WO2022198661A1 - Film de graphite thermoconducteur ultramince et son procédé de fabrication - Google Patents

Film de graphite thermoconducteur ultramince et son procédé de fabrication Download PDF

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Publication number
WO2022198661A1
WO2022198661A1 PCT/CN2021/083389 CN2021083389W WO2022198661A1 WO 2022198661 A1 WO2022198661 A1 WO 2022198661A1 CN 2021083389 W CN2021083389 W CN 2021083389W WO 2022198661 A1 WO2022198661 A1 WO 2022198661A1
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WO
WIPO (PCT)
Prior art keywords
film
graphite
temperature
graphitization
graphite film
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Application number
PCT/CN2021/083389
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English (en)
Chinese (zh)
Inventor
周志强
叶从亮
Original Assignee
浙江华熔科技有限公司
Priority date (The priority date 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 date listed.)
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Application filed by 浙江华熔科技有限公司 filed Critical 浙江华熔科技有限公司
Priority to PCT/CN2021/083389 priority Critical patent/WO2022198661A1/fr
Publication of WO2022198661A1 publication Critical patent/WO2022198661A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation

Definitions

  • the invention relates to the field of graphite film production, in particular to an ultra-thin thermally conductive graphite film and a preparation method thereof.
  • Graphite thermal conductive film is a new type of heat dissipation material developed in recent years using the excellent thermal conductivity of graphite.
  • This product is a sheet-like material with extremely high thermal conductivity, which is made by repeatedly heat-treating the polymer film based on carbon material under special sintering conditions.
  • Graphite film has a unique grain orientation, which can conduct heat evenly in two directions, and the lamellar structure can be well adapted to any surface, which can improve the performance of consumer electronic products while shielding heat sources and components.
  • the conventional method for the production of graphite thermal conductive film is to cut the polyimide film first, and then enter the carbonization furnace.
  • the temperature is kept at about 2900 degrees Celsius for half an hour, then the temperature is lowered to room temperature, and then the finished product is obtained after rolling and densification. Due to the thinness of the product, when the thickness of the graphite film is less than 10 microns, the enthalpy of the semi-finished product after carbonization is low.
  • the degree of graphitization of the product can only reach about 30%.
  • the degree of graphitization is basically not changed by heat preservation or heating, so its thermal conductivity is poor and it is basically unusable. At the same time, its general hardness is high and it is not easy to process.
  • the thickness of the mainstream graphite thermal conductive film on the market can only be above 17 microns, and the thickness of 10 microns or less is rarely used.
  • a preparation method of an artificial graphite film and a graphite film material comprises: subjecting the polyimide film to be calcined to a first staged temperature rise according to a preset size , the polyimide film is reacted, and then cooled to obtain a semi-finished film; the semi-finished film is heated in stages under the protection of inert gas for the second time, so that the semi-finished film is reacted, and then cooled to obtain a graphite film.
  • the invention uses polyimide film as raw material, through designing two subsection heating processes, using the first subsection heating process to form an appropriate dynamic temperature field to obtain a structure with high crystallinity, and then in the first subsection heating process On the basis of the second stage heating process, the two stage heating processes cooperate with each other to form a graphite film with high orientation, high crystallinity and high conductivity, but the graphite film with high thermal conductivity prepared by this method The thickness and thermal conductivity of the film need to be further improved.
  • the present invention provides an ultra-thin thermally conductive graphite film and a preparation method thereof in order to overcome the defects of the conventional thermally conductive graphite film, which generally have large thickness, high hardness and difficult processing and poor thermal conductivity.
  • An ultra-thin thermally conductive graphite film is between 1 and 10 ⁇ m, and the thermal conductivity is greater than 2800 W/(m ⁇ K).
  • the graphitization degree of the graphite film is 100%.
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • the polyimide film is cut into pieces, and water-based graphite emulsion is sprayed on its surface, and after drying, a polyimide film with graphite micropowder attached to the surface is obtained.
  • step (1) The polyimide film obtained in step (1) is placed in a carbonization furnace for carbonization treatment to obtain a carbonized film.
  • the carbonized film is placed in a graphitization furnace for multiple segmented graphitization, and then rolled to obtain an ultra-thin thermally conductive graphite film after being lowered to room temperature.
  • the thickness of the aqueous graphite milk in the step (S.1) is 0.5-5 ⁇ m.
  • the solid content of the aqueous graphite milk in the step (S.1) is 10-30%.
  • the drying temperature in the step (S.1) is 55-70°C.
  • the carbonization treatment step in the step (S.2) is as follows: in a vacuum state, through a heating program of 8 to 12 hours, until the temperature in the furnace is 1200 ° C, then stop heating and cool down to room temperature to obtain a carbonized film.
  • the multi-stage graphitization procedure in the step (S.3) is as follows.
  • the present invention has the following advantageous effects.
  • the graphite film in the present invention has an ultra-thin thickness and a great thermal conductivity, which can effectively adapt to the increasingly thin demand and trend of consumer electronic products, and also has good softness, which is beneficial to the follow-up. processing operations.
  • the water-based graphite emulsion is sprayed on the surface of the polyimide film, so that the graphite fine powder in it can enter the pores generated during the decomposition of the polyimide, so that the obtained carbonized film has a compact and complete structure. Therefore, in the graphitization process, the carbon atoms of the turbostratic structure can be guided to transform into the graphite crystal structure in an orderly manner, so that the structure of the obtained graphite crystallites is more complete.
  • the thermally conductive graphite film of the present invention undergoes multiple segmented graphitization during the preparation process, and can perform multiple carbon arrangements on the part that can be graphitized in the future during the graphitization process, thereby effectively improving the graphitization degree of the graphite film. , so that the final product can reach 100% graphitization.
  • the degree of graphitization of the graphite film in the present invention can reach 100%, so the size of the graphite crystallites in the microstructure is larger, and the crystallite structure is more complete, so that the average speed of the internal phonon motion, sound
  • the mean free path of the particles reaches the maximum, so that the thermal conductivity of the graphite film in the present invention can be effectively improved compared with the ordinary graphite film in the prior art.
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • step (2) Put the polyimide film obtained in step (1) in a carbonization furnace, and in a vacuum state, after a uniform temperature rise of 10h, the temperature in the furnace is raised to about 1200°C, and then the heating is stopped and the temperature is lowered. At room temperature, a carbonized film was obtained.
  • the thermal conductivity of the ultra-thin thermally conductive graphite film prepared in this example reaches 2905 W/(m•K).
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • step (2) The polyimide film obtained in step (1) is placed in a carbonization furnace, and in a vacuum state, the temperature in the furnace is raised to about 1200°C after a constant temperature rise of 8 hours, and then the heating is stopped and the temperature is lowered. At room temperature, a carbonized film was obtained.
  • the thermal conductivity of the ultra-thin thermally conductive graphite film prepared in this example reaches 2852 W/(m•K).
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • step (2) Put the polyimide film obtained in step (1) in a carbonization furnace, and in a vacuum state, after a constant temperature rise of 12 hours, the temperature in the furnace is raised to about 1200 ° C, and then the heating is stopped and the temperature is lowered. At room temperature, a carbonized film was obtained.
  • the thermal conductivity of the ultra-thin thermally conductive graphite film prepared in this example reaches 2825W/(m•K).
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • step (2) Put the polyimide film obtained in step (1) in a carbonization furnace, and in a vacuum state, after a uniform temperature rise of 10h, the temperature in the furnace is raised to about 1200°C, and then the heating is stopped and the temperature is lowered. At room temperature, a carbonized film was obtained.
  • the thermal conductivity of the ultra-thin thermally conductive graphite film prepared in this example reaches 2905 W/(m•K).
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • step (2) The polyimide film obtained in step (1) is placed in a carbonization furnace, and in a vacuum state, after a constant temperature rise for 9 hours, the temperature in the furnace is raised to about 1200 °C, and then the heating is stopped and the temperature is increased. The temperature was lowered to normal temperature to obtain a carbonized film.
  • the thermal conductivity of the ultra-thin thermally conductive graphite film prepared in this example reaches 2853W/(m•K).
  • a preparation method of an ultra-thin thermally conductive graphite film comprising the following steps.
  • step (2) Put the polyimide film obtained in step (1) in a carbonization furnace, and in a vacuum state, after a uniform temperature rise of 10h, the temperature in the furnace is raised to about 1200°C, and then the heating is stopped and the temperature is lowered. At room temperature, a carbonized film was obtained.
  • the thermal conductivity of the ultra-thin thermally conductive graphite film prepared in this example reaches 2856 W/(m•K).
  • the graphite film in the present invention has an ultra-thin thickness and a great thermal conductivity, which can effectively adapt to the increasingly thin demand and trend of consumer electronic products, and also has good softness, which is beneficial to the follow-up. processing operations.
  • the water-based graphite emulsion is sprayed on the surface of the polyimide film, so that the graphite micropowder in it can enter the pores generated during the decomposition of the polyimide, so that the obtained carbonized film has a compact and complete structure. Therefore, in the graphitization process, the carbon atoms of the turbostratic structure can be guided to transform into the graphite crystal structure in an orderly manner, so that the structure of the obtained graphite crystallites is more complete.
  • the thermally conductive graphite film of the present invention undergoes multiple segmented graphitization during the preparation process, and can perform multiple carbon arrangements on the part that can be graphitized in the future during the graphitization process, thereby effectively improving the graphitization degree of the graphite film. , so that the final product can reach 100% graphitization.
  • the degree of graphitization of the graphite film in the present invention can reach 100%, so the size of the graphite crystallites in the microstructure is larger, and the crystallite structure is more complete, so that the average speed of the internal phonon motion, sound
  • the mean free path of the particles reaches the maximum, so that the thermal conductivity of the graphite film in the present invention can be effectively improved compared with the ordinary graphite film in the prior art.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention se rapporte au domaine de la fabrication de film de graphite et concerne spécifiquement un film de graphite thermoconducteur ultramince. L'épaisseur du film de graphite est comprise entre 1 et 10 µm, son coefficient de conductivité thermique est supérieur à 2800 W/ (m·K), et son procédé de fabrication comprend les étapes suivantes consistant à : trancher un film de polyimide en feuilles, pulvériser sur la surface de celui-ci une émulsion de graphite à base d'eau, sécher pour produire un film de polyimide ayant une micro-poudre de graphite fixée à la surface, puis, placer le film dans un four de carbonisation pour un traitement de carbonisation afin de produire un film carbonisé, enfin, placer le film carbonisé dans un four de graphitisation pour de multiples instances de graphitisation segmentée, et refroidir à température ambiante, puis calandrer pour produire un film de graphite thermoconducteur ultrafin. La présente invention surmonte l'inconvénient de l'état de la technique dans lequel un film de graphite thermoconducteur présente généralement une grande épaisseur, une difficulté de traitement de fabrication de dureté élevée, et un faible coefficient de conductivité thermique; le film de graphite fabriqué présente une épaisseur ultra-mince, une excellente souplesse, et un coefficient de conductivité thermique maximal, et s'adapte efficacement à la demande et à la tendance des produits électroniques de consommation d'être plus minces et plus fins.
PCT/CN2021/083389 2021-03-26 2021-03-26 Film de graphite thermoconducteur ultramince et son procédé de fabrication WO2022198661A1 (fr)

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PCT/CN2021/083389 WO2022198661A1 (fr) 2021-03-26 2021-03-26 Film de graphite thermoconducteur ultramince et son procédé de fabrication

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103663444A (zh) * 2013-12-17 2014-03-26 张家港康得新光电材料有限公司 一种散热用石墨烯复合膜及其制备方法
CN104293308A (zh) * 2014-09-09 2015-01-21 湖南南方搏云新材料有限责任公司 一种高导热石墨膜及其制备工艺
CN104445174A (zh) * 2014-12-12 2015-03-25 碳元科技股份有限公司 一种超薄高导热石墨膜及其制备方法
CN104812204A (zh) * 2014-01-26 2015-07-29 斯迪克新型材料（江苏）有限公司 用于石墨散热片的制造工艺
CN107090275A (zh) * 2017-05-27 2017-08-25 杭州高烯科技有限公司 一种高导热的石墨烯/聚酰亚胺复合碳膜及其制备方法
US20180061517A1 (en) * 2016-08-30 2018-03-01 Nanotek Instruments, Inc. Highly Conductive Graphitic Films and Production Process
CN109575885A (zh) * 2018-11-28 2019-04-05 宁波墨西新材料有限公司 石墨烯导热膜及其制备方法
CN110092374A (zh) * 2019-05-28 2019-08-06 宇冠芯龙(武汉)科技有限公司 一种人工石墨膜的制备方法以及石墨膜材料

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103663444A (zh) * 2013-12-17 2014-03-26 张家港康得新光电材料有限公司 一种散热用石墨烯复合膜及其制备方法
CN104812204A (zh) * 2014-01-26 2015-07-29 斯迪克新型材料（江苏）有限公司 用于石墨散热片的制造工艺
CN104293308A (zh) * 2014-09-09 2015-01-21 湖南南方搏云新材料有限责任公司 一种高导热石墨膜及其制备工艺
CN104445174A (zh) * 2014-12-12 2015-03-25 碳元科技股份有限公司 一种超薄高导热石墨膜及其制备方法
US20180061517A1 (en) * 2016-08-30 2018-03-01 Nanotek Instruments, Inc. Highly Conductive Graphitic Films and Production Process
CN107090275A (zh) * 2017-05-27 2017-08-25 杭州高烯科技有限公司 一种高导热的石墨烯/聚酰亚胺复合碳膜及其制备方法
CN109575885A (zh) * 2018-11-28 2019-04-05 宁波墨西新材料有限公司 石墨烯导热膜及其制备方法
CN110092374A (zh) * 2019-05-28 2019-08-06 宇冠芯龙(武汉)科技有限公司 一种人工石墨膜的制备方法以及石墨膜材料

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