CN110982266A - Graphene/polymer composite heat-conducting film for heat dissipation of new energy automobile battery pack - Google Patents
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Abstract
The invention provides a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack, and relates to the field of composite heat-conducting materials.
Description
Technical Field
The invention relates to the field of composite heat conduction materials, in particular to a graphene/polymer composite heat conduction film for heat dissipation of a new energy automobile battery pack.
Background
The new energy automobile adopts unconventional automobile fuel as a power source (or adopts conventional automobile fuel and a novel vehicle-mounted power device), integrates advanced technologies in the aspects of power control and driving of the automobile, and forms an automobile with advanced technical principle, new technology and new structure. The new energy automobile comprises a pure electric automobile, a range-extended electric automobile, a hybrid electric automobile, a fuel cell electric automobile, a hydrogen engine automobile, other new energy automobiles and the like, the current new energy automobile is mainly driven by a battery, the battery is the core of the new energy automobile, electrolyte in the battery is used for isolating a combustion source, a diaphragm is used for improving heat-resistant temperature, and the full heat dissipation is used for reducing the temperature of the battery, so that the thermal runaway of the battery caused by excessive heat accumulation is avoided. If the temperature of the battery is sharply increased to 300 ℃, even if the diaphragm is not melted and shrunk, the electrolyte and the positive and negative electrodes can generate strong chemical reaction, gas is released, internal high pressure is formed, and explosion is caused, so that the adoption of a proper heat dissipation mode is very important.
General heat dissipation mode is forced air cooling and liquid cooling, the forced air cooling installs radiator fan additional at battery package one end, the ventilation hole is reserved to the other end, make the air flow with higher speed between the gap of electric core, take away the high heat that electric core during operation produced, respectively add the heat conduction membrane in electrode tip top and bottom, let the top, the heat that the bottom is difficult for giving off is conducted the metal casing through the heat conduction membrane and is dispelled the heat, the heat conduction membrane still needs high mechanical strength and puncture-proof performance simultaneously, the liquid cooling is to pass through the heat conduction membrane with the heat of battery electricity core and transmits to the liquid cooling pipe, take away the heat by the free circulation flow of coolant liquid expend with heat and contract with cold, make the temperature of whole battery package unified, the heat that the electric core during operation produced is absorbed to the powerful specific heat capacity of coolant liquid, make whole group battery operate in safe temperature, above-mentioned.
Chinese patent CN108410136A discloses a method for preparing a novel graphene film/carbon fiber heat dissipation plate with high thermal conductivity. The graphene-carbon fiber resin matrix composite material comprises a graphene layer, a carbon fiber woven net layer and a vertically-oriented carbon fiber reinforcing layer. The graphene film is punched in advance by a stamping technology to obtain a reticular graphene film, and then the reticular graphene film is soaked in epoxy to prepare a prepreg. The graphene film and the carbon fiber cloth prepreg are sequentially laid in a laminated mode, then the carbon fiber needling preform is driven into the composite board through an ultrasonic impact gun, or a needling method is used for vertically orienting part of carbon fibers and enhancing the shearing performance of the carbon fibers. According to the invention, the pure graphene powder is compounded with the carbon fiber cloth, so that the composite material has excellent heat-conducting property and good machinability. The composite plate can be used for heat dissipation of large-scale members, has heat dissipation performance comparable to that of pure metal and other heat dissipation materials, and has cuttable performance and good flexibility. The material has the advantages of simple production process, energy conservation, environmental protection, strong applicability and large-scale production.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes, cooling to 0-5 ℃, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 1-2 hours after the addition is finished, adding acetic anhydride and pyridine, raising the temperature to 80-85 ℃, continuously reacting for 6-10 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, centrifuging, leaching the solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, uniformly stirring, slowly adding potassium permanganate under the condition of stirring in an ice water bath, removing the ice water bath after the potassium permanganate is added, heating to 30-35 ℃ for reaction for 30-50min, slowly adding deionized water, continuously stirring for 15-25min, heating to 75-85 ℃, then dropwise adding a hydrogen peroxide solution to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, sequentially washing with dilute hydrochloric acid and deionized water until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 60-80 ℃;
(3) adding the dried solid into deionized water, dispersing for 5-10min by ultrasonic oscillation, heating to 90-95 ℃, dropwise adding hydrazine hydrate, reacting for 20-30h, performing suction filtration, adding the solid into methanol, heating, performing reflux treatment for 30-40min, performing hot filtration, washing with water, and performing vacuum drying at 60-80 ℃ to obtain the graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with a stabilizer and a solvent, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, carrying out hot pressing in a vacuum press, and separating to obtain the graphene/polymer composite heat-conducting film.
Preferably, the mass ratio of the diphenyl ether tetracarboxylic dianhydride to the benzophenone tetracarboxylic dianhydride is 1-5: 1-5.
Preferably, the molar mass ratio of the composite particles to the graphite powder is 1: 1.1-1.15.
Preferably, the mass ratio of the graphite powder to the potassium permanganate is 1: 3-5.
Preferably, the volume of deionized water added in step (2) is 8 to 15 times the volume of concentrated sulfuric acid.
Preferably, the hydrogen peroxide solution has a mass concentration of 30%.
Preferably, the mass concentration of the dilute hydrochloric acid is 10-18%.
Preferably, the stabilizer is polyethylene glycol and the solvent is water or ethanol.
Preferably, the hot pressing temperature is 150 ℃ and 180 ℃, and the pressure is 0.8-1.5 MPa.
(III) advantageous effects
The invention provides a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack, which has the following beneficial effects:
the effective three-dimensional heat conduction network formed by mixing the multi-walled carbon nanotube and the graphene is the key for improving the heat conduction performance of the composite heat conduction membrane material, the graphene and the multi-walled carbon nanotube have similar properties in the aspects of electricity, mechanics and the like, and respectively embody the characteristics of two-dimensional and one-dimensional materials, the graphene has extremely high heat conductivity in two directions in a graphite sheet surface of the graphene, the multi-walled carbon nanotube only has high heat conductivity in the axial direction of the multi-walled carbon nanotube, the multi-walled carbon nanotube is reasonably mixed, the heat diffusion coefficients of the heat conduction membrane in the transverse direction and the longitudinal direction can be balanced, the heat conduction efficiency is improved, the multi-walled carbon nanotube has good orientation in composite particles, the high orientation degree enables heat to be transmitted to one direction, the heat conductivity of the composite heat conduction membrane is far better than that of the traditional heat conduction material, and the graphene is dispersed in gaps of the, the graphene/polymer composite heat-conducting film has the advantages of excellent heat-conducting property, excellent mechanical property, high heat-conducting speed and high efficiency, and is suitable for radiating new energy automobile battery packs.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 2 ℃, and mixing the materials in a mass ratio of 3: 2, adding the mixture of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 2 hours after adding, adding acetic anhydride and pyridine, raising the temperature to 82 ℃ for continuous reaction for 8 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.12, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: 4, after the addition, removing the ice water bath, heating to 32 ℃ for reaction for 40min, slowly adding deionized water, wherein the volume of the added deionized water is 12 times of that of concentrated sulfuric acid, continuously stirring for 18min, heating to 80 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 12% and deionized water in sequence until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 80 ℃;
(3) adding the dried solid into deionized water, performing ultrasonic oscillation dispersion for 8min, heating to 92 ℃, dropwise adding hydrazine hydrate, reacting for 30h, performing suction filtration, adding the solid into methanol, heating and refluxing for 35min, performing heat filtration, washing with water, and performing vacuum drying at 70 ℃ to obtain a graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol serving as a stabilizer and water, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, performing hot pressing in a vacuum press at the temperature of 170 ℃ and the pressure of 1MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 2:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 2 ℃, and mixing the materials in a mass ratio of 4: 1, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 2 hours after adding, adding acetic anhydride and pyridine, raising the temperature to 82 ℃ for continuous reaction for 7 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.1, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: 3, removing the ice water bath after the addition, heating to 32 ℃ for reaction for 30min, slowly adding deionized water, wherein the volume of the added deionized water is 12 times of that of concentrated sulfuric acid, continuously stirring for 25min, heating to 78 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 18% and deionized water in sequence until no sulfate radical is detected in the filtrate, and performing vacuum drying on the obtained solid at 66 ℃;
(3) adding the dried solid into deionized water, dispersing for 5min by ultrasonic oscillation, heating to 95 ℃, dropwise adding hydrazine hydrate, reacting for 25h, performing suction filtration, adding the solid into methanol, heating and refluxing for 30min, performing heat filtration, washing with water, and performing vacuum drying at 65 ℃ to obtain the graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol and ethanol serving as stabilizing agents, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, performing hot pressing in a vacuum press at 165 ℃ and 1.5MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 3:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 4 ℃, and mixing the materials in a mass ratio of 5: 2, adding the mixture of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 2 hours after adding, adding acetic anhydride and pyridine, raising the temperature to 82 ℃ for continuous reaction for 10 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.12, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: 3, removing the ice water bath after adding, heating to 35 ℃ for reaction for 40min, slowly adding deionized water, wherein the volume of the added deionized water is 8 times of that of concentrated sulfuric acid, continuously stirring for 20min, heating to 85 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 12% and deionized water in sequence until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 75 ℃;
(3) adding the dried solid into deionized water, performing ultrasonic oscillation dispersion for 10min, heating to 92 ℃, dropwise adding hydrazine hydrate, reacting for 30h, performing suction filtration, adding the solid into methanol, heating, performing reflux treatment for 35min, performing heat filtration, washing with water, and performing vacuum drying at 75 ℃ to obtain a graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol and ethanol serving as stabilizing agents, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, performing hot pressing in a vacuum press at the temperature of 170 ℃ and the pressure of 1.5MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 4:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 5 ℃, and mixing the materials in a mass ratio of 2: 5, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 2 hours after adding, adding acetic anhydride and pyridine, raising the temperature to 85 ℃, continuously reacting for 10 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.15, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: after the addition, removing the ice water bath, heating to 35 ℃ for reaction for 40min, slowly adding deionized water, wherein the volume of the added deionized water is 8 times of that of concentrated sulfuric acid, continuously stirring for 20min, heating to 85 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 12% and deionized water in sequence until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 80 ℃;
(3) adding the dried solid into deionized water, performing ultrasonic oscillation dispersion for 10min, heating to 92 ℃, dropwise adding hydrazine hydrate, reacting for 25h, performing suction filtration, adding the solid into methanol, heating and refluxing for 40min, performing heat filtration, washing with water, and performing vacuum drying at 70 ℃ to obtain a graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol serving as a stabilizer and water, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, performing hot pressing in a vacuum press at the hot pressing temperature of 150 ℃ and the pressure of 1.5MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 5:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 0 ℃, and mixing the materials in a mass ratio of 1: 1, adding the mixture of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 1h after adding, adding acetic anhydride and pyridine, raising the temperature to 80 ℃ for continuous reaction for 6h, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.1, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: 3, removing the ice water bath after the addition, heating to 30 ℃ for reaction for 30min, slowly adding deionized water, wherein the volume of the added deionized water is 8 times of that of concentrated sulfuric acid, continuously stirring for 15min, heating to 75 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 10% and deionized water in sequence until no sulfate radical is detected in the filtrate, and performing vacuum drying on the obtained solid at 60 ℃;
(3) adding the dried solid into deionized water, ultrasonically vibrating and dispersing for 5min, heating to 90 ℃, dropwise adding hydrazine hydrate, reacting for 20h, performing suction filtration, adding the solid into methanol, heating and refluxing for 30min, performing heat filtration, washing, and performing vacuum drying at 60 ℃ to obtain a graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol serving as a stabilizer and water, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, performing hot pressing in a vacuum press at the hot pressing temperature of 150 ℃ and the pressure of 0.8MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 6:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 5 ℃, and mixing the materials in a mass ratio of 5: 1, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 2 hours after adding, adding acetic anhydride and pyridine, raising the temperature to 85 ℃, continuously reacting for 10 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.15, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: after the addition, removing the ice water bath, heating to 35 ℃ for reaction for 50min, slowly adding deionized water, wherein the volume of the added deionized water is 15 times of that of concentrated sulfuric acid, continuously stirring for 25min, heating to 85 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 18% and deionized water in sequence until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 80 ℃;
(3) adding the dried solid into deionized water, dispersing for 10min by ultrasonic oscillation, heating to 95 ℃, dropwise adding hydrazine hydrate, reacting for 30h, carrying out suction filtration, adding the solid into methanol, heating for reflux treatment for 40min, carrying out heat filtration, washing, and carrying out vacuum drying at 80 ℃ to obtain the graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol and ethanol serving as stabilizing agents, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, carrying out hot pressing in a vacuum press at the hot pressing temperature of 180 ℃ and the pressure of 1.5MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 7:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 0 ℃, and mixing the materials in a mass ratio of 5: 1, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 2 hours after adding, adding acetic anhydride and pyridine, raising the temperature to 80 ℃, continuously reacting for 10 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.1, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: after the addition, removing the ice water bath, heating to 30 ℃ for reaction for 50min, slowly adding deionized water, wherein the volume of the added deionized water is 8 times of that of concentrated sulfuric acid, continuously stirring for 25min, heating to 75 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 10% and deionized water in sequence until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 80 ℃;
(3) adding the dried solid into deionized water, dispersing for 5min by ultrasonic oscillation, heating to 95 ℃, dropwise adding hydrazine hydrate, reacting for 20h, performing suction filtration, adding the solid into methanol, heating and refluxing for 40min, performing heat filtration, washing, and performing vacuum drying at 60 ℃ to obtain the graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol and ethanol serving as stabilizing agents, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, carrying out hot pressing in a vacuum press at the hot pressing temperature of 150 ℃ and the pressure of 1.5MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
Example 8:
a graphene/polymer composite heat-conducting film for heat dissipation of a new energy automobile battery pack is prepared by adding multi-walled carbon nanotubes into modified polyimide to prepare composite particles, uniformly wrapping graphene nanosheets on the surfaces of the composite particles, and finally preparing the graphene/polymer composite heat-conducting film through hot pressing.
The preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the materials, cooling to 5 ℃, and mixing the materials in a mass ratio of 1: 5, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 1h after adding, adding acetic anhydride and pyridine, raising the temperature to 85 ℃, continuously reacting for 6h, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, leaching the centrifuged solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, and uniformly stirring, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.15, slowly adding potassium permanganate under the condition of ice-water bath stirring, wherein the mass ratio of graphite powder to potassium permanganate is 1: 3, removing the ice water bath after the addition, heating to 35 ℃ for reaction for 30min, slowly adding deionized water, wherein the volume of the added deionized water is 15 times of that of concentrated sulfuric acid, continuously stirring for 15min, heating to 85 ℃, then dropwise adding a hydrogen peroxide solution with the mass concentration of 30% to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, washing by using dilute hydrochloric acid with the mass concentration of 10% and deionized water in sequence until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 80 ℃;
(3) adding the dried solid into deionized water, dispersing for 5min by ultrasonic oscillation, heating to 95 ℃, dropwise adding hydrazine hydrate, reacting for 20h, performing suction filtration, adding the solid into methanol, heating and refluxing for 40min, performing heat filtration, washing, and performing vacuum drying at 60 ℃ to obtain the graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with polyethylene glycol and ethanol serving as stabilizing agents, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, carrying out hot pressing in a vacuum press at the hot pressing temperature of 150 ℃ and the pressure of 1.5MPa, and separating to obtain the graphene/polymer composite heat-conducting film.
And (3) performance testing:
the following table 1 shows performance test results of the graphene/polymer composite heat-conducting film prepared in embodiments 1 to 3 of the present invention:
table 1:
as can be seen from table 1 above, the graphene/polymer composite heat-conducting film of the present invention has excellent heat-conducting property, excellent mechanical property, fast heat-conducting speed and high efficiency, and is suitable for heat dissipation of new energy automobile battery packs.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The graphene/polymer composite heat-conducting film for the heat dissipation of the new energy automobile battery pack is characterized in that multi-walled carbon nanotubes are added into modified polyimide to prepare composite particles, graphene nanosheets are uniformly wrapped on the surfaces of the composite particles, and finally the graphene/polymer composite heat-conducting film is prepared through hot pressing.
2. The graphene/polymer composite heat-conducting film for heat dissipation of the new energy automobile battery pack as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) adding diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes into N, N-dimethylacetamide, stirring to fully dissolve the diaminodiphenyl ether, double-end amino organic siloxane and multi-walled carbon nano tubes, cooling to 0-5 ℃, adding a mixture consisting of diphenyl ether tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride in batches, reacting at room temperature for 1-2 hours after the addition is finished, adding acetic anhydride and pyridine, raising the temperature to 80-85 ℃, continuously reacting for 6-10 hours, naturally cooling to room temperature, pouring the mixed solution into deionized water for precipitation, centrifuging, leaching the solid with ethanol, and drying under reduced pressure to obtain composite particles;
(2) slowly adding the composite particles, graphite powder and sodium nitrate into concentrated sulfuric acid, uniformly stirring, slowly adding potassium permanganate under the condition of stirring in an ice water bath, removing the ice water bath after the potassium permanganate is added, heating to 30-35 ℃ for reaction for 30-50min, slowly adding deionized water, continuously stirring for 15-25min, heating to 75-85 ℃, then dropwise adding a hydrogen peroxide solution to reduce redundant potassium permanganate until no obvious bubbles are generated in the system, filtering while hot, sequentially washing with dilute hydrochloric acid and deionized water until no sulfate radical is detected in the filtrate, and vacuum-drying the obtained solid at 60-80 ℃;
(3) adding the dried solid into deionized water, dispersing for 5-10min by ultrasonic oscillation, heating to 90-95 ℃, dropwise adding hydrazine hydrate, reacting for 20-30h, performing suction filtration, adding the solid into methanol, heating, performing reflux treatment for 30-40min, performing hot filtration, washing with water, and performing vacuum drying at 60-80 ℃ to obtain the graphene/polymer composite material;
(4) mixing the graphene/polymer composite material with a stabilizer and a solvent, mechanically stirring to obtain mixed slurry, uniformly forming a film on a copper foil from the mixed slurry, laminating the copper foil and an aluminum plate, carrying out hot pressing in a vacuum press, and separating to obtain the graphene/polymer composite heat-conducting film.
3. The graphene/polymer composite thermal conductive film for heat dissipation of the battery pack of the new energy automobile according to claim 2, wherein the mass ratio of diphenyl ether tetracarboxylic dianhydride to benzophenone tetracarboxylic dianhydride is 1-5: 1-5.
4. The graphene/polymer composite heat-conducting film for heat dissipation of the battery pack of the new energy automobile as claimed in claim 2, wherein the molar mass ratio of the composite particles to the graphite powder is 1: 1.1-1.15.
5. The graphene/polymer composite heat-conducting film for heat dissipation of the new energy automobile battery pack as claimed in claim 2, wherein the mass ratio of the graphite powder to the potassium permanganate is 1: 3-5.
6. The graphene/polymer composite heat-conducting film for dissipating heat of the battery pack of the new energy automobile according to claim 2, wherein the volume of the deionized water added in the step (2) is 8-15 times that of the concentrated sulfuric acid.
7. The graphene/polymer composite heat-conducting film for dissipating heat of the battery pack of the new energy automobile as claimed in claim 2, wherein the mass concentration of the hydrogen peroxide solution is 30%.
8. The graphene/polymer composite heat-conducting film for heat dissipation of the battery pack of the new energy automobile as claimed in claim 2, wherein the mass concentration of the dilute hydrochloric acid is 10-18%.
9. The graphene/polymer composite heat-conducting film for dissipating heat of the battery pack of the new energy automobile as claimed in claim 2, wherein the stabilizer is polyethylene glycol, and the solvent is water or ethanol.
10. The graphene/polymer composite heat-conducting film for heat dissipation of the battery pack of the new energy automobile as claimed in claim 2, wherein the hot-pressing temperature is 150-.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807859A (en) * | 2020-06-08 | 2020-10-23 | 壹田科技(深圳)有限公司 | Composite foamed cement containing multi-walled carbon nanotubes and preparation method thereof |
| CN112455034A (en) * | 2020-11-23 | 2021-03-09 | 深圳市金海洋实业发展有限公司 | Graphene/polymer composite heat-conducting insulating film for heat dissipation of new energy automobile battery pack and preparation method thereof |
| CN113184840A (en) * | 2021-05-17 | 2021-07-30 | 浙江大学 | Thermal interface material with isotropic thermal conductivity and preparation method thereof |
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2019
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807859A (en) * | 2020-06-08 | 2020-10-23 | 壹田科技(深圳)有限公司 | Composite foamed cement containing multi-walled carbon nanotubes and preparation method thereof |
| CN112455034A (en) * | 2020-11-23 | 2021-03-09 | 深圳市金海洋实业发展有限公司 | Graphene/polymer composite heat-conducting insulating film for heat dissipation of new energy automobile battery pack and preparation method thereof |
| CN113184840A (en) * | 2021-05-17 | 2021-07-30 | 浙江大学 | Thermal interface material with isotropic thermal conductivity and preparation method thereof |
| CN113184840B (en) * | 2021-05-17 | 2024-04-16 | 浙江大学 | Thermal interface material with isotropic thermal conductivity and preparation method thereof |
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