CN102211766B - Rapid low-cost preparation method of high heat conduction carbon material - Google Patents
Rapid low-cost preparation method of high heat conduction carbon material Download PDFInfo
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- CN102211766B CN102211766B CN 201110075442 CN201110075442A CN102211766B CN 102211766 B CN102211766 B CN 102211766B CN 201110075442 CN201110075442 CN 201110075442 CN 201110075442 A CN201110075442 A CN 201110075442A CN 102211766 B CN102211766 B CN 102211766B
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Abstract
The invention relates to a rapid low-cost preparation method of a high heat conduction carbon material. The method comprises the following steps: based on graphite paper which is industrially produced as a main raw material, bonding multiple layers of graphite paper by using a binder so as to form a stack body; and then carrying out mould pressing treatment, carbonization and high temperature thermal treatment, so as to rapidly obtain the high heat conduction carbon material with high heat conductivity and anisotropy in low cost.
Description
Technical field
The present invention relates to a kind of quick, low-cost preparation method of highly-conductive hot carbon material, belong to heat management with function carbon material preparing technical field.
Background technology
Advantage such as thermal conductivity height, heat resistance are good, corrosion resistance and good is considered to the important hot transporting material in the new heat pipe reason system to the highly-conductive hot carbon material owing to having; Particularly the very high heat management occasion of chemical corrosion or temperature is being arranged, this material will be brought into play the effect that other material can not be substituted.At present, the highly-conductive hot carbon material that can be used for heat management system is an aggregate with high heat conduction components such as mesophase pitch-based carbon fibers, mesophase pitch Jiao mainly, is that sticker obtains through compression molding, carbonization, greying with the mesophase pitch.Mesophase pitch has only obtained suitability for industrialized production in few countries, and its price is higher, and the price of the goods that on the mesophase pitch basis, form (like mesophase pitch-based carbon fibers) is higher, has caused the cost of preparation highly-conductive hot carbon material very high.Simultaneously, must carry out processing such as preoxidation in the preparation process owing to used a large amount of mesophase pitch, complicated process of preparation, and be not suitable for the manufacturing of large size highly-conductive hot carbon material.In addition, do not sell, being prepared into of highly-conductive hot carbon material cooked a meal without rice because some mesophase pitch goods still has matured product at home.
Summary of the invention
Technology of the present invention is dealt with problems and is: overcome the deficiency of prior art, provide a kind of employing the graphite paper of suitability for industrialized production be main raw material(s), can reduce manufacturing cost significantly, prepare the method for highly-conductive hot carbon material fast.
Technical solution of the present invention is: a kind of quick, low-cost preparation method of highly-conductive hot carbon material, realize through following steps:
The first step is cut out graphite paper by desired size, parallel being adhesively fixed of several graphite papers of cutting out forms the graphite paper stacked body;
Second step, the bonding back of the first step graphite paper stacked body is carried out mold pressing handle under certain pressure, obtain the graphite paper stacked body of half densification;
In the 3rd step, the half fine and close graphite paper stacked body that second step was obtained carries out carbonizing treatment;
The 4th step; The intact graphite paper stacked body of the 3rd step carbonizing treatment is heat-treated, obtain the highly-conductive hot carbon material, the thermal treatment of thermal treatment process in 200 ℃～3000 ℃ inert gas environment, carrying out; Wherein in 200 ℃～1700 ℃ heat-treatment temperature range; Temperature rise rate is 0.01 ℃/min～20 ℃/min, and the constant temperature time under the top temperature is 0h～50h, in 1700 ℃～3000 ℃ heat-treatment temperature range; Temperature rise rate is 0.1 ℃/min～20 ℃/min, and the constant temperature time under the top temperature is 0h～100h.
Also comprised for the 5th step, the highly-conductive hot carbon material that the 4th step was obtained carries out the density processing.
Said density handle adopt normal pressure dipping/carbonization, impregnating by pressure/carbonization, vacuum impregnation/carbonization, chemical vapor infiltration/deposition or etc. any one or more mode in the static pressure treatment process make up.
It is pitch, resin, carbohydrate, alkane or alkene carbonaceousmaterial that the carbon source precursor body that adopts is handled in said density.
The said the first step is bonding to comprise that carrying out with pitch, resin, carbohydrate, alkane or alkene carbon source precursor body to graphite paper is the adhesion process of sticker, also comprises the melt bonded process of graphite paper and the range upon range of back of powder binder.
Add the catalyzed graphitization component in the said carbon source precursor body, the catalyzed graphitization component is simple substance, compound or the mixture of Si, Ti, Zr or Y.
The described second step mold pressing is treated to cold forming or hot moulding.
Graphite paper employing natural flake graphite or expansible black lead are paper shape or the sheet-like material that starting material are processed in the said the first step.
The present invention compared with prior art beneficial effect is:
(1) the present invention overcomes the shortcoming that present technological method too relies on mesophase pitch and goods thereof; With the cheap graphite paper with directed high heat conduction is main raw material(s); Adopt quick preparation bonding, that mould pressing process has been realized the highly-conductive hot carbon material; Not only can shorten the manufacturing cycle (manufacturing cycle drops in 20 days from 2～3 months of original technology) of highly-conductive hot carbon material significantly, reduce its manufacturing cost, but also can realize the quick manufacturing of large size highly-conductive hot carbon material;
(2) carbon material of the present invention's acquisition has high thermal conductivity anisotropy, and thermal conductivity can be up to more than the 360W/ (mK), and thermal conductivity opposite sex degree can be fit to the requirement of heat management system to the directed transporting of heat up to more than 7 very much;
(3) the present invention is specially adapted to the quick manufacturing of large size highly-conductive hot carbon material.
Description of drawings
Fig. 1 is the highly-conductive hot carbon material structure synoptic diagram that obtains after bonding graphite paper stacked body process mold pressing processing, the thermal treatment among the present invention;
Fig. 2 is a process flow sheet of the present invention.
Embodiment
The present invention adopts, and the graphite paper of suitability for industrialized production is a main raw material(s); With its carry out cutting, align, bonding back forms stacked body; Carry out mold pressing then and handle, obtain high-density graphite paper stacked body, obtain the highly-conductive hot carbon material through high temperature graphitization thermal treatment.Concrete technology is as shown in Figure 2, comprises the following steps:
1, the bonding graphite paper stacked body that obtains of graphite paper
Graphite paper is cut out, obtained many graphite papers of certain size.With being adhesively fixed after many graphite paper stacked in parallel, form the graphite paper stacked body.Graphite paper be with crystalline flake graphite or (can) expanded graphite is paper shape or the sheet-like material that main raw material(s) is processed.The process of being adhesively fixed that graphite paper is carried out is to be any adhesion process that sticker carries out with rich carbon organic precursors such as pitch, resin, carbohydrate, alkane or alkene, also comprises the melt bonded process of graphite paper and the range upon range of back of powder binder.Can add the catalyzed graphitization component in the sticker, like simple substance, compound and their mixture of Si, Ti, Zr, Y etc.
2, the graphite paper stacked body is carried out mold pressing and handle, obtain the graphite paper stacked body of half densification, this moment, the density of graphite paper stacked body can reach 1.2g/cm
3More than.Adopt this step to make the graphite paper stacked body before carbonization, reach higher density, the density after the goods carbonization is improved, thereby improve thermal conductivity.
Mold pressing is handled and is meant cold forming (only pressurization, the pressing process that does not heat) or hot moulding (pressurized, heated pressing process) processing of in mould, the graphite paper stacked body being carried out.Mold pressing processing mode, molding pressure and molding temperature can be selected arbitrarily according to actual production technology, but generally can with produce in the use temperature of highly-conductive hot carbon material of the equipment that adopts and required production adapt.
3, carbonizing treatment
The temperature of carbonizing treatment, pressure and time are set according to the tackiness agent of selecting in the reality by the concrete tackiness agent decision of selecting for use.Can press from both sides the graphite paper stacked body after the mold pressing in the carbonization process with or add press fit, prevent the cracking.
4, thermal treatment
Half fine and close graphite paper stacked body is heat-treated, obtain the highly-conductive hot carbon material.High-temperature heat treatment is meant the heat treatment process of in temperature is 200 ℃～3000 ℃ inert gas environment, carrying out; Wherein in 200 ℃～1700 ℃ scopes, temperature rise rate is between 0.01 ℃/min～20 ℃/min, and the constant temperature time under the top temperature is 0h～50h; In 1700 ℃～3000 ℃ scopes, temperature rise rate is between 0.1 ℃/min～20 ℃/min, and the constant temperature time under the top temperature is 0h～100h.Can carry out clamping or add press fit graphite stacks in the heat treatment process to prevent the material cracking.
Thermal treatment temp is according to the use temperature decision of the highly-conductive hot carbon material of required production, and use temperature is low, and heat treated temperature is low accordingly, but thermal treatment temp can not be lower than the use temperature of highly-conductive hot carbon material.
5, densification
The carbon material that can continue that for the raising that realizes the carbon material thermal conductivity step 4 is obtained carries out the density processing.Density is handled and to be meant that with carbon source precursor body (comprising carbonaceousmaterials such as pitch, resin, carbohydrate, alkane, alkene) be presoma, through normal pressure dipping, impregnating by pressure, vacuum impregnation, chemical vapor infiltration/deposition, etc. one or more modes such as static pressure processing make the process of the material density of step 4; Can add the catalyzed graphitization component in the carbon source precursor body, like simple substance, compound and their mixture of Si, Ti, Zr, Y etc.Carrying out carrying out the thermal treatment of temperature in 600 ℃～1700 ℃ scopes in the density process repeatedly, the treatment time generally is no less than 0.1h, becomes carbon and the densification of highly-conductive hot carbon material to promote the carbon source component.Thermal treatment can be carried out after each or several times density are accomplished, and also can after having repeated all density, carry out.
As shown in Figure 1, the carbon material that the highly-conductive hot carbon material that the present invention obtains forms after by sticker thermal treatment in the graphite paper that is arranged in parallel and the slit constitutes, and wherein 1 is the graphite scraps of paper, and 2 is the carbon material that forms after the sticker thermal treatment in the graphite paper slit.
Specify the present invention below in conjunction with specific embodiment.
(1) is the graphite flake that the graphite paper of 1mm is cut into 100mm * 50mm with thickness, uses the acetone-furfural resin that contains the 4wt% yttrium to be sticker, form the bonding graphite paper stacked body that thickness is about 50mm.
(2) bonding graphite paper stacked body is carried out hot moulding and handle, technological process is following: cold conditions is pressurized to 300MPa, and the temperature rise rate with 15 ℃/h is warmed up to 180 ℃ then, naturally cooling behind the constant temperature 2h, and the acquisition volume density is 1.7g/cm
3Die-pressed graphite paper stacked body.
(3) place carbide furnace to carry out carbonizing treatment die-pressed graphite paper stacked body: the temperature rise rate with 1 ℃/min is warmed up to 1000 ℃, and constant temperature 2h obtains carbonized samples then.
(3) place the high-temperature heat treatment stove to heat-treat according to follow procedure carbonized samples: the temperature rise rate with 200 ℃/h is warmed up to 1000 ℃; Temperature rise rate with 100 ℃/h is warmed up to 1700 ℃ then; Temperature rise rate with 200 ℃/h is warmed up to 3000 ℃ again, and naturally cooling behind the constant temperature 3h obtains the highly-conductive hot carbon material; Is 320W/ (mK) through the test carbon material in the normal temperature thermal conductivity of graphite paper in-plane, is 40W/ (mK) in the normal temperature thermal conductivity perpendicular to the graphite paper in-plane.
(1) be the graphite flake that the graphite paper of 0.5mm is cut into 100mm * 50mm with thickness; Graphite paper is piled up as sticker with the mesophase pitch powder then; In inert environments, be heated to softening temperature+50 ℃ of mesophase pitch then; Make the melt bonded graphite paper of mesophase pitch, form bonding graphite paper stacked body.
(2) adherent graphite paper stacked body is carried out hot moulding and handle, technological process is following: cold conditions is pressurized to 300MPa, is warmed up to pitch softening point+100 ℃ with the temperature rise rate of 15 ℃/h then, and naturally cooling behind the constant temperature 5h obtains density and is about 1.75g/cm
3Die-pressed graphite paper stacked body.
(3) place carbide furnace to carry out carbonizing treatment die-pressed graphite paper stacked body: the temperature rise rate with 3 ℃/h is warmed up to 1000 ℃, and constant temperature 2h obtains carbonized samples then.
(4) carbonized samples is placed in the high-temperature heat treatment stove with the anchor clamps clamping heat-treats according to follow procedure: the temperature rise rate with 200 ℃/h is warmed up to 1000 ℃; Temperature rise rate with 80 ℃/h is warmed up to 1700 ℃ then; Temperature rise rate with 150 ℃/h is warmed up to 3000 ℃ again; Naturally cooling behind the constant temperature 3h; Obtaining the highly-conductive hot carbon material, is 368W/ (mK) through the test carbon material in the normal temperature thermal conductivity of graphite paper in-plane, is 45W/ (mK) in the normal temperature thermal conductivity perpendicular to the graphite paper in-plane.
Embodiment 3
(1) is the graphite flake that the graphite paper of 0.2mm is cut into 200mm * 100mm with thickness, as sticker, forms the bonding graphite paper stacked body that thickness is about 20mm with resol.
(2) adherent graphite paper stacked body is carried out cold forming and handle, molding pressure is 250MPa, and the acquisition volume density is 1.8g/cm
3Die-pressed graphite paper stacked body.
(3) the folded body and function graphite clamping plate of die-pressed graphite pile being carried out clamping is placed on and carries out carbonizing treatment in the carbide furnace: the temperature rise rate with 15 ℃/h is warmed up to 200 ℃, and the temperature rise rate with 60 ℃/h behind the constant temperature 2h is warmed up to 1000 ℃, and constant temperature 2h obtains carbonized samples.
(4) place the high-temperature heat treatment stove to heat-treat according to follow procedure carbonized samples: the temperature rise rate with 500 ℃/h is warmed up to 1000 ℃; Temperature rise rate with 100 ℃/h is warmed up to 1700 ℃ then; Temperature rise rate with 200 ℃/h is warmed up to 3000 ℃ again, and naturally cooling behind the constant temperature 3h obtains the highly-conductive hot carbon material; Is 350W/ (mK) through the test carbon material in the normal temperature thermal conductivity of graphite paper in-plane, is 36W/ (mK) in the normal temperature thermal conductivity perpendicular to the graphite paper in-plane.
The unspecified part of the present invention belongs to general knowledge as well known to those skilled in the art.
Claims (7)
1. quick, the low-cost preparation method of a highly-conductive hot carbon material is characterized in that realizing through following steps:
The first step is cut out graphite paper by desired size, said graphite paper is paper shape or the sheet-like material that starting material are processed for adopting natural flake graphite or expansible black lead; Parallel being adhesively fixed of several graphite papers of cutting out forms the graphite paper stacked body; Saidly bondingly comprise that carrying out with pitch, resin or carbohydrate carbon source precursor body to graphite paper is the adhesion process of sticker;
In second step, the graphite paper stacked body that the first step is formed carries out the mold pressing processing under certain pressure, obtain the graphite paper stacked body of half densification;
In the 3rd step, the half fine and close graphite paper stacked body that second step was obtained carries out carbonizing treatment;
The 4th step; The intact graphite paper stacked body of the 3rd step carbonizing treatment is heat-treated, obtain the highly-conductive hot carbon material, the thermal treatment of thermal treatment process in 200 ℃～3000 ℃ inert gas environment, carrying out; Wherein in 200 ℃～1700 ℃ heat-treatment temperature range; Temperature rise rate is 0.01 ℃/min～20 ℃/min, and the constant temperature time under the top temperature is 0h～50h, in 1700 ℃～3000 ℃ heat-treatment temperature range; Temperature rise rate is 0.1 ℃/min～20 ℃/min, and the constant temperature time under the top temperature is 0h～100h.
2. quick, the low-cost preparation method of a kind of highly-conductive hot carbon material according to claim 1 is characterized in that: also comprised for the 5th step, the highly-conductive hot carbon material that the 4th step was obtained carries out the density processing.
3. quick, the low-cost preparation method of a kind of highly-conductive hot carbon material according to claim 2 is characterized in that: said density handle adopt normal pressure dipping/carbonization, impregnating by pressure/carbonization, vacuum impregnation/carbonization, chemical vapor infiltration/deposition or etc. any one or more mode in the static pressure treatment process make up.
4. quick, the low-cost preparation method of a kind of highly-conductive hot carbon material according to claim 3 is characterized in that: it is pitch, resin, carbohydrate, alkane or alkene carbonaceousmaterial that the carbon source precursor body that adopts is handled in said density.
5. quick, the low-cost preparation method of a kind of highly-conductive hot carbon material according to claim 1 is characterized in that: bonding also the comprising the melt bonded process of graphite paper and the range upon range of back of powder binder in the said the first step.
6. according to quick, the low-cost preparation method of claim 4 or 5 described a kind of highly-conductive hot carbon materials; It is characterized in that: add the catalyzed graphitization component in the said carbon source precursor body, the catalyzed graphitization component is simple substance, compound or the mixture of Si, Ti, Zr or Y.
7. quick, the low-cost preparation method of a kind of highly-conductive hot carbon material according to claim 1 is characterized in that: the described second step mold pressing is treated to cold forming or hot moulding.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI599540B (en) * | 2016-08-26 | 2017-09-21 | National Chung-Shan Institute Of Science And Tech | A method for making graphite sheet with high thermal conductivity and changing orientation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105000885A (en) * | 2015-06-30 | 2015-10-28 | 东莞市思泉实业有限公司 | Method for producing graphite film |
| CN106219525B (en) * | 2016-07-11 | 2018-07-24 | 武汉大学 | A kind of preparation method of expanded graphite paper |
| CN106626578B (en) * | 2016-12-30 | 2019-05-31 | 株洲晨昕中高频设备有限公司 | A kind of heat conductive graphite plate and preparation method thereof |
| CN110451964A (en) * | 2019-09-10 | 2019-11-15 | 北京中石伟业科技无锡有限公司 | A kind of preparation method of high orientation Graphite block material |
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| WO1994023466A1 (en) * | 1993-03-31 | 1994-10-13 | International Fuel Cells Corporation | Laminated electrolyte reservoir plate |
| CN101164875A (en) * | 2007-10-10 | 2008-04-23 | 中国科学院山西煤炭化学研究所 | Method for preparing high heat conducting foam carbon material |
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| TWI599540B (en) * | 2016-08-26 | 2017-09-21 | National Chung-Shan Institute Of Science And Tech | A method for making graphite sheet with high thermal conductivity and changing orientation |
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