CN105084810A - Composite carbon-material slice and manufacturing method therefor - Google Patents
Composite carbon-material slice and manufacturing method therefor Download PDFInfo
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Abstract
The invention discloses a manufacturing method of a composite carbon-material slice. The making method comprises the following steps of: mixing graphite powder or graphite oxide powder, carbon nanotube powder or a little viscose to form a mixture, stirring the mixture by using a stirring device, so that the materials are uniformly spread, and then performing calendering or hot pressing on the uniformly spread mixture so as to obtain the composite carbon-material slice. The manufacturing process can be distinguished into a dry method manufacturing process or a wet method manufacturing process by depending upon whether an aqueous solution is added in the manufacturing process.
Description
Technical field
The invention relates to a kind of production method of composite carbon material and the composite carbon material according to this made by mode, particularly about a kind of composite carbon material with the good conductive capacity of heat transmission.
Background technology
Carbon can have multiple multi-form molecular structure, comprises graphite and CNT (carbon nano-tube); These carbon molecular structures all can have good electroconductibility and thermal conductivity usually, such as, when graphite being separated to graphene platelet, and its resistance about 10
-4to 10
-6Ω-cm, its thermal conductivity is about 5000W/mK to 6000W/mK.
Due to the characteristic of carbon molecule, electronic product can use carbon to increase thermal conductivity widely, and meanwhile, the electroconductibility of carbon also can be used in electromagnetic interference EMI(electromagneticdisturbance) above, certainly, also can by electroconductibility and thermal conductivity R. concomitans; In order to the demand making the characteristic of carbon material, structure and shape meet user, just need the processing of carbon molecule to form specific carbon material.
Generally speaking; only utilize the carbon source such as Graphene or CNT (carbon nano-tube); a carbon material cannot be prepared into; usually can add polymer and make one and there is Graphene or CNT (carbon nano-tube) be scattered in polymer composite carbon material in polymer, but this composite carbon material does not have excellent electrical and thermal conductivity usually.
To Graphene be pushed to practical application, the preparation method of a big area and high quality synthesizing graphite alkene must be developed.In the past, the prior art manufacturing Graphene comprises mechanically peel method (mechanicalexfoliation), epitaxial growth method (Epitaxialgrowth), chemical Vapor deposition process (chemicalvapordeposition, CVD) and chemical stripping method (chemicalexfoliation) etc.Wherein, mechanically peel method and epitaxial growth method, although the Graphene that can obtain better quality, these two kinds of methods all cannot big area synthesizing graphite alkene.The preparation process of chemical Vapor deposition process, then must use the high temperature of nearly thousand degrees Celsius and the metal base (as copper or nickel) of costliness, and have the bottleneck in manufacturing cost.
Become known for the carbon material of electronic product at present, mainly contain two kinds of processing modes, the first is for be first heated to 1000 degrees Celsius by graphite oxide, and at high temperature graphite oxide can expand, then expanded graphite is formed graphite flake via extruding; The second is that fragrant adoption sub-acyl ammonium macromolecule membrane is heated to 3000 degrees Celsius, makes polymer meeting carbonization and then form graphite flake when high temperature.
Because above-mentioned making processes needs the condition of high temperature, therefore high cost, energy dissipation, the making processes time is long and making processes is numerous and diverse problem is had, in addition, a large amount of strong acid or strong oxidizer can be used first by graphite or CNT (carbon nano-tube) oxidation in the making processes processing graphite or CNT (carbon nano-tube), in this kind of oxidising process, the lattice of Graphene or CNT (carbon nano-tube) can be destroyed, and all oxidation functional groups cannot be reduced, therefore cannot obtain the large-area Graphene of high quality, and have the doubt causing environmental pollution; Therefore, it is considered herein that need propose a kind of new carbon material making method.
Summary of the invention
As previously mentioned, the present invention proposes a kind of composite carbon material thin slice and making method, use simple making processes, graphite or graphite oxide, CNT (carbon nano-tube) and a small amount of sizing agent can be made electroconductibility and the good composite carbon material of thermal conductivity.
According to above object, the present invention proposes a kind of composite carbon material thin slice, comprise: a plurality of graphite or graphite oxide particle and a plurality of CNT (carbon nano-tube), wherein, graphite or graphite oxide particle are tabular and neat stack arrangement each other, and a plurality of space can be produced between each graphite or graphite oxide particle, be filled with CNT (carbon nano-tube) and sizing agent in space.
The present invention also been proposed a kind of making method of composite carbon material thin slice, comprising: graphite or graphite oxide powder, carbon nanotube powder and sizing agent powder are mixed to get a mixed powder; Mixed powder is stirred to stir mixing device; Mixed powder is stirred to shake whipping appts; And calendering mixed powder, make mixed powder form composite carbon material thin slice.
The present invention also been proposed a kind of making method of composite carbon material thin slice, comprising: by carbon nanotube powder, graphite or the graphite oxide aqueous solution and sizing agent mixing, obtain a mixing solutions; Mixing solutions is stirred with whipping appts; By mixing solutions with rocking equipment concussion evenly; Filter mixing solutions, obtain a moistening film material; And the film material that hot pressing is moistening, make moistening film material form composite carbon material thin slice.
According to composite carbon material thin slice proposed by the invention and making method, by the making processes of a small amount of sizing agent, calendering or hot pressing, make between carbon material, to produce linkage force and can be in conjunction with, and then produce good electroconductibility and thermal conductivity.
According to composite carbon material thin slice proposed by the invention and making method, heat is not needed in making processes, make the cost of manufacture more existing conductive and heat-conductive carbon material of composite carbon material thin slice lower, also can reduce the impact making conductive and heat-conductive carbon material and environment is caused.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of graphite itself and oxidising process;
Fig. 2 is the microstate schematic diagram of carbon material mixture of the present invention;
Fig. 3 is the microstate schematic diagram of composite carbon material thin slice of the present invention;
Fig. 4 is the composite carbon material thin slice dry fabrication process approach schematic flow sheet of the present invention first to the 3rd embodiment;
Fig. 5 is the composite carbon material thin slice wet method making processes method flow schematic diagram of the present invention the 4th to the 6th embodiment.
Description of reference numerals:
Graphite 1
Graphite particle 11
Graphite oxide particle 12
Graphite oxide 2
CNT (carbon nano-tube) 20
Sizing agent 30
Composite carbon material 4
Composite carbon material thin slice 4a
Step 701 ~ 704,801 ~ 805.
Specific embodiment
The object of this invention is to provide a kind of composite carbon material thin slice and preparation method thereof; for the accompanying drawing of the description institute reference in following content; the correlated characteristic of composite carbon material thin slice of the present invention and preparation method thereof is only expressed in its effect in signal; claimed technology contents scope not thereby limiting the invention, this should first illustrate.
Graphite is rare is by the crystalline network of monolayer carbon atom tightly packed one-tenth bi-dimensional cellular shape, and CNT (carbon nano-tube) is then by the rare tubular structure be wound into of graphite, wherein, the change of carbon structure can bring CNT (carbon nano-tube) or graphite rare different electrical.With single-walled carbon nanotubes, according to mode or its carbon pipe diameter of the rare winding of graphite, can form the CNT (carbon nano-tube) of tool metal or characteristic of semiconductor, its energy gap is between 0 ~ 2 electron-volt (eV); And the conductor of multi-layer nano carbon Guan Zewei zero energy gap.Complete and independently mono-layer graphite is rare is the conductor of zero energy gap, its electrical property can be affected by the base material kind, surface imperfection etc. of the rare size of graphite, attaching.
First, please join part Fig. 1, Fig. 1 is the schematic diagram that graphite 1 carries out being oxidizing to the process be dispersed in solvent.As shown in Figure 1, graphite 1 can be considered and formed by graphite particle 11 storehouse, and graphite oxide 2 is chemical method stripping graphite 1, graphite 1 is via the grapheme material of a kind of surface bond oxide group obtained after oxidation or delamination, via step (1), graphite after oxidation, graphite oxide understands a large amount of oxidation functional group of bonding, such as epoxy group(ing) (epoxy, and hydroxyl (hydroxyl C=O), C-OH) can be formed on basal plane, and carboxyl (carboxyl, COOH), carbonyl (carbonyl, etc. C-O) boundary is then distributed in, Graphene is made to overcome the Van der Waals force of graphite 1 interlayer and peel off, and in step (2), be aided with ultrasonic vibrating and help follow-up strip step, it is made to disperse in a solvent, in addition, by the time of regulation and control concussion, the graphite flake of different size can be obtained.When microcosmic, can be considered as being formed by the neat storehouse of a plurality of graphite oxide particle 12, each graphite oxide particle 12 has the accumulation of multiple oxidized graphite flake and forms, and under better condition, each graphite oxide particle 12 is single oxidized graphite flake.
Then, referring to Fig. 2, is the microstate schematic diagram of carbon material mixture 4 of the present invention.Graphite 1 as shown in Figure 1, CNT (carbon nano-tube) 20 and sizing agent 30 are mixed and stir, wherein according to the different demands of making processes, dry fabrication process and wet method making processes can be divided into; In dry fabrication process, be by graphite 1 and CNT (carbon nano-tube) 20 with 9: 1 ~ 1: 9 ratio mix and blend, add sizing agent 30 again and again stir, now observe carbon material mixture 4 with the angle of microcosmic, just situation as shown in Figure 3 can be formed, in addition, before being mixed by above-mentioned materials, graphite 1 can be passed through further oxide treatment and forms graphite oxide 2, then mixes with other material; In wet method making processes, be by graphite 1 or graphite oxide 2 and be mixed with the aqueous solution of CNT (carbon nano-tube) 20 and stir, wherein the solids fraction of graphite oxide 2 and CNT (carbon nano-tube) 20 is 9: 1 ~ 1: 9, then add the sizing agent 30 of water-based and again stir, wherein sizing agent 30 accounts for overall weight percent is 0.3% ~ 30%, now observe carbon material mixture 4 with the angle of microcosmic, just can form situation as shown in Figure 3.
Then, refer to Fig. 3, Fig. 3 is the microstate schematic diagram of composite carbon material thin slice 4a of the present invention.Carbon material mixture 4 is as shown in Figure 2 rolled, just can obtain composite carbon material thin slice 4a as shown in Figure 4, wherein, if obtain carbon material mixture 4 with dry fabrication process, then directly roll carbon material mixture 4, just can obtain composite carbon material thin slice 4a, if making processes obtains the aqueous solution of carbon material mixture 4 in a wet process, then need aqueous solution carbon material mixture 4 to obtain a film with filter paper filtering, then by film to add the mode process of hot calender, just can obtain composite carbon material thin slice 4a as shown in Figure 3, through the composite carbon material thin slice 4a as above-mentioned making processes gained, observe in the mode of microcosmic, situation as shown in Figure 3 can be obtained, flat graphite particle 11 is neat stack arrangement each other, such as, in the X-axis direction in arranged in parallel, it is neat stack arrangement in the Y direction vertical with X-axis simultaneously, space can be formed between different graphite particles 11, the whole carbon material by a plurality of graphite particle 11 storehouse is made to have a plurality of space, and each space of carbon material is all by CNT (carbon nano-tube) 20 and sizing agent 30 filling, make the particle alignment of composite carbon material thin slice 4a even, and then on the direction of plane (and X-axis) with vertical (i.e. Y-axis), good electroconductibility and thermal conductivity can be had, in addition, under other enforcement state, the graphite particle 11 in composite carbon material thin slice 4a also can be graphite oxide particle 12.
Graphite of the present invention can be natural graphite also can be synthetic graphite, graphite oxide of the present invention, can be to carry out oxide treatment by Han Mofa (Hummer ' smethod).Such as, by 10 grams, graphite, 1 liter, sulfuric acid and SODIUMNITRATE 5 grams mixing, and stir under ice bath environment, then add potassium permanganate 30 grams and stir 30 minutes again, then add the water of 500 milliliters again and be heated to 98 degrees Celsius, holding temperature 15 minutes, finally add concentration expressed in percentage by weight be 3% aqueous hydrogen peroxide solution 1 liter carry out diluting, stirring, carry out again filtering, drying, just can obtain graphite oxide 2 powder required for the present invention; Or via improvement Han Mofa, strong acid and strong base usage quantity can be reduced and carry out oxide treatment.Such as, graphite 10g, sulfuric acid 50ml and SODIUMNITRATE 0.1g are mixed, and stir under the environment of 100 degrees Celsius, then add potassium permanganate 1g and stir 30 minutes again, then add 25ml water again and sustaining temperature at 100 degrees Celsius, maintain 30 minutes, finally carry out filtering, drying, just can obtain graphite oxide 2 powder required for the present invention.Such as, but the present invention does not restrict the making processes of graphite oxide 2, the consumption of each material, concentration, and, the graphite used also can be the graphite of synthetic.
In the first embodiment of the invention, the dry method of composite carbon material thin slice is made, be use Laixi, Shandong to produce 90 grams, natural flaky graphite powder, compound wall CNT (carbon nano-tube) (BayCarbonInc.) 10 grams and platform rubber (TAIPOL) rubber powder (BR0150L) 5 grams mixing, at room temperature 1 hour is stirred with the speed of 50rpm again, with by three kinds of solid powder Homogeneous phase mixing via stirring blending machine; Then the mixed powder obtained by said process stirs 1 hour through oscillator, makes mixed powder dispersed, then mixed powder through cylinder prolong be installed with standby (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm
2) be treated to the thin slice of mean thickness 0.3 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 550W/mK, and vertical direction thermal conductivity is 5W/mK; In-plane specific resistance is 0.0001 ohm meter, and vertical direction specific resistance is 0.1 ohm meter.
In second embodiment of the invention, the dry fabrication process of composite carbon material thin slice, it is rubber powder (NBR8052) the 30 grams mixing using Qingdao Tianyuan produces 150 grams, natural flaky graphite powder, Nanotech is produced compound wall CNT (carbon nano-tube) 150 grams and platform rubber, at room temperature 1 hour is stirred with the speed of 50rpm again, with by three kinds of solid powder Homogeneous phase mixing via stirring blending machine; Then the mixed powder obtained by said process stirs 1 hour through oscillator, makes mixed powder dispersed, then mixed powder through cylinder prolong be installed with standby (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm
2) be treated to the thin slice of mean thickness 1 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 450W/mK, and vertical direction thermal conductivity is 13W/mK; In-plane specific resistance is 0.001 ohm meter, and vertical direction specific resistance is 1 ohm meter.
In third embodiment of the invention, the dry fabrication process of composite carbon material thin slice, be use Heilungkiang space difficult to understand to produce 5 grams, natural flaky graphite powder, compound wall CNT (carbon nano-tube) (BayCarbonInc.) 45 grams and platform rubber rubber powder (BR015H) 2 grams mixing, at room temperature 1 hour is stirred with the speed of 50rpm again, with by three kinds of solid powder Homogeneous phase mixing via stirring blending machine; Then the mixed powder obtained by said process stirs 1 hour through oscillator, makes mixed powder dispersed, then mixed powder through cylinder prolong be installed with standby (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm
2) be treated to the thin slice of mean thickness 0.5 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 330W/mK, and vertical direction thermal conductivity is 25W/mK; In-plane specific resistance is 0.0001 ohm meter, and vertical direction specific resistance is 0.05 ohm meter.
In fourth embodiment of the invention, the dry fabrication process of composite carbon material thin slice, be use Laixi, Shandong to produce 45 grams, graphite oxide powder, the compound wall CNT (carbon nano-tube) 5 grams of natural flaky graphite (BayCarbonInc.) and rubber powder (BR0150L) the 1 gram mixing of platform rubber (TAIPOL), at room temperature 1 hour is stirred with the speed of 50rpm again, with by three kinds of solid powder Homogeneous phase mixing via stirring blending machine; Then the mixed powder obtained by said process stirs 1 hour through oscillator, make mixed powder dispersed, then mixed powder through cylinder prolong be installed with standby (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm2) be treated to the thin slice of mean thickness 0.3 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 500W/mK, and vertical direction thermal conductivity is 5W/mK; In-plane specific resistance is 1 ohm meter, and vertical direction specific resistance is 1000 ohm meters.
In fifth embodiment of the invention, the dry fabrication process of composite carbon material thin slice, it is rubber powder (NBR8052) the 20 grams mixing of 70 grams, the graphite oxide powder using Qingdao Tianyuan to produce, compound wall CNT (carbon nano-tube) 70 grams that Nanotech is produced and platform rubber, at room temperature 1 hour is stirred with the speed of 50rpm again, with by three kinds of solid powder Homogeneous phase mixing via stirring blending machine; Then the mixed powder obtained by said process stirs 1 hour through oscillator, makes mixed powder dispersed, then mixed powder through cylinder prolong be installed with standby (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm
2) be treated to the thin slice of mean thickness 1 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 400W/mK, and vertical direction thermal conductivity is 10W/mK; In-plane specific resistance is 0.01 ohm meter, and vertical direction specific resistance is 5 ohm meters.
In sixth embodiment of the invention, the dry fabrication process of composite carbon material thin slice, it is rubber powder (BR015H) the 5 grams mixing of 10 grams, the graphite oxide powder using Heilungkiang space difficult to understand to produce, compound wall CNT (carbon nano-tube) 90 grams that natural flaky graphite is produced and platform rubber, at room temperature 1 hour is stirred with the speed of 50rpm again, with by three kinds of solid powder Homogeneous phase mixing via stirring blending machine; Then the mixed powder obtained by said process stirs 1 hour through oscillator, makes mixed powder dispersed, then mixed powder through cylinder prolong be installed with standby (under best enforcement state, temperature 120 degree, pressure 300kg/cm
2) be treated to the thin slice of mean thickness 0.5 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 300W/mK, and vertical direction thermal conductivity is 20W/mK; In-plane specific resistance is 0.0001 ohm meter, and vertical direction specific resistance is 0.8 ohm meter.
In seventh embodiment of the invention, the wet method making processes of composite carbon material thin slice, be sigma Ao Ruiqi is produced compound wall CNT (carbon nano-tube) powder 3 grams, by Heilungkiang space production difficult to understand weight concentration per-cent be 20% the natural graphite aqueous solution 60 grams and high-molecular polyvinyl alcohol 3 grams mixing, and at room temperature in stirrer, stir 1 hour with the speed of 100rpm; Then the mixing solutions obtained by said process shakes 1 hour through concussion pond, mixed powder dissolution homogeneity is disperseed, then mixed powder solution is directly used filter paper filtering, obtain a moistening thin slice, again through hot-press equipment process (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm2), become the thin slice of mean thickness 0.5 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 400W/mK, and vertical direction thermal conductivity is 5W/mK; In-plane specific resistance is 0.001 ohm meter, and vertical direction specific resistance is 3 ohm meters.
In eighth embodiment of the invention, the wet method making processes of composite carbon material thin slice, be sigma Ao Ruiqi is produced compound wall CNT (carbon nano-tube) powder 30 grams, by the score of Qingdao Tianyuan production weight concentration than the graphite aqueous solution 300 grams and the polyvinyl alcohol high score 15 grams mixing that are 10%, and at room temperature in stirrer, stir 1 hour with the speed of 100rpm; Then the mixing solutions obtained by said process shakes 1 hour to shake pond, mixed powder dissolution homogeneity is disperseed, then mixed powder solution is directly used filter paper filtering, obtain a moistening thin slice, again with hot-press equipment process (under best enforcement state, temperature 120 degrees Celsius, the every kg/cm2 of pressure 250), become the thin slice of mean thickness 0.2 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 350W/mK, and vertical direction thermal conductivity is 10W/mK; In-plane specific resistance is 0.01 ohm meter, and vertical direction specific resistance is 1 ohm meter.
In ninth embodiment of the invention, the wet method making processes of composite carbon material thin slice, be sigma Ao Ruiqi is produced compound wall CNT (carbon nano-tube) powder 10 grams, by the score of Laixi, Shandong production weight concentration than the graphite aqueous solution 20 grams and the high-molecular polyvinyl alcohol 0.5 gram mixing that are 10%, and at room temperature in stirrer, stir 1 hour with the speed of 100rpm; Then the mixing solutions obtained by said process shakes 1 hour to shake pond, mixed powder dissolution homogeneity is disperseed, then mixed powder solution is directly used filter paper filtering, obtain a moistening thin slice, again through hot-press equipment process (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm2), become the thin slice of mean thickness 1 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 200W/mK, and vertical direction thermal conductivity is 28W/mK; In-plane specific resistance is 0.0001 ohm meter, and vertical direction specific resistance is 0.1 ohm meter.
In tenth embodiment of the invention, the wet method making processes of composite carbon material thin slice, be sigma Ao Ruiqi is produced compound wall CNT (carbon nano-tube) powder 1 gram, by the score of Heilungkiang space production difficult to understand weight concentration than the graphite oxide aqueous solution 20 grams and the high-molecular polyvinyl alcohol 0.5 gram mixing that are 20%, and at room temperature in stirrer, stir 1 hour with the speed of 100rpm; Then the mixing solutions obtained by said process shakes 1 hour through concussion pond, mixed powder dissolution homogeneity is disperseed, then mixed powder solution is directly used filter paper filtering, obtain a moistening thin slice, again through hot-press equipment process (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm2), become the thin slice of mean thickness 0.5 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 600W/mK, and vertical direction thermal conductivity is 8W/mK; In-plane specific resistance is 0.5 ohm meter, and vertical direction specific resistance is 400 ohm meters.
In eleventh embodiment of the invention, the wet method making processes of composite carbon material thin slice, be sigma Ao Ruiqi is produced compound wall CNT (carbon nano-tube) powder 20 grams, by the score of Qingdao Tianyuan production weight concentration than the graphite oxide aqueous solution 200 grams and the high-molecular polyvinyl alcohol 10 grams mixing that are 10%, and at room temperature in stirrer, stir 1 hour with the speed of 100rpm; Then the mixing solutions obtained by said process shakes 1 hour through concussion pond, mixed powder dissolution homogeneity is disperseed, then mixed powder solution is directly used filter paper filtering, obtain a moistening thin slice, again through hot-press equipment process (under best enforcement state, temperature 120 degrees Celsius, the every kg/cm2 of pressure 250), become the thin slice of mean thickness 0.2 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 450W/mK, and vertical direction thermal conductivity is 12W/mK; In-plane specific resistance is 0.007 ohm meter, and vertical direction specific resistance is 1 ohm meter.
In twelveth embodiment of the invention, the wet method making processes of composite carbon material thin slice, be sigma Ao Ruiqi is produced compound wall CNT (carbon nano-tube) powder 5 grams, by the score of Laixi, Shandong production weight concentration than the graphite oxide aqueous solution 10 grams and the high-molecular polyvinyl alcohol 0.5 gram mixing that are 10%, and at room temperature in stirrer, stir 1 hour with the speed of 100rpm; Then the mixing solutions obtained by said process shakes 1 hour through concussion pond, mixed powder dissolution homogeneity is disperseed, then mixed powder solution is directly used filter paper filtering, obtain a moistening thin slice, again through hot-press equipment process (under best enforcement state, temperature 120 degrees Celsius, pressure 300kg/cm2), become the thin slice of mean thickness 1 millimeter, be composite carbon material thin slice of the present invention; The composite carbon material thin slice obtained under this enforcement state, its in-plane thermal conductivity is 350W/mK, and vertical direction thermal conductivity is 25W/mK; In-plane specific resistance is 0.0005 ohm meter, and vertical direction specific resistance is 1 ohm meter.
Each embodiment above, independent graphite particle (or graphite oxide particle) can be considered a plane, pile up and pass through the graphite particle (or graphite oxide particle) rolled and can form plane, and when graphite particle (or graphite oxide particle) is larger with the ratio of CNT (carbon nano-tube), more smooth plane can be formed, make its plane thermal conductivity effect better, this is because heat conduction is via phonon transmission, smooth continuous surface can increase phonon transmission capacity.When the amount increase gradually of CNT (carbon nano-tube), contact between different graphite particle (or graphite oxide particle) planes improves, the heat conduction of vertical surface can be made to increase, but due to from Vertical Square always, not still a continuous level between graphite particle (or graphite oxide particle) plane, so the heat conduction in the X-direction of level is still better, and in vertical Y-direction, heat conduction is relatively low.
The part of conduction, graphite particle electroconductibility can comparatively graphite oxide be better, and the ratio of CNT (carbon nano-tube) more time, electroconductibility also can increase, because electroconductibility is by electron transmission, its electron transmission be do not have directive, as long as there is continuous print conductive path just can increase electroconductibility, all carbon material thin slices formed via calendering, have excellent contact and form good electroconductibility.On the other hand, when the sizing agent added is more, electroconductibility also can decline.
According to above each embodiment, the present invention proposes a kind of dry fabrication method of composite carbon material thin slice, and as shown in Figure 4, the making method of composite carbon material thin slice comprises:
Step 701: powdered graphite, carbon nanotube powder and rubber powder are mixed to form a kind of mixed powder; Wherein, CNT (carbon nano-tube) can be the structure of individual layer, bilayer or compound wall;
Step 702: the material in Homogeneous phase mixing mixed powder; Such as, be uniformly mixed powder to stir mixing device, make the powdered graphite in mixed powder, carbon nanotube powder and rubber powder Homogeneous phase mixing;
Step 703: the material in dispersed mixed powder; Such as be uniformly mixed powder to shake whipping appts, make the powdered graphite in mixed powder, carbon nanotube powder and rubber powder dispersed;
Step 704: calendering mixed powder, makes mixed powder formation composite carbon material thin slice 4a as shown in Figure 4; Wherein, under preferably status of implementation, pressure range during calendering is 10Kgf/cm
2to 800Kgf/cm
2, temperature range during its calendering is 60 to 200 degrees Celsius.
Above flow process does not need to add any liquid, is kept dry to last finished product whole process by raw material, is a kind of production method of dry method, quite convenient in making; In addition, under preferably enforcement state, the part by weight scope of the graphite in above making processes and CNT (carbon nano-tube) is 9: 1 to 1: 9, and the weight percentage ranges that rubber powder accounts for composite carbon material thin slice is 0.3% to 30.0%; Under other enforcement state, graphite also can be graphite oxide; In above making processes, rubber uses as sizing agent, the present invention does not limit the kind of sizing agent, such as, can be polyvinyl alcohol, aqueous polyurethane, thermoplastic polyurethanes, polyvinylpyrrolidone, chitin, Mierocrystalline cellulose, polypropylene, polyethylene and polyethylene terephthalate.
The present invention also proposes the wet method making method of another kind of composite carbon material thin slice, and as shown in Figure 5, the making method of composite carbon material thin slice comprises:
Step 801: carbon nanotube powder, the graphite oxide aqueous solution and sizing agent are mixed, forms mixing solutions; Wherein, CNT (carbon nano-tube) can be the structure of individual layer, bilayer or compound wall; In addition, sizing agent can be pulverous solid matter;
Step 802: the material in Homogeneous phase mixing mixing solutions; Such as, be uniformly mixed solution with whipping appts, make the carbon nanotube powder in mixing solutions, graphite oxide and sizing agent Homogeneous phase mixing;
Step 803: the material in dispersed mixing solutions; Such as, with rocking equipment concussion mixing solutions, the carbon nanotube powder in mixing solutions, graphite oxide and sizing agent are on average disperseed;
Step 804: adopt filter paper filtering mixing solutions, obtain evenly moistening film material;
Step 805: the mode process film material adopting hot pressing, makes film material formation composite carbon material thin slice 4a as shown in Figure 4; Wherein, under preferably status of implementation, pressure range during hot pressing is 10Kgf/cm
2to 800Kgf/cm
2, temperature range during its hot pressing is 60 to 200 degrees Celsius.
Above Making programme using water as solvent by carbon nanotube powder, graphite or graphite oxide and sizing agent dispersion, can evenly the various material of dispersion, and more easily can control the thickness of composite carbon material thin slice; In addition, under preferably enforcement state, the part by weight scope of the graphite of above flow process or graphite oxide and CNT (carbon nano-tube) is 9: 1 to 1: 9, and the weight percentage ranges that the weight adding sizing agent accounts for final composite carbon material thin slice is 0.3% to 30.0%; In addition, the graphite that above Making programme is mentioned can be natural graphite or artificial synthetic graphite, and the present invention is not limited; In addition, the CNT (carbon nano-tube) that above Making programme is mentioned can be the form of individual layer, bilayer or compound wall, and the present invention is not limited.
The present invention produces composite carbon material thin slice 4a mainly through rolling, calendering can make each material can contact more closely in the X-direction of level and in vertical Y-direction, more neat arrangement, difform various carbon material is made to form a kind of sheet material or film material of external phase, such as: CNT (carbon nano-tube) 20 in composite carbon material thin slice 4a can be allowed all towards identical direction, become continuous print burnishing surface, and then reach the effect promoting conduction and thermal conductivity, under preferably enforcement state, the thermal conductivity scope of its X-direction of composite carbon material thin slice 4a of the present invention is 200 ~ 2000W/mK, the thermal conductivity scope of Y-direction is 2 ~ 30W/mK, in addition, the resistivity range of its X-direction of composite carbon material thin slice 4a is 1 ~ 0.00001 ohm meter, the resistivity range of Y-direction is 0.01 ~ 1000 ohm meter, when the insufficient pressure of rolling, CNT (carbon nano-tube) 20 in composite carbon material thin slice 4a may be different towards each other direction, or do not combine closely between graphite oxide particle 10 and CNT (carbon nano-tube) 20, such situation all can cause negative impact to thermal conductivity and electroconductibility, in addition, the electroconductibility of length-to-diameter ratio and the composite carbon material thin slice 4a of CNT (carbon nano-tube), thermal conductivity can be directly proportional.
Composite carbon material thin slice 4a Making programme of the present invention is under the help of a small amount of sizing agent 30, make to produce affine linkage force between various carbon material by calendering, and in whole making processes, do not need the high temperature making processes through more than 1000 degrees Celsius, saving cost of manufacture also can not to environment.
To sum up, the present invention is encyclopaedized by the above embodiments and change case.But, those skilled in the art it should be understood that, embodiments all in the present invention is only exemplary at this but not is restricted, that is, do not departing within connotation of the present invention and scope, based on described above and other change case of composite carbon material thin slice and preparation method thereof and fixed case be the present invention and contain, the present invention is defined by accompanying patent claim.
Claims (12)
1. a composite carbon material thin slice, comprise plural graphite particle, plural CNT (carbon nano-tube) and a sizing agent, it is characterized in that, those graphite particles are tabular and are arranged in parallel on a first direction, and in neat stack arrangement in a second direction, this first direction and this second direction orthogonal, there is a plurality of space between those graphite particles, those CNT (carbon nano-tube) and this sizing agent are filled in those spaces.
2. composite carbon material thin slice according to claim 1, it is characterized in that, described graphite particle comprises graphite oxide particle.
3. composite carbon material thin slice according to claim 1, is characterized in that, described CNT (carbon nano-tube) can be the one in solid wall CNT (carbon nano-tube), double wall CNT (carbon nano-tube) and compound wall CNT (carbon nano-tube).
4. composite carbon material thin slice according to claim 1, it is characterized in that, described sizing agent is the one in rubber, polyvinyl alcohol, aqueous polyurethane, thermoplastic polyurethanes, polyvinylpyrrolidone, chitin, Mierocrystalline cellulose, polypropylene, polyethylene and polyethylene terephthalate.
5. composite carbon material thin slice according to claim 1, is characterized in that, composite carbon material thin slice has a thickness, and this thickness is between 0.001 millimeter to 1 millimeter.
6. composite carbon material thin slice according to claim 1, is characterized in that, the part by weight of described graphite oxide particle and described CNT (carbon nano-tube) is between 9: 1 to 1: 9.
7. a making method for composite carbon material thin slice, comprising:
Powdered graphite, carbon nanotube powder and sizing agent powder are mixed to get a mixed powder;
Described powdered graphite in this mixed powder of Homogeneous phase mixing, described carbon nanotube powder and described sizing agent powder;
Described powdered graphite in dispersed described mixed powder, institute's carbon nanotube powder of telling and described sizing agent powder; And
Roll described mixed powder, make described mixed powder form described composite carbon material thin slice.
8. the making method of composite carbon material thin slice according to claim 7, is characterized in that, when carrying out rolling this mixed powder, is be 10Kgf/cm in pressure range
2to 800Kgf/cm
2pressure state under to implement.
9. the making method of composite carbon material thin slice according to claim 7, is characterized in that, when carrying out rolling described mixed powder, is implement under temperature range is the state of temperature of 60 degrees Celsius to 200 degrees Celsius.
10. a making method for composite carbon material thin slice, comprising:
Carbon nanotube powder, the graphite oxide aqueous solution and sizing agent are mixed, obtains a mixing solutions;
Described carbon nanotube powder in mixing solutions described in Homogeneous phase mixing, the described graphite oxide aqueous solution and described sizing agent;
Described carbon nanotube powder in the described mixing solutions of average dispersion, the described graphite oxide aqueous solution and described sizing agent;
Filter described mixing solutions, obtain a moistening film material; And
Film material moistening described in hot pressing, makes described moistening film material form described composite carbon material thin slice.
The making method of 11. composite carbon material thin slices according to claim 10, is characterized in that, when carrying out film material moistening described in hot pressing, is be 10Kgf/cm in pressure range
2to 800Kgf/cm
2pressure state under to implement.
The making method of 12. composite carbon material thin slices according to claim 10, is characterized in that, when carrying out the step of film material moistening described in hot pressing, is implement under temperature range is the state of temperature of 60 degrees Celsius to 200 degrees Celsius.
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Cited By (1)
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| CN107840330A (en) * | 2017-10-18 | 2018-03-27 | 复旦大学 | A kind of preparation method of carbon/carbon composite radiating film |
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