile battery pack is 0.3-0.6 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210463078.1A CN114773825B (en) | 2022-04-28 | 2022-04-28 | New energy automobile battery pack heat conduction insulating sheet and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210463078.1A CN114773825B (en) | 2022-04-28 | 2022-04-28 | New energy automobile battery pack heat conduction insulating sheet and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114773825A true CN114773825A (en) | 2022-07-22 |
| CN114773825B CN114773825B (en) | 2023-09-29 |
Family
ID=82434365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210463078.1A Active CN114773825B (en) | 2022-04-28 | 2022-04-28 | New energy automobile battery pack heat conduction insulating sheet and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114773825B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150210554A1 (en) * | 2014-01-29 | 2015-07-30 | Zhejiang University Of Technology | Carbon-separated Ultrafine Nano Tungsten Carbide Material And Preparation Method And Use Thereof |
| CN112940332A (en) * | 2021-04-13 | 2021-06-11 | 吉林大学 | Polyaryletherketone containing amino side chain and preparation method and application thereof |
-
2022
- 2022-04-28 CN CN202210463078.1A patent/CN114773825B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150210554A1 (en) * | 2014-01-29 | 2015-07-30 | Zhejiang University Of Technology | Carbon-separated Ultrafine Nano Tungsten Carbide Material And Preparation Method And Use Thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114773825B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20030129471A1 (en) | Composite material for fuel cell separator molding and production method thereof, and fuel cell separator which uses the composite material and production method thereof | |
| KR20070110531A (en) | Electrically conducting curable resin composition, cured product thereof and molded article of the same | |
| WO2003079472A2 (en) | Electroconductive curable resin composition, cured product thereof and process for producing the same | |
| CN113666368B (en) | Artificial graphite negative electrode material and preparation method thereof | |
| CN110797533A (en) | Lignin hard carbon microsphere, hydrothermal preparation method and application of lignin hard carbon microsphere in alkali metal ion battery cathode | |
| CN108101043B (en) | Preparation method and application of coal-derived artificial graphite material | |
| KR100762883B1 (en) | Curable composition, cured product thereof, molded product thereof and use as fuel cell separator | |
| CN112265990A (en) | Preparation method and application of furfural residue porous activated carbon material | |
| CN116332157A (en) | Preparation method of nitrogen-metal doped carbon material and application of nitrogen-metal doped carbon material in rubber | |
| CN114773825B (en) | New energy automobile battery pack heat conduction insulating sheet and preparation method thereof | |
| CN113322473A (en) | Loaded Ni-CeO2Preparation method and application of heterojunction nitrogen-doped porous carbon nanofiber material | |
| CN113178562A (en) | Fabric-like carbon-coated silicon dioxide composite material and application thereof | |
| CN110407189B (en) | Coal needle coke and preparation method thereof, lithium ion battery cathode material and lithium ion battery | |
| CN112479207A (en) | Method for recycling activated carbon, double-electric-layer capacitor comprising activated carbon recycled by method and preparation method of double-electric-layer capacitor | |
| CN112993294A (en) | Carbon-plastic composite bipolar plate for fuel cell and preparation and application thereof | |
| US20230113236A1 (en) | Crystalline graphite and composites from melt-flowable polylignin | |
| CN116014106A (en) | Preparation method and application of carbon/tungsten disulfide intercalation composite material | |
| CN113067002B (en) | PEM fuel cell, ball-milling intercalation graphite bipolar plate and preparation method thereof | |
| Hui et al. | Characteristics and preparation of polymer/graphite composite bipolar plate for PEM fuel cells | |
| JP5013680B2 (en) | Curable composition, cured product thereof and molded article thereof | |
| CN113346097A (en) | Preparation method of graphite-based composite material bipolar plate for proton exchange membrane fuel cell | |
| JP2005129507A (en) | Graphitic powder for fuel cell separator, and fuel cell separator | |
| CN110600738A (en) | Method for preparing low-temperature lithium ion battery hard carbon negative electrode material | |
| CN111377442A (en) | Method for preparing sulfur-free expanded graphite by using natural fine flakes | |
| CN110002881B (en) | Preparation method of carbon fiber reinforced porous molybdenum disilicide ceramic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |