CN102897753A - Preparation method for graphite with high thermal conductivity - Google Patents
Preparation method for graphite with high thermal conductivity Download PDFInfo
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- CN102897753A CN102897753A CN2012103353896A CN201210335389A CN102897753A CN 102897753 A CN102897753 A CN 102897753A CN 2012103353896 A CN2012103353896 A CN 2012103353896A CN 201210335389 A CN201210335389 A CN 201210335389A CN 102897753 A CN102897753 A CN 102897753A
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Abstract
The invention discloses a preparation method for graphite with high thermal conductivity. The preparation method is characterized by comprising the following steps: weighing natural crystalline flake graphite with a size of no less than 400 meshes and mixing the crystalline flake graphite with an intercalator to obtain intercalated graphite; subjecting the intercalated graphite to expansion at a temperature of 200 to 1100 DEG C to obtain expanded graphite, wherein an expansion ratio is set to be 1.5 to 2.0 times; soaking the expanded graphite with a liquid carbon source, taking the expanded graphite out, heating the expanded graphite to a temperature of 500 to 1000 DEG C in a manner of hot pressing with pressure controlled to be 5 to 100 MPa and taking the heated graphite out from a kettle after cooling so as to obtain intermediate graphite; and placing the intermediate graphite in a graphitization furnace, heating the intermediate graphite to a temperature of 2000 to 3000 DEG C in inert gas flow and taking the heated intermediate graphite out after cooling so as to obtain finished graphite. According to the invention, the prepared graphite has high thermal conductivity (350 to 650 W/mK); and after slight expansion, the crystalline flake graphite has a small particle size and a firm structure, so the phenomenon of slag falling of graphite with high thermal conductivity can be well overcome.
Description
Technical field
The present invention relates to a kind of graphite its preparation method with high heat conduction characteristics.
Background technology
Development along with electronic technology and Aeronautics and Astronautics technology, the miniaturization of electronics trend, Highgrade integration, for guaranteeing the steady-state operation of high power density electronic equipment and miniature/small-sized integrated functionality system, the heat that its operational process is produced is strengthened to derive and will inevitably be proposed higher requirement.Therefore the various countries researchist has carried out large quantity research for thermally conductive material.Graphite material is studied widely as a kind of material with high thermal conductivity, lightweight, is a kind of material that has very large potentiality in this field.But at present, general complex process in the preparation process of high-heat conductivity graphite material, and its material structure and the difficult control of performance, thereby need the further new preparation path of research and development.
Existing solution has with natural flake graphite and prepares high conductive graphite as starting material, because natural flake graphite itself has high thermal conductivity.But because the particle of the material that crystalline flake graphite prepares behind sintering under the effect of binding agent is larger, the phenomenon that slag in further use procedure, can occur coming off, falling, so can cause its heat conductivility to descend and even inefficacy, so this defective use that natural flake graphite prepares high conductive graphite technique has limited its widespread use.With regard to this class technique, overcome the slag-off phenomenon of goods in the time of the high heat conduction that how to keep natural flake graphite, thereby widen the range of application of high conductive graphite, be to be problem demanding prompt solution.
Summary of the invention
Utilize technique that natural flake graphite prepares high conductive graphite in conjunction with insecure, the easy defective of falling slag, inefficacy for above-mentioned, the present invention proposes a kind of preparation method of high conductive graphite, and its technical scheme is as follows:
A kind of preparation method of high conductive graphite may further comprise the steps:
Intercalation: get particle and be not less than 400 purpose natural flake graphites, sneak into intercalator, obtain intercalated graphite;
Expand: this intercalated graphite is placed under the 200-1100 ° of C carry out expansion process, setting its expansion multiple is 1.5-20 times, obtains expanded graphite;
Prefabricated: take out after this expanded graphite soaked into liquid carbon source, be heated to 500-1000 ° of C in the mode with hot pressing, then pressure-controlling goes out still after the cooling in 5-100MPa, graphite in the middle of obtaining; And
Moulding: should place a graphitizing furnace by middle graphite, and be heated to 2000-3000 ° of C under inert gas flow, at last cooling is come out of the stove and is namely obtained finished product graphite.
As the preferred person of the technical program, can have improvement aspect following:
In the preferred embodiment, in this intercalation step, this intercalator comprises: the mixture of iron(ic) chloride, cobalt chloride, nickelous chloride, the vitriol oil-concentrated nitric acid, organic intercalation agent and two or more mixture thereof.
In the preferred embodiment, in this prefabricated step, this liquid carbon source comprises: coal tar, coal-tar pitch, petroleum residual oil, CONPA resin, mesophase pitch and two or more mixture thereof.
In the preferred embodiment, this rare gas element is argon gas.
In the preferred embodiment, in this prefabricated step, take the mode of naturally cooling to go out still after the hot pressing heating is complete.
In the preferred embodiment, in this forming step, heat and take the mode of naturally cooling to come out of the stove after complete.
In the preferred embodiment, in this prefabricated step, its heat-processed has atmosphere of inert gases.
In the preferred embodiment, in this forming step, the uniform rate that adds thermal recovery 1-50 ° C/min of this centre graphite is heated up.
The beneficial effect of the technical program is:
1. the processing of intercalation and expansion step, regulate the expansion multiple of natural flake graphite, regulate the arrangement behavior of graphite microcrystal, and under hot pressing function, binding agent and expanded graphite wafer are arranged regular, further have higher thermal conductivity (350-650W/mK) after the greying in forming step.
2. crystalline flake graphite is through microdilatancy, and its particle diameter is less, sound construction, thereby can overcome preferably the slag-off phenomenon of high conductive graphite.
3. from above-mentioned institute employed material in steps, the advantage such as it is extensive that the present invention has raw material sources, cheap, with short production cycle.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing embodiment:
Fig. 1 is the schema of the embodiment of the invention 1 to embodiment 6.
Embodiment
Embodiment 1
Intercalation 10: get particle diameter and be not less than 400 purpose natural flake graphite 200g, sneak into the vitriol oil-concentrated nitric acid mixture as intercalator, intercalation processing;
Expand 20: afterwards 200-1100 ℃ of lower expansion process, obtain expansion multiple and be 1.5 times microdilatancy graphite.
Prefabricated 30: expanded graphite is immersed liquid charcoal source mesophase pitch.Be placed in the hot pressing furnace after soaking into taking-up, under inert atmosphere, with the heat-up rate of 0.1～100 ℃/min, pressure is 5-100MPa, initial goods is heated to 600 ℃～2000 ℃ obtains prefabricated graphite.
Moulding 40: place a graphitizing furnace under argon gas stream in prefabricated graphite, with the heat-up rate of 1～50 ℃/min, intermediate is heated to 2000 ℃～3000 ℃.Come out of the stove behind the naturally cooling and namely obtain high-heat conductivity graphite material.The density of the graphite material that obtains is at 2.20g/cm3, and thermal conductivity is 650W/mK.
Embodiment 2
Intercalation 10: get particle diameter and be not less than 400 purpose natural flake graphite 200g, sneak into the vitriol oil-concentrated nitric acid mixture as intercalator, intercalation processing;
Expand 20: afterwards 200-1100 ℃ of lower expansion process, obtain expansion multiple and be 3 times expanded graphite.
Prefabricated 30: expanded graphite immersed to take out behind the liquid charcoal source obtain initial goods.Place hot pressing furnace under inert atmosphere in initial goods, with the heat-up rate of 0.1～100 ℃/min, pressure is 5-100MPa, initial goods is heated to 600 ℃～2000 ℃ obtains the prefabricated graphite of intermediate.
Moulding 40: place a graphitizing furnace under argon gas stream in the prefabricated graphite of intermediate, with the heat-up rate of 1～50 ℃/min, intermediate is heated to 2000 ℃～3000 ℃.Come out of the stove behind the naturally cooling and namely obtain high-heat conductivity graphite material.The density of the graphite material that obtains is at 2.12g/cm3, and thermal conductivity is 542W/mK.
Embodiment 3
Intercalation 10: get particle diameter and be not less than 400 purpose natural flake graphite 200g, sneak into the vitriol oil-concentrated nitric acid mixture as intercalator, intercalation processing;
Expand 20: 200-1100 ℃ of lower expansion process, obtain expansion multiple and be 5 times microdilatancy crystalline flake graphite.
Prefabricated 30: the microdilatancy crystalline flake graphite immersed to take out behind the liquid charcoal source obtain initial goods.Place hot pressing furnace under inert atmosphere in initial goods in initial goods afterwards, with the heat-up rate of 0.1～100 ℃/min, pressure is 5-100MPa, initial goods is heated to 600 ℃～2000 ℃ obtains the prefabricated graphite of intermediate.
Moulding 40: place a graphitizing furnace under argon gas stream in the prefabricated graphite of intermediate, with the heat-up rate of 1～50 ℃/min, intermediate is heated to 2000 ℃～3000 ℃.Come out of the stove behind the naturally cooling and namely obtain high-heat conductivity graphite material.The density of the graphite material that obtains is at 2.04g/cm3, and thermal conductivity is 485W/mK.
Embodiment 4
Intercalation 10: get particle diameter and be not less than 400 purpose natural flake graphite 200g, sneak into the vitriol oil-concentrated nitric acid mixture as intercalator, intercalation processing;
Expand 20: 200-1100 ℃ of lower expansion process, obtain expansion multiple and be 8 times expanded graphite.
Prefabricated 30: will: taking-up obtained initial goods after expanded graphite immersed liquid charcoal source.Place hot pressing furnace under inert atmosphere in initial goods in initial goods afterwards, with the heat-up rate of 0.1～100 ℃/min, pressure is 5-100MPa, initial goods is heated to 600 ℃～2000 ℃ obtains the prefabricated graphite of intermediate
Moulding 40: place a graphitizing furnace under argon gas stream in the prefabricated graphite of intermediate, with the heat-up rate of 1～50 ℃/min, intermediate is heated to 2000 ℃～3000 ℃.Come out of the stove behind the naturally cooling and namely obtain high-heat conductivity graphite material.The density of the graphite material that obtains is at 1.94g/cm3, and thermal conductivity is 448W/mK.
Embodiment 5
Intercalation 10: get particle diameter and be not less than 400 purpose natural flake graphite 200g, sneak into the vitriol oil-concentrated nitric acid mixture as intercalator, intercalation processing;
Expand 20: afterwards 200-1100 ℃ of lower expansion process, obtain expansion multiple and be 10 times expanded graphite.
Prefabricated 30: expanded graphite immersed to take out behind the liquid charcoal source obtain initial goods.Place hot pressing furnace under inert atmosphere in initial goods in initial goods afterwards, with the heat-up rate of 0.1～100 ℃/min, pressure is 5-100MPa, initial goods is heated to 600 ℃～2000 ℃ obtains the prefabricated graphite of intermediate.
Moulding 40: place a graphitizing furnace under argon gas stream in the prefabricated graphite of intermediate, with the heat-up rate of 1～50 ℃/min, intermediate is heated to 2000 ℃～3000 ℃.Come out of the stove behind the naturally cooling and namely obtain high-heat conductivity graphite material.The density of the graphite material that obtains is at 1.92g/cm3, and thermal conductivity is 415W/mK.
Embodiment 6
Intercalation 10: get particle diameter and be not less than 400 purpose natural flake graphite 200g, sneak into the vitriol oil-concentrated nitric acid mixture as intercalator, intercalation processing;
Expand 20: afterwards 200-1100 ℃ of lower expansion process, obtain expansion multiple and be 20 times expanded graphite.
Prefabricated 30: the microdilatancy crystalline flake graphite immersed to take out behind the liquid charcoal source obtain initial goods.Place hot pressing furnace under inert atmosphere in initial goods in initial goods afterwards, with the heat-up rate of 0.1～100 ℃/min, pressure is 5-100MPa, initial goods is heated to 600 ℃～2000 ℃ obtains the prefabricated graphite of intermediate.
Moulding 40: place a graphitizing furnace under argon gas stream in the prefabricated graphite of intermediate, with the heat-up rate of 1～50 ℃/min, intermediate is heated to 2000 ℃～3000 ℃.Come out of the stove behind the naturally cooling and namely obtain high-heat conductivity graphite material.The density of the graphite material that obtains is at 1.90g/cm3, and thermal conductivity is 354W/mK.
In above-described embodiment, processing by intercalation and expansion step, regulate the expansion multiple of natural flake graphite, regulate the arrangement behavior of graphite microcrystal, and under hot pressing function, binding agent and expanded graphite wafer are arranged regular, further have higher thermal conductivity (350-650W/mK) after the greying in forming step.Because crystalline flake graphite is through microdilatancy, its particle diameter is less, sound construction, thereby can overcome preferably the slag-off phenomenon of high conductive graphite.On the other hand, from above-mentioned institute employed material in steps, the advantage such as it is extensive that the present invention has raw material sources, cheap, with short production cycle.
The above, only for preferred embodiment of the present invention, therefore can not limit according to this scope of the invention process, the equivalence of namely doing according to claim of the present invention and description changes and modifies, and all should still belong in the scope that the present invention contains.
Claims (8)
1. the preparation method of a high conductive graphite is characterized in that: may further comprise the steps:
Intercalation: get particle and be not less than 400 purpose natural flake graphites, sneak into intercalator, obtain intercalated graphite;
Expand: this intercalated graphite is placed under the 200-1100 ° of C carry out expansion process, setting its expansion multiple is 1.5-20 times, obtains expanded graphite;
Prefabricated: take out after this expanded graphite soaked into liquid carbon source, be heated to 500-1000 ° of C in the mode with hot pressing, then pressure-controlling goes out still after the cooling in 5-100MPa, graphite in the middle of obtaining; And
Moulding: should place a graphitizing furnace by middle graphite, and be heated to 2000-3000 ° of C under inert gas flow, at last cooling is come out of the stove and is namely obtained finished product graphite.
2. the preparation method of described a kind of high conductive graphite according to claim 1, it is characterized in that: in this intercalation step, this intercalator comprises: the mixture of iron(ic) chloride, cobalt chloride, nickelous chloride, the vitriol oil-concentrated nitric acid, organic intercalation agent and two or more mixture thereof.
3. the preparation method of described a kind of high conductive graphite according to claim 1, it is characterized in that: in this prefabricated step, this liquid carbon source comprises: coal tar, coal-tar pitch, petroleum residual oil, CONPA resin, mesophase pitch and two or more mixture thereof.
4. the preparation method of each described a kind of high conductive graphite in 3 according to claim 1, it is characterized in that: this rare gas element is argon gas.
5. the preparation method of described a kind of high conductive graphite according to claim 1 is characterized in that: in this prefabricated step, take the mode of naturally cooling to go out still after the hot pressing heating is complete.
6. the preparation method of described a kind of high conductive graphite according to claim 1 is characterized in that: in this forming step, heat and take the mode of naturally cooling to come out of the stove after complete.
7. the preparation method of described a kind of high conductive graphite according to claim 1, it is characterized in that: in this prefabricated step, its heat-processed has atmosphere of inert gases.
8. the preparation method of described a kind of high conductive graphite according to claim 1 is characterized in that: in this forming step, the uniform rate that adds thermal recovery 1-50 ° C/min of this centre graphite is heated up.
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| CN103450857A (en) * | 2013-09-05 | 2013-12-18 | 中国科学院青岛生物能源与过程研究所 | Composite graphite heat-conducting membrane material with controllable heat conductivity and preparation process thereof |
| CN104003373A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
| CN104943223A (en) * | 2015-06-17 | 2015-09-30 | 天津大学 | Graphite sheet with high heat conductivity coefficients along plane and thickness directions at the same time and preparation method |
| CN110265850A (en) * | 2019-07-23 | 2019-09-20 | 自贡恒基电碳厂 | A kind of preparation method of brush for electromachine and brush obtained |
| CN116081616A (en) * | 2022-12-30 | 2023-05-09 | 湛江市聚鑫新能源有限公司 | Low-sulfur high-expansion-temperature expandable graphite and preparation method and application thereof |
| CN116534854A (en) * | 2023-04-25 | 2023-08-04 | 广东思泉新材料股份有限公司 | Expanded foaming graphite film, preparation method thereof and application thereof in semiconductor heat dissipation device |
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Cited By (11)
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| CN104003373A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
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| CN104943223A (en) * | 2015-06-17 | 2015-09-30 | 天津大学 | Graphite sheet with high heat conductivity coefficients along plane and thickness directions at the same time and preparation method |
| CN104943223B (en) * | 2015-06-17 | 2016-09-07 | 天津大学 | There is graphite flake and the preparation method of high thermal conductivity coefficient along plane and thickness direction simultaneously |
| CN110265850A (en) * | 2019-07-23 | 2019-09-20 | 自贡恒基电碳厂 | A kind of preparation method of brush for electromachine and brush obtained |
| CN110265850B (en) * | 2019-07-23 | 2021-06-25 | 自贡恒基电碳厂 | Preparation method of electric brush for motor and obtained electric brush |
| CN116081616A (en) * | 2022-12-30 | 2023-05-09 | 湛江市聚鑫新能源有限公司 | Low-sulfur high-expansion-temperature expandable graphite and preparation method and application thereof |
| CN116081616B (en) * | 2022-12-30 | 2024-06-11 | 湛江市聚鑫新能源有限公司 | Low-sulfur high-expansion-temperature expandable graphite and preparation method and application thereof |
| CN116534854A (en) * | 2023-04-25 | 2023-08-04 | 广东思泉新材料股份有限公司 | Expanded foaming graphite film, preparation method thereof and application thereof in semiconductor heat dissipation device |
| CN116534854B (en) * | 2023-04-25 | 2024-05-10 | 广东思泉新材料股份有限公司 | Expanded foaming graphite film, preparation method thereof and application thereof in semiconductor heat dissipation device |
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